Functionalized and crosslinked materials

Abstract

Functionalized and crosslinked material, which may optionally be employed as a sorbent, as well as methods of making such materials and systems of using such materials are provided. The processes, methods, systems and materials herein can be used for the separation of carbon dioxide from fluid streams. In one aspect, a method of forming functionalized crosslinked particles comprises introducing at least a portion of a surface of each porous particle in at least a subset of a plurality of porous particles to a crosslinking agent and a first reagent comprising at least one adsorbing moiety. Examples of adsorbing moiety include silane-functionalized amines, amino-functionalized silanes (aminosilane), and polyamines. In some aspects the method further comprises introducing the porous particles to a second reagent comprising at least one interaction moiety such as a silane-functionalized amine, amino-functionalized silane (aminosilane), or polyamine. Examples of crosslinking agent include dialdehyde, diisocyanates, dihaloalkane, diepoxide and dianhydrides.

Description

CROSS REFERENCE TO RELATED PATENT APPLICATIONS

[0001] This application claims priority to United States Provisional Patent Application No. 63 / 614,833, entitled “FUNCTIONALIZED CROSSLINKED MATERIALS,” fded December 26, 2023, which is hereby incorporated by reference. FIELD OF THE DISCLOSURE

[0002] The disclosure relates to a functionalized and crosslinked material, which may optionally be employed as a sorbent, as well as methods of making such materials and systems of using such materials. The processes, methods, and systems herein are used for the separation of carbon dioxide from fluid streams. BACKGROUND

[0003] Atmospheric carbon concentrations have risen in correlation with industrialized activity for decades. Carbon dioxide is a primary contributor to the total carbon concentration. Concern over global climate warming has led to interest in capturing carbon dioxide emissions. SUMMARY

[0004] In general, the disclosure relates to functionalized and crosslinked materials, methods of making and using thereof, and systems that are configured to use such materials.

[0005] In particular embodiments, the functionalized material is used to capture and remove carbon dioxide from gaseous environments. In some embodiments, the functionalized material exhibits lifetime improvement. In some embodiments, the functionalized material includes a linking moiety (e.g., provided by way of a crosslinking agent).

[0006] In general, an aspect disclosed herein are methods that introduce a plurality of porous particles to a crosslinking agent, a first reagent including at least one adsorbing moiety (e.g., an aminosilane or a polyamine), and an optional second reagent including at least one interaction moiety (e.g., an aminosilane or a silane) to at least a portion of a surface of each porous particle in at least a subset of the plurality of porous particles, thereby providing a plurality of functionalized, crosslinked particles. In some embodiments, the subset of the plurality of porous particles consists of at least five percent, ten percent, fifteen percent, twenty percent, twenty-five percent, thirty percent, forty-five percent, fifty percent, fifty-five percent, sixty percent, sixty-five percent, seventy percent, or seventy-five percent of the original plurality of porous particles.

[0007] Examples may include one or more of the following features. In some embodiments, the crosslinking agent is a multivalent crosslinking agent. In some embodiments, the multivalent crosslinking agent includes a structure of formula VII. In some embodiments, the multivalent crosslinking agent is a bivalent crosslinking agent that includes a structure of any of formulas Vlla-VIIm.

[0008] In some embodiments the introduction of the plurality of porous to the crosslinking agent, the first reagent and optionally the second reagent includes introducing the crosslinking agent to the plurality of porous particles to form a plurality of crosslinked particles. In some embodiments, the introducing includes introducing the crosslinking agent with the first reagent to form a plurality of functionalized crosslinked particles. In some embodiments, the introducing includes introducing the crosslinking agent with the first reagent and the second reagent to form a plurality of functionalized crosslinked particles.

[0009] In some embodiments, the introducing the crosslinking agent includes introducing the crosslinking agent, the first reagent, and the optional second reagent to the plurality of coated particles. In some embodiments, before crosslinking the crosslinking agent with the first reagent, a third reagent comprising a polymer is introduced to the plurality of porous particles, thereby providing a plurality of coated particles. Subsequently, in such embodiments, the crosslinking agent, the first reagent, and the optional second reagent is introduced to the plurality of coated particles.

[0010] In some embodiments, before crosslinking the crosslinking agent with the first reagent, the plurality of coated particles are dried in a vacuum oven at between 60 °C and 100 °C (e.g., 80 °C) until a hydration threshold is reached. In some embodiments this hydration threshold is less than 5% (wt / wt) of water to the plurality of coated particles. In some embodiments this hydration threshold is less than 10% (wt / wt) of water to the plurality of coated particles. In some embodiments this hydration threshold is less than 15% (wt / wt) of water to the plurality of coated particles. In some embodiments this hydration threshold is less than 2.5% (wt / wt) of water to the plurality of coated particles. In some embodiments this hydration threshold is less than X% (wt / wt) of water to the plurality of coated particles, where X is a real value between 0.01 and 25 (e.g., 12.3%).

[0011] In some embodiments, the third reagent is poly(vinyl alcohol) (PVA).

[0012] In some embodiments, the plurality of porous particles are introduced to a solvent at a ratio in a range between 1.5 wt / wt and 4:1 wt / wt of the solvent to the plurality of porous particles. In some embodiments, the crosslinking agent is introduced to a first solvent at a ratio in a range of up to 15% (wt / wt) of the crosslinking agent to the plurality of porous particles. In some embodiments, the crosslinking agent is introduced to the first solvent at a ratio in a range of up to 50 mol % of the crosslinking agent to the second reagent.

[0013] In some embodiments, the first reagent is introduced to a second solvent at a ratio from about 20% (wt / wt) to 80% (wt / wt) of the first reagent to the plurality of porous particles.

[0014] In some embodiments the first reagent is an aminosilane. In some embodiments the aminosilane has a structure of any of formulas I, la-If, II, Ila, lib, lie,, lid, Illa, Illb, or IV.

[0015] In some embodiments the aminosilane includes at least one amino moiety and at least one silane moiety. In some embodiments the at least one silane moiety is an alkoxysilane moiety, a trihalosilane moiety, a dihalosilane moiety, a monohalosilane moiety, a silanetriol moiety, a dialkoxysilanol moiety, a monoalkoxysilanol moiety, or an aminosilane oligomer.

[0016] In some embodiments, the first reagent is a polyamine. In some embodiments, the first reagent is a linear or a branched polyamine. In some embodiments, the polyamine has a structure of any one of formulas Via, VIb, Vic, Vid, Vie, VIf, Vig, VIh, or Vli.

[0017] In some embodiments, the first reagent and the second reagent are introduced to the plurality of porous particles before the crosslinking agent is introduced. In some embodiments, the second reagent comprises an aminosilane or a silane. In some embodiments the aminosilane has a structure of one formulas I, la-If, II, Ila-IId, Illa, Illb or IV. In some embodiments, the silane has a structure of formulas V and Va.

[0018] In some embodiments, introducing the first reagent and the second reagent includes mixing the first reagent and the second reagent in a second solvent to form a functionalization mixture and introducing the functionalization mixture on at least a portion of the surface of each porous particle in at least the subset of the plurality of porous particles. In some embodiments, the functionalization mixture further includes the crosslinking agent.

[0019] In some embodiments, the plurality of porous particles comprises 1000 or more porous particles, 10,000 or more porous particles, 100,000 more porous particles, 1 x 106 or more porous particles, 1 x 107 or more porous particles. In some embodiments, the plurality of porous particles comprises 50 grams or more of porous particles, 100 grams or more of porous particles, 500 grams or more of porous particles, 1 kilogram or more of porous particles, 10 kilograms or more of porous particles, 100 kilograms or more of porous particles, or 1000 kilograms or more of porous particles.

[0020] In general, an aspect disclosed herein is a composition including a plurality of crosslinked particles modified according to any of the method aspects herein. In some embodiments, the plurality of crosslinked particles comprises 1000 or more crosslinked particles, 10,000 or more crosslinked particles, 100,000 more crosslinked particles, 1 x 106 or more crosslinked particles, 1 x 107 or more crosslinked particles. In some embodiments, the plurality of crosslinked particles comprises 50 grams or more of crosslinked particles, 100 grams or more of crosslinked particles, 500 grams or more of crosslinked particles, 1 kilogram or more of crosslinked particles, 10 kilograms or more of crosslinked particles, 100 kilograms or more of crosslinked particles, or 1000 kilograms or more of crosslinked particles.

[0021] In general, an aspect disclosed herein is a composition including a plurality of functionalized crosslinked particles modified according to any of the method aspects herein. In some embodiments, the plurality of functionalized crosslinked particles comprises 50 grams or more of functionalized crosslinked particles, 100 grams or more of functionalized crosslinked particles, 500 grams or more of functionalized crosslinked particles, 1 kilogram or more of functionalized crosslinked particles, 10 kilograms or more of functionalized crosslinked particles, 100 kilograms or more of functionalized crosslinked particles, or 1000 kilograms or more of functionalized crosslinked particles.

[0022] Examples include one or more of the following features. In some embodiments, the first reagent is configured to adsorb carbon dioxide. In some embodiments, the composition adsorbs CO2 per dry kilogram in a range from 0.5 mol to 2.5 mol. In some embodiments, the composition desorbs in a temperature range between about 65 °C to 90 °C. In some embodiments, the composition adsorb CO2 at a relative humidity in a range from 5% to 95% relative humidity. In some embodiments, the composition has a 50% strain crush strength of at least l.OMPa, at least l.IMPa, at least 1.2 MPa, at least 1.3MPa, at least 1.4MPa, at least 1.5 MPa, at least 1.6MPa, at least 1.7MPa, at least 1.8MPa, at least 1.9MPa, or at least 2.0MPa. In some embodiments the composition has a 50% strain crush strength of between l.OMPa and 5.0MPa, between 1.3MPa and 4.0MPa, between 1.5MPa and 3.5MPa, or between 1.5MPa and 8MPa.

[0023] In some embodiments, the composition further includes a hydrophobic compound attached to at least a portion of the surfaces of at least a subset of the particles. In some embodiments, the hydrophobic compound is a hydrophobic silane compound or a hydrophobic polymer. In some embodiments, the hydrophobic silane compound includes a silane moiety and one, two, or three alkyl chains. In some embodiments, the hydrophobic polymer is polydimethylsiloxane (PDMS), silicone oil, polyethylene, polytetrafluoroethylene, polyurethane, or any mixture thereof.

[0024] In general, an aspect disclosed herein is a method including using any of compositions disclosed herein (e.g., functionalized crosslinked particles) to remove atmospheric CO2 from air by direct air capture.

[0025] An aspect disclosed herein is a functionalized composition including a plurality of porous particles, a surface modification layer disposed on at least a portion of a surface of each porous particle in at least a subset of the plurality of porous particles, where the surface modification layer includes an adsorbing moiety (e.g., one or more amine moi eties) and / or a linking moiety. The composition is configured to adsorb atmospheric CO2 under a first condition and reversibly desorb adsorbed CO2 under a second condition. In some embodiments, the subset of the plurality of porous particles consists of at least five percent, ten percent, fifteen percent, twenty percent, twenty-five percent, thirty percent, forty-five percent, fifty percent, fifty-five percent, sixty percent, sixty-five percent, seventy percent, or seventy-five percent of the original plurality of porous particles.

[0026] In general, an aspect disclosed herein is a functionalized composition including a plurality of porous particles. A coating is disposed on at least a portion of the surface of each porous particle in at least a subset (at least five percent, ten percent, fifteen percent, twenty percent, twenty-five percent, thirty percent, forty-five percent, fifty percent, fifty-five percent, sixty percent, sixty-five percent, seventy percent, or seventy-five percent of the original plurality of porous particles) of the plurality of porous particles, thereby forming coated particles. In some embodiments the coating includes a polymer. Moreover, a surface modification layer is disposed on at least a portion of the surface of at least a subset (at least five percent, ten percent, fifteen percent, twenty percent, twenty-five percent, thirty percent, forty-five percent, fifty percent, fifty-five percent, sixty percent, sixty-five percent, seventy percent, or seventy-five percent of the original plurality of porous particles) of the plurality of porous particles. In some embodiments the surface modification layer includes an adsorbing moiety (e.g., one or more amine moi eties) and optionally a linking moiety. In some embodiments the functionalized composition is configured to adsorb atmospheric CO2 under a first condition and reversibly desorb adsorbed CO2 under a second condition.

[0027] Examples include one or more of the following features. In some embodiments, the plurality of porous particles include a plurality of porous silica particles, a plurality of porous metal-organic framework (MOF) particles, or a plurality of ion-exchange resin particles. In some embodiments, the surface modification layer includes (i) an amine moiety and a silane moiety, (ii) a plurality of amine moieties, (iii) a linking moiety, (vi) both (i) and (iii), (vi) both (ii) and (iii), or (vii) each of (i), (ii), and (iii). In some embodiments, the surface modification layer is provided by interacting one or more compounds with at least a portion of the surface of each porous particle in at least a subset (at least five percent, ten percent, fifteen percent, twenty percent, twenty-five percent, thirty percent, forty-five percent, fifty percent, fifty-five percent, sixty percent, sixty-five percent, seventy percent, or seventy-five percent of the original plurality of porous particles) of the plurality of porous particles. In some such embodiments, the one or more compounds is an aminosilane, a polyamine, and / or a crosslinking agent. In some embodiments, the aminosilane has a structure of one of formulas I, la-If, II, Ila-IId, Illa, Illb, or IV. In some embodiments, the polyamine has a structure of formula Via, VIb, Vic, Vid, Vie, VIf, Vig, VIh, or Vii. In some embodiments, the crosslinking agent has a structure of formula VII, Vila, Vllb, Vile, Vlld, Vile, Vllf, Vllg, Vllh, Vlli, Vllj, Vllk, or Vllm.

[0028] In some embodiments, the composition includes a chelating agent.

[0029] In some embodiments, the composition include an antioxidant. In some embodiments, the antioxidant is a cyclic antioxidant, a hindered amine light stabilizer, or an organic sulfur-containing compound. In some embodiments, the antioxidant is an organic sulfur-containing compound selected from the group consisting of 2,2-thiodiethanol, 2-hydroxyethyl disulfide, and 3,3’-dithiodipropionic acid.

[0030] In some embodiments the plurality of porous particles are porous silica or silicate, a porous ceramic, a porous metal-organic substrate, a porous polymeric substrate, a porous ceramic / metal oxide together with porous silica, a porous alumina, a metal-organic framework (MOF), or a resin.

[0031] In some embodiments, the plurality of porous particles include a substrate provided in a precipitated form, a sol-gel form, a fumed form, a calcined form, an agglomerated form, a granulated form, a powder, or as granules.

[0032] In some embodiments, the plurality of porous particles include a plurality of pores. The plurality of pores may include a dimension from about 1 to 200 nm, an average pore size from about 30 to 80 nm, and / or a volume greater than about 0.5 ml / g or from 0.1 to 5 ml / g.

[0033] In some embodiments the plurality of porous particles may include a greatest dimension of at least 25 pm. In some embodiments, the plurality of porous particles have a sieve diameter of from 0.4 millimeters to 4 millimeters.

[0034] In some embodiments, the plurality of porous particles have a plurality of pores that, in turn, each have a dimension of at least about 1 nm and a volume greater than about 0.5 ml / g. In some embodiments the plurality of pores have (i) a distribution of pore sizes from 50 Angstroms to 300 Angstroms.

[0035] In some embodiments, the surface modification layer is a polyamine the represents between 5% to 60% of the total weight of the composition.

[0036] In some embodiments, the surface modification layer is an aminosilane that represents between 5% to 80% of the total weight of the composition.

[0037] In some embodiments, the surface modification layer includes a crosslinke agent that represents less than 5% of the total weight of the composition..

[0038] In some embodiments, the plurality of porous particles has a total surface area greater than about 100 m2 per dry gram.

[0039] In some embodiments, the composition adsorbs greater than about 0.5 mol of CO2 per dry kilogram or from about 0.5 to 2.5 mol of CO2 per dry kilogram.

[0040] In some embodiments, the material adsorbs CO2 at a relative humidity in a range from about 5% to 95%.

[0041] In some embodiments, the first condition is a first temperature range and the second condition is a second temperature range higher than the first temperature range.

[0042] In some embodiments, the first condition is a first gas pressure and the second condition is a second gas pressure lower than the first gas pressure.

[0043] In some embodiments, the first condition is a first CO2 concentration and the second condition is a second CO2 concentration lower than the first CO2 concentration.

[0044] In some embodiments, the composition further includes an additive, a hydrophobic silane compound, and / or a hydrophobic polymer bound to the porous particles.

[0045] In some embodiments, the composition 15% wt / wt poly(vinyl alcohol), 1% wt / wt etidronic acid, 10% wt / wt polyethyleneimine, 45% wt / wt N-2-aminoethyl-3-aminoproplytrimethoxysilane, 1% wt / wt hindered amine light stabilizer, and 1% wt / wt terephthalaldehyde. Here, N-2-aminoethyl-3-aminoproplytrimethoxy silane (DAMO) has the molecular structure:

[0046] In some embodiments, the composition comprises: between 5% wt / wt and 25% wt / wt poly(vinyl alcohol), between 0.3% wt / wt and 2% wt / wt etidronic acid, between 5% wt / wt and 15% wt / wt polyethyleneimine, between 35% wt / wt and 55% wt / wt N-2-aminoethyl-3-aminoproplytrimethoxysilane, between 0.5% wt / wt and 2 % wt / wt hindered amine light stabilizer, and between 0.5% wt / wt and 2% wt / wt terephthalaldehyde.

[0047] In any embodiment herein, the crosslinking agent is any described herein (e.g., such as in formulas VII or Vila - Vllm. In some embodiments, the crosslinking agent is present in an amount of about 1% to 50% (wt / wt) of the crosslinking agent to the plurality of porous particles (e.g., an amount of 1% to 2%, 1% to 3%, 1% to 4%, 1% to 10%, 1% to 20%, 1% to 40%, 5% to 40%, 5% to 30%, 10% to 50%, 10% to 40%, 10% to 30%, 20% to 50%, 20% to 40%, 20% to 30%, or 30% to 50% (wt / wt)). In some embodiments, the crosslinking agent is present in an amount of about 0.1 mol % to 50 mol % of the crosslinking agent to the number of moles of amines present, (e.g., an amount of 0.1% to 2%, 0.1% to 3%, 0.1% to 4%, 1% to 2%, 1% to 3%, 1% to 4%, 2% to 3%, 2% to 4%, 1% to 10%, 1% to 20%, 1% to 40%, 5% to 40%, 5% to 30%, 10% to 50%, 10% to 40%, 10% to 30%, 20% to 50%, 20% to 40%, 20% to 30%, or 30% to 50%(mol %)). Mole percent (mol %) is the percentage of the number of moles of a particular component compared to the total moles in a mixture.

[0048] In any embodiment herein, the aminosilane is any described herein (e.g., such as in formulas I, la-If, II, Ila-IId, Illa, Illb, or IV). In some embodiments, the aminosilane is present in an amount of about 5% to 80% (wt / wt) of the aminosilane to the plurality of porous particles (e.g., an amount of 5% to 70%, 5% to 60%, 5% to 50%, 5% to 40%, 5% to 30%, 10% to 80%, 10% to 70%, 10% to 60%, 10% to 50%, 10% to 40%, 10% to 30%, 20% to 80%, 20% to 70%, 20% to 60%, 20% to 50%, 20% to 40%, 20% to 30%, 30% to 80%, 30% to 70%, 30% to 60%, 30% to 50%, 40% to 80%, 40% to 70%, 40% to 60%, 50% to 80%, 50% to 70%, or 50% to 60% (wt / wt)).

[0049] In any embodiment herein, the silane is any described herein (e.g., such as in formulas V-Va). In some embodiments, the silane is present in an amount of about 5% to 80% (wt / wt) of the silane to the plurality of porous particles (e.g., an amount of 5% to 70%, 5% to 60%, 5% to 50%, 5% to 40%, 5% to 30%, 10% to 80%, 10% to 70%, 10% to 60%, 10% to 50%, 10% to 40%, 10% to 30%, 20% to 80%, 20% to 70%, 20% to 60%, 20% to 50%, 20% to 40%, 20% to 30%, 30% to 80%, 30% to 70%, 30% to 60%, 30% to 50%, 40% to 80%, 40% to 70%, 40% to 60%, 50% to 80%, 50% to 70%, or 50% to 60% (wt / wt)).

[0050] In any embodiment herein, the polyamine is any described herein (e.g., such as in formulas Via, VIb, Vic, Vid, Vie, VIf, Vig, VIh, or Vli. In some embodiments, the polyamine is present in an amount of about 5% to 60% (wt / wt) of the polyamine to the plurality of porous particles (e.g., an amount of 5% to 50%, 5% to 40%, 5% to 30%, 10% to 60%, 10% to 50%, 10% to 40%, 10% to 30%, 20% to 60%, 20% to 50%, 20% to 40%, 20% to 30%, 30% to 60%, 30% to 50%, 40% to 60%, or 50% to 60% (wt / wt)).

[0051] In any embodiment herein, the monoamine is any described herein (e.g., any compound or moiety having one amine group, such as -NRN1RN2, in which RN1 and RN2 is any described herein, and in which the amine group may be attached to a linker (e.g., any described herein)). In some embodiments, the monoamine is present in an amount of about 5% to 60% (wt / wt) of the monoamine to the plurality of porous particles (e.g., an amount of 5% to 50%, 5% to 40%, 5% to 30%, 10% to 60%, 10% to 50%, 10% to 40%, 10% to 30%, 20% to 60%, 20% to 50%, 20% to 40%, 20% to 30%, 30% to 60%, 30% to 50%, 40% to 60%, or 50% to 60% (wt / wt)).

[0052] The details of one or more embodiments are set forth in the accompanying drawings and the description below. Other features and advantages will be apparent from the description and drawings, and from the claims.

[0053] As used herein, the terms “top,” “bottom,” “upper,” “lower,” “above,” and “below” are used to provide a relative relationship between structures. The use of these terms does not indicate or require that a particular structure must be located at a particular location in the apparatus. DESCRIPTION OF DRAWINGS

[0054] FIGS. 1A-1E are non-limiting schematic illustrations of functionalized, crosslinked materials, in accordance with some embodiments of the present disclosure.

[0055] FIGS. 2A-2K are chemical illustrations of non-limiting, exemplary compounds, amine moieties, and silane moieties. Provided are illustrations of (A) an aminosilane compound, (B, C) non-limiting amine moieties, (D-G) non-limiting aminosilane compounds, and (H-K) non-limiting polyamine compounds in accordance with some embodiments of the present disclosure.

[0056] FIGS. 2L-M are chemical illustrations of non-limiting, exemplary crosslinking agents. Provided are illustrations of (L) a dihaloalkane, or (M) an epoxide compound in accordance with some embodiments of the present disclosure.

[0057] FIGS. 3 A-3E are non-limiting flow chart diagrams showing the steps of producing enhanced particles in accordance with some embodiments of the present disclosure.

[0058] FIGS. 4A-4B are schematic illustrations of (A) an example dip-coating method using a double cone mixing and drying system and (B) an example drying method using a double cone mixing and drying system in accordance with some embodiments of the present disclosure.

[0059] FIG. 5 is a schematic illustration of an example Nutsche filter mixing / filtration / drying system for producing functionalized particles from particles in accordance with some embodiments of the present disclosure.

[0060] FIG. 6 is a schematic illustration of an example bag dip-coating system for producing functionalized particles from particles in accordance with some embodiments of the present disclosure.

[0061] FIG. 7 is a schematic illustration of an example paddle dryer for producing functionalized particles from particles in accordance with some embodiments of the present disclosure.

[0062] FIG. 8 is a schematic illustration of an example ribbon dryer for producing functionalized particles from particles in accordance with some embodiments of the present disclosure.

[0063] FIGS. 9A-9B are schematic illustrations of (A) an example drying method using a conveyor dryer and (B) operation of an example drying method in continuous mode in accordance with some embodiments of the present disclosure.

[0064] FIGS. 10A-10B are schematic illustrations of (A) an exploded view and an assembled view of a non-limiting sample holder for testing sample CO2 adsorption and (B) a non-limiting experimental setup for testing sample adsorption of CO2 in accordance with some embodiments of the present disclosure.

[0065] FIGS. 11A-11B are schematic illustrations of non-limiting, exemplary implementations of a carbon dioxide extraction system in accordance with some embodiments of the present disclosure.

[0066] FIG. 12 is a schematic illustration of a non-limiting, exemplary implementation of an integrated power and carbon dioxide extraction system in accordance with some embodiments of the present disclosure.

[0067] FIGS. 13 A and 13B illustrate exemplary aminosilanes, in accordance with some embodiments of the present disclosure.

[0068] FIG. 14 is a line chart depicting CO2 uptake over a plurality of cycles by a nonlimiting functionalized material including a silica substrate, in accordance with some embodiments of the present disclosure. Provided are the testing cycle number (x-axis) and uptake at each cycle (y-axis).

[0069] FIG. 15 is a schematic illustration of a compression strength test fixture for testing particle samples, in accordance with some embodiments of the present disclosure.

[0070] FIGS. 16A and 16B are schematic illustrations of an attrition and abrasion test fixture for testing particle samples, in accordance with some embodiments of the present disclosure.

[0071] In the figures, like references indicate like elements. DETAILED DESCRIPTION

[0072] Amorphous silica is used as a porous structure for functionalization to achieve carbon capture. Silica substrates with amine functionalization, e.g., one or more amine-containing groups covalently bonded on surfaces, achieve reversible capture of carbon dioxide from gaseous mixtures (e.g., the atmosphere). In some embodiments, other porous substrates, such as MOFs, resins, or any described herein, are employed to provide a functionalized material (e.g., a functionalized porous material) that has been functionalized with an adsorbing moiety (e.g., an amine moiety provided by a compound, such as an amine, an aminosilane, a polyamine, a monoamine, or a combination thereof). In certain embodiments, the functionalized material is used as a sorbent.

[0073] Described herein is a functionalized and crosslinked material (e.g., a functionalized, crosslinked porous material) that has been functionalized with an adsorbing moiety (e.g., an amine moiety provided by a compound, such as an amine, an aminosilane, a polyamine, a monoamine, or a combination thereof) and that has been crosslinked with a linking moiety (e.g, provided by a compound, such as a crosslinking agent). In some embodiments, functionalization further comprises the use of an interaction moiety (e.g, a silane moiety provided by a compound, such as a silane, an aminosilane, and the like). In some embodiments, such moi eties (e.g., amine moi eties and / or silane moi eties) are any compound and any useful combination of two or more compounds (e.g., one or more of amines, aminosilanes, polyamines, monoamines, or any combination of any of these). To enhance lifetime improvement, in some embodiments, the adsorbing moiety and / or the interaction moiety is crosslinked by use of a crosslinker agent and / or is protected from oxidation by use of an oxygen barrier (e.g., provided by way of a polymer coating), an antioxidant, a chelating agent, or a combination of any of these.

[0074] Many factors can affect the chemical lifetime and / or physical lifetime of sorbents. For example and without limitation, when an amine is employed as the adsorbing moiety, volatilization and / or oxidation of such moieties can minimize its adsorption capacity. Without wishing to be limited by mechanism, amine volatilization is generally a process in which the amine functional group (e.g., on exposed surfaces and in the pores of a substrate) is released from the surface of the substrate during vacuum desorption. Amine volatilization rates are reduced by process controls such as lowering the exposure of the amine-based sorbents to vacuum, elevated temperatures (e.g., > 40°C) and, as described herein, by use of chemical compounds that provide reduced amine volatilization. Without wishing to be limited by mechanism and theory, it has been discovered that a crosslinking agent (e.g., dialdehydes, isocyanates, dihaloalkanes, diepoxides, dianhydrides (e.g., EDTA dianhydride), diacid chlorides, and the like) are used to reduce amine leaching from sorbent and / or to improve physical strength of the sorbent by the presence of crosslinks.

[0075] Amino oxidation may also be a factor. Without wishing to be limited by mechanism, amine oxidation is generally a process in which the amine functional group (e.g., on exposed surfaces and in the pores of a substrate) can degrade due to oxidation with atmospheric oxygen and / or other Reactive Oxygen Species (ROS), thereby forming a variety of non-functional products. Amine oxidation rates can be reduced by process controls such as lowering the exposure of the amine-based sorbents to oxygen at elevated temperatures (e.g., > 40 °C) and, as described herein, by use of chemical compounds that provide reduced amine oxidation.

[0076] For example and without limitation, amine oxidation can be catalyzed by the presence of oxygen or other oxidative species (e.g., ROS, e.g., but not limited to, superoxide, ozone, hydroxyl radicals, hydroperoxyls). Without wishing to be limited by mechanism and theory, it has been discovered that a polymer (e.g., polyvinyl alcohol (PVA)) disposed on a surface of the substrate can reduce oxidation of adsorbing species, such as an amine-containing functional group. In some embodiments, the polymer coating may serve as an oxygen barrier. Other oxygen barriers may be employed. The oxygen barrier can be provided to be in proximity to the porous substrate of the functionalized material. Without wishing to be limited by mechanism or theory, an oxygen barrier can be employed to extend chemical lifetime (e.g., by blocking oxygen or oxidative species from oxidizing adsorbing moi eties) and / or to extend physical lifetime (e.g., by forming a coating on a surface of the porous substrate, thereby enhancing its structural integrity).

[0077] In another non-limiting embodiment, oxygen or other oxidative species are scavenged by using a chemical antioxidant. Either sacrificial antioxidants or cyclic antioxidants such as hindered amine light stabilizers (HALS) is added, in some embodiments, to the functionalized material to reduce the oxidation of the amines, thereby extending the chemical lifetime of the sorbent. In some embodiments, the antioxidant is provided in any useful component of the functionalized particle. For example and without limitation, in some embodiments the antioxidant is provided in proximity to the surface of the substrate, within the coating of a coated substrate (e.g., a coated particle), and / or in proximity to the functional portion (e.g., an adsorbing moiety, such as an amine) of a functionalized material.

[0078] In yet another non-limiting embodiment, amine oxidation is e catalyzed by transition metals, such as iron, copper, and the like. In one instance, silica substrates are contaminated with metals, e.g., transition metals, e.g., iron or copper, due to the sand from which they are derived. In various examples, chelating agents are used to chelate or otherwise interact with metals, thereby reducing its oxidative action and extending the chemical lifetime of the sorbent. In some embodiments, the chelating agent is provided in any useful component of the functionalized particle. For example and without limitation, the chelating agent is provided, in some embodiments, in proximity to the surface of the substrate, within the coating of a coated substrate (e.g., a coated particle), and / or in proximity to the functional portion (e.g., an adsorbing moiety, such as an amine) of a functionalized material.

[0079] Any useful combination of an oxygen barrier (e.g., provided by way of a polymer), an antioxidant, or a chelating agent is employed in some embodiments. For example and without limitation, an oxygen barrier may be used alone or in combination with an antioxidant and / or a chelating agent. In another example, the antioxidant may be used alone or in combination with an oxygen barrier and / or a chelating agent. In yet another example, the chelating agent may be used alone or in combination with an oxygen barrier and / or an antioxidant. Furthermore, the oxygen barrier, antioxidant, and chelating agent may be present in any useful component of the functionalized material, such as in proximity to the surface of the substrate and / or in proximity to the functional portion (e.g., including an adsorbing moiety of the functional portion).

[0080] I. Functionalized material

[0081] The present disclosure relates to a functionalized compositions having one or more functional groups. For example and without limitation, an initial material or substrate is functionalized, in some embodiments, to include one or more functional groups (e.g., one or more amine groups) configured to capture carbon dioxide (CO2). As used herein and without limitation, a monofunctional molecule possesses one functional group (e.g., one reactive group), and a multivalent molecule possess a plurality of functional groups (e.g., a plurality of reactive groups). In some embodiments, the multivalent molecule includes a difunctional (e.g., or bifunctional) molecule possessing two functional groups (e.g., two reactive groups), a trifunctional molecule possessing three functional groups (e.g., three reactive groups), and so forth. In some non-limiting embodiments, the composition has any useful structure (e.g., as a particle), any useful substructure (e.g., one or more pores), and any useful composition (e.g., silica or others described herein). In some non-limiting embodiments, amorphous silica is used as a porous substrate for functionalization to achieve carbon capture. In some embodiments, silica substrates with amine functionalization, e.g., one or more amine-containing moieties covalently bonded on a surface, exhibit reversible capture of carbon dioxide from gaseous mixtures (e.g., the atmosphere). Other substrates and moieties are also described herein, which can provide functionalized compositions for carbon capture.

[0082] Disclosed herein is a functionalized material (e.g., functionalized porous silica) having a surface modification layer including a linking moiety and a method of producing such protected materials. Also, disclosed herein is a functionalized material (e.g., functionalized porous silica) having a protective polymer coating (e.g., as an oxygen barrier) and a method of producing such protected materials. In turn, the functionalized material is used, in some embodiments, for reversibly capturing (e.g., adsorbing) carbon dioxide (CO2). In use, the functionalized material is provided, in some embodiments, in any useful format (e.g., as a layer of beads or powder) over or through which gaseous mixtures including CO2 are flowed. Gas exiting the layer of functionalized material has a lower concentration of CO2 than the entering gas. During carbon capture adsorption and desorption processes, the functionalized material experiences mechanical attrition through handling, use, and transport through the capture and regeneration processes. Providing a protective polymer coating on the functionalized material (composition) can decrease friability and attrition of the sorbents, leading to longer product life and reduced production of fines. Furthermore, in some embodiments, when the protective polymer coating also serves as an oxygen barrier, the functionalized material (composition) has an extended chemical lifetime due to reduced oxidation.

[0083] For example, FIG. 1A provides a non-limiting functionalized material (composition) 100A comprises a substrate 102A having a plurality of pores 104A-a, 104A-b. In turn, the surface 103 A of the substrate 102A includes a functional portion 106A, which in turn includes an adsorbing moiety 110A (e.g., a CO2 adsorbing moiety) and an interaction moiety 108A (e.g., a silane-containing interaction moiety). In some embodiments, the functional portion 106 A further include other moi eties, groups, or molecules to provide an adsorbing material for use as a sorbent. In some embodiments, such moieties, groups, or molecules include an amine group (e.g., -NRN1RN2, as described herein, which in turn is present in amines, aminosilanes, polyamines, and the like in some embodiments), polymers (e.g., hydrophobic polymers or polyamines), antioxidants, and the like. Furthermore, in some embodiments, such moieties, groups, or molecules form interactions (e.g., covalent and / or non-covalent interactions) between themselves or between itself and the substrate surface.

[0084] A surface modification layer is disposed, in some embodiments, on at least a portion of the surface 103 A. The surface modification layer includes an adsorbing moiety having one or more amine moieties (e.g., any described herein). As seen in FIG. 1A, the surface modification layer includes any useful combination of an adsorbing moiety 110A (e.g., a CO2 adsorbing moiety) and an interaction moiety 108A. In some embodiments, the material (composition) is configured to adsorb atmospheric CO2 under a first condition and reversibly desorb adsorbed CO2 under a second condition. The surface modification layer is disposed, in some embodiments, in proximity to the surface 103 A of the substrate 102A.

[0085] In some embodiments, the surface modification layer include a linking moiety 114A. In general and without limitation, in some embodiments, the linking moiety 114A forms interactions between one or more of the adsorbing moieties, the interaction moieties, the substrate, or a combination thereof. In the example of FIG. 1 A, the linking moiety 114Aa forms interactions between the interaction moieties 108 A of multiple functional groups 106 A, e.g., between the interaction moieties 108A that are each provided on two different functional groups 106A. In such examples, the linking moiety 114Aa is considered difunctional, e.g., comprises two interaction sites. In other examples, the linking moiety 114Ab forms interactions between the interaction moiety 108A and the adsorbing moiety 110A of multiple functional groups 106A, e.g., between the interaction moiety 108A of a first functional group and the adsorbing moiety 110A of a second functional group. In yet other examples, the linking moiety 114Ac forms interactions between the adsorbing moieties 110A of multiple functional groups 106A, e.g., between the adsorbing moieties 110A that are each provided on two different functional groups 106A.

[0086] The linking agent 114A is shown forming interactions between a portion of the functional groups 106 A. In some embodiments, the portion of the functional groups 106 A that the linking moieties 114A form interactions is in a range from 0.1 mol % to 50 mol % of the functional groups 106 A to the number of moles of amines present.

[0087] The linking moiety 114A is provided in any useful manner in some embodiments, e.g., by use of one or more crosslinking agents (e.g., any described herein). In some embodiments, the crosslinking agent includes a linking moiety disposed between one or more reactive groups, in which the reactive group is configured to react with an amine functional group (e.g., as provided by an adsorbing moiety 110A).

[0088] In some embodiments, the linking moiety 114B forms interactions with the surface of the substrate, the adsorbing moieties, and the interaction moieties. As seen in FIG. IB, in some embodiments the surface modification layer includes an adsorbing moiety HOB (e.g., a CO2 adsorbing moiety) and the linking moiety 114B. The surface modification layer is disposed, in some embodiments, in proximity to the surface 103B of the substrate 102B. The linking moiety 114B is provided, in some embodiments, by a reaction between a functional group present in the surface modification layer (e.g., an amine group) with a reactive group of any crosslinking agent described herein.

[0089] In some embodiments, the functional group 106B includes the linking moiety 114B and the adsorbing moiety HOB. In some embodiments, the linking moiety 114B interacts with the surface 103B and the adsorbing moiety 110B. A portion of the functional groups 106B include a linking moiety 114Ba forming interactions between two linking moieties 114B in two functional groups 106B. As shown in FIG. IB, the functional group 106B is shown crosslinked to functional group 106B-a by a linking moiety 114Ba. In some examples, the linking moiety 114B forms interactions between higher numbers of functional groups 106B, e.g., three or more functional groups 106B. In other examples, the linking moiety 114Bb forms interactions between the linking moiety 114A and the adsorbing moiety 110B of multiple functional groups 106B. In yet other examples, the linking moiety 114Bc forms interactions between adsorbing moieties 110B of multiple functional groups 106B.

[0090] Optionally, a polymer coating 105C is disposed on the surface 103C, as seen in FIG. IC. In some embodiments, the polymer, or mixture of polymers, increases the mechanical characteristics of the functionalized, crosslinked, and coated material 100C. One example of the polymer that makes up the polymer coating is polyvinyl alcohol (PVA), a water-soluble synthetic polymer having the formula [CH2CH(OH)]n, where n is a positive integer (e.g., in the tens, hundreds or thousands, etc.). PVA is readily available from commercial sources and has low toxicity for safe handling during application. The PVA can have a molecular weight (MW) in a range from 10,000 to 200,000 (e.g., in a range from 10,000 to 23,000).

[0091] In general, the polymer coating 105 A is illustratively depicted as a continuous layer on the surface 103A, though in practice there may exist one or more gaps, e.g., holes, in the polymer coating 105 A that can facilitate the amines, aitioxidants, or crosslinkers interacting with the surface 103 A. Moreover, the substrate has any number of pores that each cause a gap in the polymer coating layer as illustrated in FIG IC. Although the polymer coating 105 A is a discontinuous layer, in some embodiments, the coating 105 A is effective at blocking oxygen by reducing the area of the surface 103 A exposed to oxygen.

[0092] As seen in FIG. IC, in some embodiments the surface modification layer includes an adsorbing moiety 110C (e.g., a CO2 adsorbing moiety) and a linking moiety 114C that form a functional group 106C. The surface modification layer is disposed, in some embodiments, in proximity to the surface 103C of the substrate 102C and / or the surface of the polymer coating 105C.

[0093] Additional examples of polymers that provide the coating include Pebax, polyether block amide (PEBA), polysulfones, polyethersulfones, polyethers, polyamides, ethylcellulose, polyethylene glycol, cellulose acetate, polyurethanes, polystyrenes, polyesters, polyolefins, polyacrylamides, polyacrylates, and combinations, copolymers, and / or block copolymers of those listed herein.

[0094] A polymer is provided in a coating liquid, in some embodiments, that in turn includes the polymer and a solvent medium (e.g., any described herein). In general, the amount of polymer depends on the type of polymer, the molecular weight of the polymer, the number of amino moieties in the polymer, etc. In some embodiments, the amount of polymer is up to 20% (wt / wt) to the substrate (e.g., silica particles), such as, e.g., up to 15% (wt / wt), up to 10% (wt / wt), up to 8% (wt / wt), less than 12% (wt / wt), or less than 9% (wt / wt). In some embodiments, the amount of polymer(s) is from about 1% to 20% (wt / wt) to the substrate (e.g, from about 1% to 5%, 1% to 10%, 1% to 15%, 3% to 5%, 3% to 10%, 3% to 15%, 3% to 20%, 5% to 10%, 5% to 15%, 5% to 20%, 7% to 10%, 7% to 15%, 7% to 20%, 10% to 15%, 10% to 20%, 1 3% to 15%, 13% to 20%, or 15% to 20% (wt / wt)).

[0095] In some embodiments, the solvent medium includes water. In some embodiments, the solvent medium includes a polar aprotic solvent or a neutral aprotic solvent. In some embodiments, the solvent medium includes an organic solvent selected from toluene, hexane, cyclohexane, tetrahydrofuran, or mixtures thereof. In some embodiments, the solvent medium includes methanol, cyclohexane, hexane, ethanol, water, or mixtures thereof.

[0096] The polymer coating is disposed on a surface of the substrate, in some embodiments, to achieve desirable outcomes for the functionalized material under mechanical stresses, such as abrasion. In some embodiments, the polymer coating decreases the attrition of the functionalized material according to one or more standardized testing requirements. Briefly, attrition is the propensity of a product to produce fines in the course of transportation, handling, and use. The polymer coating reduces the attrition such that attrition loss of the particles is 1% or less (e.g., 0.9 % or less, 0.8 % or less) as measured by ASTM D4058-96 or comparable standards by which attrition, or attrition loss, is quantified. In many examples, the functionalized material is characterized, in some embodiments, by mechanical properties that includes compressive strength. In some embodiments, the functionalized material is durable, e.g., having a crush strength of at least 100 N / mm (e.g., at least 150 N / mm, at least 200 N / mm).

[0097] In some implementations, the functionalized material includes one or more chelating agents. In some embodiments the chelating agent is present in proximity to the surface 103 A of the substrate 102A, the functional portion 106A, the adsorbing moiety 110A (e.g., a CO2 adsorbing moiety), and / or the interaction moiety 108A. In some embodiments, the chelating agent is present within the polymer coating 105 A. In some embodiments the chelating agent interacts with metals present on the surface or pores of the substrate and reduces potential oxidation of the functionalized particles, thereby increasing the chemical lifetime for the functionalized particles to adsorb CO2. For example, PVA is functional as a chelating agent.

[0098] Examples of the chelating agent include phosphate-based chelating agents, such as potassium phosphate, or phosphonate-based chelating agent, such as etidronic acid or a salt thereof. Other examples of the chelating agents include metal salts including phosphate (e.g., alkali metal salts, such as sodium phosphate), non-nitrogenous bisphosphonate compounds (e.g., clodronic acid and the like), and nitrogenous biphosphonate compounds (e.g., alendronic acid and the like). In some embodiments, the chelating agent is a bisphosphonate compound including a nitrogen or lacking a nitrogen. In some embodiments, the amount of chelating agent(s) is up to 2% (wt / wt) to the substrate (e.g., silica particles), such as, e.g., up to 0.3% (wt / wt), up to 0.4% (wt / wt), up to 0.6% (wt / wt), or up to 1% (wt / wt). In some embodiments, the amount of chelating agent(s) is from about 0.1% to 5% (wt / wt) to the substrate (e.g., from about 0.1% to 1%, 0.1% to 2%, 0.1% to 3%, 0.1% to 4%, 0.2% to 1%, 0.2% to 2%, 0.2% to 3%, 0.2% to 4%, 0.2% to 5%, 0.5% to 1%, 0.5% to 2%, 0.5% to 3%, 0.5% to 4%, 0.5% to 5%, 1% to 2%, 1% to 3%, 1% to 4%, or 1% to 5% (wt / wt)).

[0099] In some embodiments, the chelating agent(s) is added during any useful steps of the following synthesis procedure or afterward. In one example, the chelating agent is chelating agent / methanol mixture for 1 hour. In another example, the chelating agent is added to a solution including the polymer employed to form a coating.

[0100] In some embodiments, the functionalized material includes one or more antioxidants. Without being bound to any particular mechanism or theory, the antioxidant prevents the degradation of amine functional groups by atmospheric oxygen and extends the cycling lifetime of the functionalized material. In some embodiments the antioxidant is present in proximity to the surface 103 A of the substrate 102A, the functional portion 106A, the adsorbing moiety 110A (e.g., a CO2 adsorbing moiety), and / or the interaction moiety 108A. In some embodiments, the antioxidant is present within the polymer coating 105 A.

[0101] Examples of antioxidants for use in the method include sacrificial antioxidants and cyclic antioxidants. Sacrificial antioxidants are generally irreversibly consumed in an oxidation reaction while cyclic antioxidants are regenerable. In some embodiments, the amount of anti oxi dant(s) in the functionalized material is up to about 5% (wt / wt) to the substrate (e.g., silica particles), such as, e.g., up to 3% (wt / wt), 4% (wt / wt), 6% (wt / wt), or 8% (wt / wt). In some embodiments, the amount of antioxidant(s) is from about 0.1% to 3% (wt / wt) to the substrate (e.g., from about 0.1% to 1%, 0.1% to 2%, 0.1% to 3%, 0.1% to 4%, 0.2% to 1%, 0.2% to 2%, 0.2% to 3%, 0.2% to 4%, 0.2% to 5%, 0.5% to 1%, 0.5% to 2%, 0.5% to 3%, 0.5% to 4%, 0.5% to 5%, 1% to 2%, 1% to 3%, 1% to 4%, or 1% to 5% (wt / wt)).

[0102] For example, is some embodiments the antioxidant(s) is an organic sulfur-containing compound, such as 2,2-thiodiethanol, 2-hydroxyethyl disulfide, and 3,3’-dithiodipropionic acid. In another example, the antioxidant is a hindered amine light stabilizer (HALS) compound. HALS are antioxidant compounds containing an amine functional group and, in some non-limiting embodiments, constitute optionally substituted piperidine compounds. HALS is used, in some embodiments, at low concentrations and neutralize many oxidizing radicals and, in some embodiments, is continually regenerated by heat from the air, CO2 adsorption, desorber heat. In some embodiments, HALS extends the lifetime of the sorbent longer than sacrificial antioxidants.

[0103] In some examples, more than one antioxidant is introduced. In such examples, the antioxidants introduced may exhibit synergism, e.g., one antioxidant is regenerated by the second, one antioxidant protects the other by sacrificial oxidation, and / or when the antioxidants exhibit different antioxidant mechanisms.

[0104] In some embodiments, the antioxidant(s) are added during steps 302A-E, 304B-E, and / or 306A-E of the following synthesis procedure or afterward. In one example, the antioxidant is added through dissolving in methanol, or like organic solvent, and then soaking the substrate in the antioxidant / methanol mixture for between 30 minutes and 5 hours (e.g., 1 hour). In another example, the chelating agent is added to a solution including a reagent (e.g., including an adsorbing moiety) that is employed to form a functionalized material.

[0105] A functionalized material having any useful combination and number of moieties to facilitate capture of CO2 is illustrated in FIG. ID. As seen in FIG. ID, in some embodiments a surface modification layer includes any useful combination of a first adsorbing moiety HOD (e.g., a first CO2 adsorbing moiety), a second adsorbing moiety 112D (e.g., a second CO2 adsorbing moiety), and an interaction moiety 108D, in which the chelating agent and / or the antioxidant is associated with the surface modification layer. In some embodiments, the surface modification layer is disposed in proximity to the surface 103D of the substrate 102D. As described herein, in some embodiments a portion of the functional groups 106D and / or second adsorbing moieties 112D is crosslinked by the linking moiety 114D.

[0106] As shown in FIG. ID, the functional group 106D is shown crosslinked to functional group by a linking moiety 114Da. In some examples, the linking moiety 114Da forms interactions between the interaction moieties 108D of multiple functional groups 106D. In other examples, the linking moiety 114Dd forms interactions between the interaction moieties 108D and adsorbing moieties 110D of multiple functional groups 106D. In yet other examples, the linking moiety 114Dc forms interactions between adsorbing moieties 110D of multiple functional groups 106D. In other examples, the linking moiety 114Dd forms interactions between first adsorbing moieties HOD and second adsorbing moieties 112D. In yet other examples, the linking moiety 114De forms interactions between interaction moieties 108D and second adsorbing moieties 112D.

[0107] In some embodiments, a polymer coating is employed with second adsorbing moieties. For example, FIG. IE provides a non-limiting functionalized material 100E including a substrate 102E having a plurality of pores 104E-a, 104E-b. In turn, the surface 103E of the substrate 102E includes a polymer coating 105E and a functional portion 106E that, in turn, includes a combination of a first adsorbing moiety 110E (e.g., a first CO2 adsorbing moiety), a second adsorbing moiety 112E (e.g., a second CO2 adsorbing moiety), and an interaction moiety 108E (e.g., a silane-containing interaction moiety). Optionally, the chelating agent and / or the antioxidant is present in proximity to the surface 103E of the substrate 102E, the functional portion 106E, the first adsorbing moiety 110E (e.g., a first CO2 adsorbing moiety), the second adsorbing moiety 112E (e.g., a second CO2 adsorbing moiety), and / or the interaction moiety 108E. In some embodiments, the chelating agent and / or the antioxidant is present within the polymer coating 105E. As described herein, a portion of the functional groups 106E and / or second adsorbing moieties 112E are crosslinked by the linking moiety 114E in some embodiments.

[0108] In some embodiments, the moieties of a functionalized material are provided in any useful manner. In some embodiments, the surface of a substrate is functionalized by use of a first CO2 adsorbing compound (e.g., including an aminosilane) and a second CO2 adsorbing compound (e.g., a polyamine). In turn, in some embodiments, the first CO2 adsorbing compound provides a first adsorbing moiety (e.g., moiety 110E in FIG. IE), and the second CO2 adsorbing compound provides a second adsorbing moiety (e.g., moiety 112E in FIG. IE).

[0109] In some embodiments, when the first CO2 adsorbing compound is an aminosilane, the aminosilane includes a silane moiety as a non-limiting interaction moiety (e.g., interaction moiety 108E in FIG. IE) and an amine moiety as a non-limiting first adsorbing moiety (e.g., first adsorbing moiety 110E in FIG. IE). In some embodiments, the aminosilane is covalently bonded to the exterior surface of the substrate (e.g., surface 102E in FIG. IE) and within the pores (e.g., pores 104E-a, 104E-b in FIG. IE). Other examples of adsorbing compounds include any compounds described herein (e.g., any aminosilanes or other compounds including one or more amine moieties). In some embodiments, together an aminosilane and a polyamine form a network and provide the stable CO2 adsorbing function.

[0110] In some embodiments, the second adsorbing moiety is provided by any useful second adsorbing compound. Examples of adsorbing compounds include any compounds described herein (e.g., any compounds including one or more amine moieties). In some embodiments, any useful combination of second and first adsorbing compounds are employed, and such compounds interact in any useful manner to provide a functionalized network or coating disposed over the surface of the substrate. In turn, in some embodiments, such a network or coating is characterized by any useful combination of adsorbing moieties and interaction moieties.

[0111] In some embodiments, the second adsorbing moiety is provided with or without a second interaction moiety. In some embodiments the second interaction moiety provides direct or indirect attachment to a surface of the substrate. For example and without limitation, in some embodiments, a polyamine include a plurality of amine moieties and at least one linker disposed between at least two amine moi eties (e.g., -(RA-L)n-, in which RA is an amine moiety, Lisa linker, and n is an integer). In some embodiments, the amine moiety RA acts as an adsorbing moiety. Depending on other components present in the functionalized material, either the amine moiety RA or the linker L acts as an interaction moiety in some embodiments. For example, in some embodiments an amine moiety RA of a polyamine interacts with other amine moi eties or silane moi eties by way of hydrogen bonding or ionic interactions.

[0112] In some embodiments, the second adsorbing compound is a polyamine, that can include an amine moiety as a non-limiting second adsorbing moiety (e.g., second adsorbing moiety 112E in FIG. IE). In some embodiments, the second adsorbing moiety is represented by a certain functional group (e.g., an amine group of -NRN1RN2 or -NRN1-as described herein) or a certain compound having certain functional groups (e.g., a compound including one or more amine groups of -NRN1RN2 or -NRn1- as described herein). Other examples of adsorbing compounds include any compounds described herein (e.g., any polyamines or other compounds including one, two, or more amine moieties).

[0113] In some embodiments, the second adsorbing moiety interacts with other functional groups, moieties, or compounds in the functionalization material in various ways. For example and without limitation, in some embodiments, the second adsorbing moiety interacts with the first adsorbing moiety, the interaction moiety, the surface of the substrate, or another second adsorbing moiety. Such interactions include covalent and / or non-covalent bonding interactions (e.g., any described herein). In some embodiments, the second adsorbing moiety interacts with the first adsorbing moiety. In some embodiments, the second adsorbing moiety interacts with the interaction moiety.

[0114] In some embodiments, the second adsorbing moiety comprises a polyamine or amine moieties from a polyamine. When the first adsorbing moiety is an aminosilane, the polyamine interacts with amine moieties of the aminosilane or interaction moieties of the aminosilane in some embodiments. In some embodiments, amine moieties of the aminosilane and the polyamine interact with silanol groups of the aminosilane through hydrogen bonding and ionic interactions to form a functional group, thereby forming a complex network over the surface of the substrate. Using FIG. IE as a reference, in some embodiments a functional group 106E includes amine moieties 110E of aminosilane and amine moieties 112E of the polyamine that interact with silanol groups 108E of the aminosilane.

[0115] In some embodiments, a plurality of adsorbing moieties is provided for the functionalized material. For instance, in some embodiments, a polyamine (e.g., such as polyethyleneimine (PEI)) having a plurality of adsorbing moieties is reacted with the substrate. In some embodiments, the polyamine is characterized by a high interaction surface area that facilitates one dimensional or two dimensional van der Waals interactions with the substrate surface. In some embodiments, the polyamine introduced to the substrate forms a surface modification layer for reversibly binding CO2 from atmospheric gases. In some embodiments, a polyamine (e.g., PEI having a larger molecular weight such as, e.g., greater than about 800 Da or from about 800 Da to 1 MDa (or 1,000,000 Da)), as compared to short chain amine functionalization) is less volatile overall.

[0116] In some embodiments, the plurality of adsorbing moieties are provided by way of one or more oligomeric amines or small molecule polyamines or mixtures of any of these. In some embodiments, the oligomeric amine includes an oligomeric ethylene amine or a mixture including such oligomers (e.g., an ethylene amine / oligomer mixture). For example, in some embodiments the oligomer includes ethylene amine-containing molecules (e.g., molecules including a -CH2CH2NRn1- group) or oligomers such as H2N[CH2CH2NH]nH (e.g., in which n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more and RN1 can be any described herein). Tetraethylenepentamine (TEPA) and triethylenetetramine (TETA) are non-limiting examples of oligomeric amines with low volatility. In some embodiments, the oligomeric amine is a small molecule polyamine (e.g., having a molecular weight (MW) between 100 to 800 g / mol). Other examples of oligomers are described herein.

[0117] In some embodiments, a small molecule amine mixture (e.g., such as Amix 1000) includes amine-containing molecules, such as 2-[(2-aminoethyl)amino]ethanol, (aminoethyl)piperazine, and / or (hydroxyethyl)piperazines as a commercially available mixture of amines.

[0118] In some non-limiting embodiments, Amix 1000, TEPA, TETA, or a mixture of these or similar compounds is used to functionalize a substrate to form a functionalized material (compound). In some embodiments, Amix 1000, TEPA, TETA, and similar compounds are a low-cost source of reactable amines facilitating low-cost functionalization and carbon capture from atmospheric gases.

[0119] In some embodiments, the oligomeric amine or small molecule amine mixture is reacted with a porous silica substrate to form a functionalized substrate. In some embodiments, the oligomeric amine or the small molecule amine mixture is a compound bonded to a surface of the substrate and forms a surface modification layer on the surface through van der Waals interactions.

[0120] Using FIG. IE as a reference, in some embodiments a functional group 106E includes a polyamine group. In some embodiments, the polyamine group includes one or more primary, secondary, or tertiary amine groups, repeat units of ethylamine or propylamine; or more than one amine groups connected through various linkers (e.g., alkylene groups), or linear or branched polyamines. In some embodiments, the polyamine group has an increased interaction surface area compared to short chain amine-containing compounds due to the increased number of amine groups in the polymeric chain. In some embodiments, the polyamine group is bonded to the substrate 102E through van der Waals interactions, hydrogen bonding, and / or ionic interactions.

[0121] In some embodiments of any of the functional materials (compounds) herein, the functional portion includes an adsorbing moiety that captures CO2 (e.g., as in a CO2 adsorbing moiety). In some embodiments, the CO2 adsorbing moiety includes one or more amine-containing moieties. In some embodiments, the amine-containing moieties are an aminosilane, an amine, a polyamine, or any combination of these. Additional details regarding CO2 adsorbing moieties are described herein.

[0122] As also described herein, in some embodiments the functional portion includes an interaction moiety that interacts with at least a portion of the surface of a substrate. In some embodiments, the interaction moiety is selected based on the substrate to be functionalized. In some embodiments, the substrate to be functionalized includes silica, and the interaction moiety is configured to react with silica. In some embodiments, the interaction moiety comprises a silane moiety that reacts with the surface of the silica substrate. In other embodiments, the substrate to be functionalized includes a metal-organic framework (MOF) material, and the interaction moiety is configured to react with the MOF material. In some embodiments, the interaction moiety comprises a silane moiety that reacts with the surface of the MOF substrate. In other embodiments, the substrate to be functionalized includes a resin material, and the interaction moiety is configured to react with the resin material. In some embodiments, the interaction moiety comprises an amine moiety that reacts with the surface of the resin substrate. The interaction moiety can interact with the substrate surface by way of covalent and / or non-covalent bonding interactions (e.g., as described herein). Additional details regarding interaction moieties and substrates are described herein.

[0123] Such moieties can be introduced in any useful manner. For instance, such moieties can be present in one or more compounds, which in turn can be provided within a suspension or a mixture (e.g., a functionalization mixture). When a substrate is also present, then the compounds can interact with the substrate to provide a functionalized material. Any useful compound(s) can be employed. In one non-limiting instance, the amine moiety and silane moiety are provided by way of an aminosilane compound, which in turn reacts with or interacts with the substrate surface to provide amine-containing groups. In another non-limiting embodiment, the amine moiety is provided by way of a polyamine compound, which in turn reacts with or interacts with the substrate surface to provide amine-containing groups. In yet another non-limiting instance, both an aminosilane compound and a polyamine compound are employed to provide a functionalized surface. In some embodiments, such reactions result in covalent and / or non-covalent interactions, in which a linking group (e.g., by way of optionally substituted aliphatic, alkylene, alkenylene, alkynylene, heteroaliphatic, heteroalkylene, heteroalkenylene, heteroalkynylene, aromatic, arylene, heteroaromatic, heteroarylene, and the like) is present between a functional group (or a moiety) and the substrate surface. In some embodiments, an amine moiety is an amine functional group itself (e.g., -NRN1RN2, as described herein) or a portion of a compound including the amine functional group (e.g., -L-NRN1RN2, in which L, RN1, and RN2 is any described herein). Additional details regarding compounds, suspensions, and mixtures to provide functional portions are described herein.

[0124] In use, the functionalized material is provided as a layer (e.g., a layer of beads or powder) or a bed over which or through which a gaseous mixture including CO2 is flowed. Such a material is considered a “sorbent” or “adsorbent,” in which these terms are used interchangeably unless otherwise specified. Gas exiting the sorbent has a lower concentration of CO2 than the entering gas. In some embodiments, the functionalized material reversibly adsorbs CO2 over a number of cycles, e.g., a number of adsorption and desorption steps, in which a cycle includes at least one adsorption step and at least one desorption step. Higher cycle counts are used to characterize materials having longer product lifetimes when used in CO2 capture applications. In some non-limiting implementations, the functionalized material reversibly adsorbs CO2 over 100 cycles (e.g., over 500 cycles, over 1000 cycles, over 2000 cycles, or over 3000 cycles). Here and throughout the specification, reference to a measurable value such as an amount, a temporal duration, and the like, the recitation of the value encompasses the precise value, approximately the value, and within ±10% of the value. For example, here 100 cycles include precisely 100 cycles, approximately 100 cycles, and within ±10% of 100 cycles.

[0125] CO2 adsorbed to the functionalized material may be released (e.g., desorbed) under some conditions. As one example, reducing the gas pressure surrounding the functionalized material desorbs captured CO2. As another example, reducing the partial pressure of CO2 surrounding the functionalized material desorbs captured CO2 (e.g., by purging with N2 or another gas). In some embodiments, one or more of these approaches facilitates recapture of the adsorbed CO2 in a secondary environment. In some embodiments, the functionalized material is exposed to a reduced gas pressure of less than 5 psi (e.g., less than 3 psi, 1.5 psi, 1 psi, or 0.1 psi).

[0126] In some embodiments, increasing the temperature of the functionalized material destabilizes bonding between the amine group and CO2, thereby desorbing the CO2 from the functionalized material. In some implementations, the functionalized material desorbs CO2 at temperatures above 60°C (e.g., above 60°C, 70°C, 80°C, or 90°C). In some embodiments, increasing the temperature and decreasing gas pressure concurrently increases the rate at which the CO2 desorbs from the functionalized material.

[0127] Indeed, release of gas from a sorbent can include any useful process. In one example, a swing process can be employed. Such swing processes can include application of a change in temperature, of a change in pressure, and / or of a vacuum to release the gas from the sorbent composition. Swing processes can include Temperature Swing Adsorption (TSA), Pressure Swing Adsorption (PSA), and Vacuum Swing Adsorption (VSA), or a combination of these. In some embodiments, the released gas can be provided as outputs, and such outputs can be generated by exposing the sorbent to a temperature swing adsorption process, a pressure swing adsorption, a vacuum swing adsorption process, or a combination of any of these.

[0128] i. Substrate

[0129] In some embodiments the functionalized material includes any useful substrate. In some embodiments the substrate is in the form of a plurality of porous particles. In some embodiments, the substrate has a porous surface upon which a functional portion is disposed. In some embodiments, the substrate comprises a porous substrate, such as a porous ceramic (e.g., a porous metal oxide, a porous metalloid oxide, or combinations thereof or mixed forms thereof), a porous metal-organic substrate, or a porous polymeric substrate. In some embodiments, the substrate comprises a porous ceramic / metal oxide together with porous silica (e.g., including porous alumina, calcium silicate, sodium aluminosilicate). Yet other non-limiting examples of substrates include porous silica or silicate (e.g., amorphous silica, calcium silicate, sodium aluminosilicate), porous alumina (e.g., including sodium aluminosilicate), metal-organic framework (MOF), or resin (e.g., as described herein). In some embodiments, the substrate is provided in any form (e.g., precipitated, sol-gel, fumed, calcined, agglomerated, or granulated forms, which in turn can be provided as a powder, a granule, and the like). In some embodiments the substrate is sourced from standard industrial sources or is synthesized. In some embodiments, the substrate is water-stable and / or resistant to corrosion and oxidation.

[0130] The dimension of the substrate can vary based on the application and / or the source. Depending on the shape of the substrate, a dimension of the substrate can include a length, width, height, cross-sectional dimension, circumference, radius (e.g., external or internal radius), diameter, or another metric to indicate a size of the substrate.

[0131] In some embodiments, the substrate comprises a plurality of porous particles, in which the plurality of porous particles is characterized by a certain effective average particle size and / or by a certain distribution of sizes. For example and without limitation, in some embodiments the plurality of porous particles has an effective average particle size in which at least 50% of the porous particles therein are of a specified size. For example and without limitation, in some embodiments the plurality of porous particles exhibits a distribution of sizes that is from about 25 micrometers (pm) to 3 millimeter (mm) or from 25 pm to 4 mm. Thus, in some embodiments where the plurality of porous particles exhibits a distribution of sizes, at least 60 percent, at least 70 percent, at least 80 percent, at least 90 percent, at least 95 percent, at least 99 percent, or all of the porous particles have a sieve diameter that is within the upper and lower bounds of the specified distribution.

[0132] In some embodiments, the plurality of porous particles exhibits a distribution of sieve diameters, with an average sieve diameter that is in a range from 25 pm to 4 mm (e.g., from 45 to 800 pm, 50 to 500 pm, 60 to 300 pm, 45 to 150 pm, 70 to 80 pm, 25 pm to 3 mm, 25 pm to 2 mm, 25 pm to 1 mm, 50 pm to 4 mm, 50 pm to 3 mm, 50 pm to 2 mm, 50 pm to 1 mm, 100 pm to 4 mm, 100 pm to 3 mm, 100 pm to 2 mm, 100 pm to 1 mm, 200 pm to 4 mm, 200 pm to 3 mm, 200 pm to 2 mm, 200 pm to 1 mm, 250 pm to 4 mm, 250 pm to 3 mm, 250 pm to 2 mm, 250 pm to 1 mm, 500 pm to 4 mm, 500 pm to 3 mm, 500 pm to 2 mm, 500 pm to 1.5 mm, 1 to 2 mm, 1 to 2.5 mm, 1 to 3 mm, or 1 to 4 mm). In some implementations, the average sieve diameter of the plurality of porous particles is less than 500 pm (e.g., less than 400 pm, less than 350 pm, less than 300 pm, less than 200 pm, or less than 100 pm). In some embodiments, the substrate (e.g., porous silica particles) has an average sieve diameter of at least 0.5 mm.

[0133] In some embodiments, the sieve diameter of the plurality of porous substrate particles is a measure of central tendency determined over the sieve diameter of the plurality of porous particles. As used herein, the term sieve diameter is the smallest mesh size through which a particle can pass. As used herein, the term “measure of central tendency” refers to a central or representative value for a distribution of values. Non-limiting examples of measures of central tendency include a mean, arithmetic mean, weighted mean, midrange, midhinge, trimean, geometric mean, geometric median, Winsorized mean, median, and mode of the distribution of values. For instance, in some embodiments, the sieve diameter of the plurality of porous particles is an average sieve diameter of the plurality of porous particles used for generating the functionalized crosslinked particles.

[0134] In some embodiments, the plurality of porous particles comprises a distribution of sieve diameters.

[0135] In some embodiments, the sieve diameter, or the measure of central tendency (e.g., mean) thereof, for the plurality of porous particles (substrate) is at least 0.2 millimeters (mm), at least 0.3 mm, at least 0.4 mm, at least 0.5 mm, at least 0.6 mm, at least 0.7 mm, at least 1 mm, at least 1.5 mm, at least 2 mm, at least 2.5 mm, at least 3 mm, at least 3.5 mm, at least 4 mm, or at least 5 mm. In some embodiments, the sieve diameter, or the measure of central tendency (e.g., mean) thereof, of the plurality of porous particles is no more than 10 mm, no more than 5 mm, no more than 4 mm, no more than 3.5 mm, no more than 3 mm, no more than 2.5 mm, no more than 2 mm, no more than 1.5 mm, no more than 1 mm, no more than 0.5 mm, or no more than 0.3 mm. In some embodiments, the sieve diameter, or the measure of central tendency (e.g, mean) thereof, for the plurality of porous particles is from 0.2 mm to 1 mm, from 0.5 mm to 2 mm, from 1 mm to 4 mm, from 0.4 mm to 4 mm, from 3 mm to 5 mm, or from 4 mm to 10 mm. In some embodiments, the sieve diameter, or the measure of central tendency (e.g, mean) thereof, for the plurality of porous particles falls within another range starting no lower than 0.2 mm and ending no higher than 10 mm.

[0136] In some embodiments, the sieve diameter of the porous particles (substrate) varies based on the application and / or the source. In some embodiments, the porous particles (substrate) have an average sieve diameter in the range from 0.25 mm to 4.0 mm (e.g., 0.25 mm to 1.5 mm, 0.5 mm to 1.5 mm, 0.5 mm to 1.0 mm, 1.0 mm to 2.0 mm, 1.5 to 2.0 mm, 0.5 mm to 4.0 mm, 1.0 mm to 4.0 mm, or 2.0 mm to 4.0 mm). In some embodiments, the porous particles have a distribution of sieve diameters having an average (e.g., mean) diameter ranging from 1 mm to 1.2 mm. In some embodiments, the distribution of sieve diameters for the plurality of porous particles comprises sieve diameters of from 0.2 mm to 1 mm, from 0.5 mm to 2 mm, from 1 mm to 4 mm, from 0.4 mm to 4 mm, from 3 mm to 5 mm, from 0.2 mm to 5 mm, from 1 mm to 8 mm, from 0.3 mm to 5 mm, from 0.2 mm to 10 mm, or from 4 mm to 10 mm. In some embodiments, the distribution of sieve diameters for the plurality of porous particles falls within another range starting no lower than 0.2 mm and ending no higher than 10 mm.

[0137] The width of the distribution around the average can affect adsorption performance of the substrate (e.g., plurality of porous particles). In some non-limiting implementations, the width of the distribution is in a range from 5 to 50 pm around the average (e.g., from 10 to 40 pm or 20 to 30 pm). In some examples, the width of the distribution is in a range from 50 pm to 2 mm around the average (e.g., from 75 pm to 1.5 mm, 100 pm to 1.25 mm, 200 pm to 1 mm, 300 to 800 pm, 500 pm to 2 mm, 500 pm to 1.5 mm, 500 pm to 1 mm, 1 to 2 mm, 1.2 to 1.8 mm, 1.4 to 2 mm, or 1.5 to 2 mm).

[0138] In some embodiments, the width of the distribution is alternatively described using D90, D50, and / or Dio values. These values signify a percentage of the total distribution of sizes for material within a sample, up to and including the value. For example, a D90 value of 500 pm indicates that 90% of the material (e.g., the plurality of porous particles) within a sample has a size of 500 pm or smaller. In some embodiments, the functionalized material (e.g., the plurality of functionalized crosslinked particles) has a Dio value of 30 pm or a D-90 value of 150 pm. In some embodiments, the functionalized material has a Dio value of 100 pm or a D90 value of 500 pm, a Dio value of 150 pm or a D90 value of 1000 pm, a Dio value of 400 pm or a D90 value of 1500 pm, a Dio value of 500 pm or a D90 value of 2000 pm, or a Dio value of 1000 pm or a D90 value of 3000 pm. In some embodiments, the functionalized material has aDso value of 1000 pm, 1100 pm, 1200 pm, 1300 pm, 1400 pm, or 1500 pm.

[0139] In general and without wishing to be bound by theory, a smaller particle size with high porosity or high pore volume and BET surface area can facilitate better functionalized material synthesis results, which in turn can enable higher CO2 capture capacity due to relatively higher surface area leading to higher amine coating concentrations. Such types of smaller particles could permit faster adsorption inside of the particle as the gas diffusion path may be shorter. If gas diffusion to the particle surface rate is not limited, then a smaller particle size may be beneficial to gas adsorption. Smaller particle size (e.g., having a small average diameter, radius, or width) could reduce the adsorption process energy cost for a fluidization process.

[0140] Yet other particle effects for smaller particle sizes can include smaller interparticle volume, slower interparticle gas kinetics (e.g., due to longer interparticle diffusion length), faster intraparticle gas kinetics (e.g., due to shorter intraparticle diffusion length), higher packed bed back pressure, higher packing density, and / or higher external surface area. Particle effects for larger particle sizes can include larger interparticle volume, faster interparticle gas kinetics (e.g., due to shorter interparticle diffusion length), slower intraparticle gas kinetics (e.g., due to longer intraparticle diffusion length), lower packed bed back pressure, lower packing density, and / or lower external surface area. A skilled artisan could adapt such sizes and effects to provide a certain adsorbent for particular uses.

[0141] In some embodiments the substrate (e.g., plurality of porous particles) is characterized by the presence of one or more pores. As seen in FIG. 1 A, pores 104 can be considered openings that extend from the exterior surface of the substrate into the interior of the particles. In some embodiments, the presence of such pores increase the surface area of the substrate. Pore dimension varies from pore to pore, and can vary within an individual pore, see, e.g., pores 104A-a, 104A-b. Furthermore, depending on pore shape, a pore dimension can be a length, width, height, cross-sectional dimension, circumference, radius (e.g., external or internal radius), diameter, or another metric to indicate pore size.

[0142] In some embodiments, the pore size of the pores is in a range from 60 angstroms (A) to 700 angstroms (A) (e.g., from 60 to 400 A, 60 to 300 A, 80 to 300 A, 100 to 700 A, 100 to 500 A, 100 to 200 A, 150 to 250 A, 200 to 700 A, 300 to 700 A, 300 to 500 A, or 500 to 700 A). In some embodiments, the pore have an average pore size or a mane pore size that is from about 60 A 100 to about 400 A. In some implementations, the dimension (e.g., a diameter, cross-sectional length, etc.) of the pore(s) is greater than 90 A (e.g., greater than 100 A, 120 A, or 150 A). Without wishing to be limited by theory, a larger diameter of the pore could increase adsorption and desorption rates and could facilitate higher filling of the pores with amine moieties without pore-clogging, which in turn could reduce adsorption and desorption efficiency.

[0143] In some embodiments, the substrate is characterized by a porosity of 1 to 200 nm and / or an average pore size of 30 to 80 nm. In some embodiments, a dimension (e.g., a diameter, a cross-sectional length, etc.) of the pore(s) is in a range from 1 to 200 nm (e.g., 1 to 180 nm, 1 to 160 nm, 1 to 120 nm, 1 to 100 nm, 1 to 70 nm, 1 to 30 nm, 1 to 20 nm, 10 to 200 nm, 10 to 180 nm, 10 to 160 nm, 10 to 120 nm, 10 to 100 nm, 10 to 70 nm, 10 to 50 nm, 30 to 200 nm, 30 to 180 nm, 30 to 160 nm, 30 to 120 nm, 30 to 100 nm, 30 to 90 nm, 30 to 70 nm, 70 to 200 nm, 70 to 180 nm, 70 to 160 nm, or 70 to 120 nm). In some embodiments, an average dimension (e.g., an average diameter) of the pore(s) is in a range from 30 to 80 nm, 20 to 100 nm, or 20 to 70 nm).

[0144] In some embodiments, the substrate (e.g., the plurality of porous particles) is characterized by a plurality of pores of different sizes. For example and without limitation, smaller pores in the range of 1 to 30 nm can contribute to relatively higher surface areas, which can allow for more surface anchoring with amine moieties to improve stability of the coating or surface functionalization layer. Larger pores in the range of 30 to 90 nm can contribute to relatively larger pore volumes that allow for larger volumes of active amine moieties to be contained within the pores to improve the CO2 uptake. The largest pores in the range of 70 to 200 nm can provide open channels that contribute to relatively higher gas diffusion rates for improved CO2 adsorption kinetics. Without wishing to be limited by mechanism, a substrate (e.g., a silica substrate) that possesses significant porosity in these three ranges may be employed as substrates for amine-coated sorbents. In some non-limiting embodiments, a substrate having reduced porosity in one or two of these ranges may suffer from relatively decreased performance in the corresponding function but may still function as substrates for amine-coated sorbents.

[0145] In some embodiments, a substrate (e.g., plurality of porous particles) is characterized by a plurality of pores, where each pore is characterized by a pore dimension, where at least one pore dimension is in a first range of about 1 to 30 nm, a second range of about 30 to 90 nm, and / or a third range of about 70 to 200 nm. Such ranges can be any other ranges of pore dimensions described herein.

[0146] Pores can have any useful shape (e.g., cylindrical, spherical, tubular, and the like), configuration, distribution, and arrangement (e.g., hexagonal, cubic, and the like). In some embodiments, the pores have an irregularly round cross-sectional shape, or a hexagonal cross-sectional shape, though this is not limiting. Pores may also be characterized by pore size distributions, which can be determined in any useful manner (e.g., using mercury, nitrogen, argon, helium, etc. in porosimetry or using Brunauer-Emmett-Teller (BET) analysis with appropriate methods such as the Barrett Joyner Halenda (BJH) or Non-Local Density Functional Theory (NLDFT) models).

[0147] Pore size distribution profiles can include those for non-limiting sorbents with only narrow pores having high surface areas but relatively lower pore volumes and gas kinetics, non-limiting sorbents with only moderately sized pores having high pore volumes and moderate surface areas and gas kinetics, non-limiting sorbents with only large pores having fast gas kinetics and high pore volumes but relatively lower surface areas, and non-limiting sorbents with pores in a plurality of ranges having high surface areas, pore volumes, and channels for gas diffusion allowing for stable surface coating, relatively higher concentrations of active amines, and fast gas kinetics.

[0148] The pores can have any useful configuration. In some embodiments, pores may be provided on a surface of the substrate. Such pores may or may not be interconnected. For example and without limitation, pores could extend into the central volume of the substrate and form interconnected channels. Without wishing to be limited by theory, the pores can create a volume within the substrate in which gases may flow for enhanced capture of such gases. Furthermore, such pores may create additional (e.g., and accessible) surface area for functionalization.

[0149] In some embodiments, pores are characterized by pore volume, total surface area, accessible surface area, porosity, and the like. In some embodiments, the volume of the pores is greater than 0.1 mL / g, (e.g., greater than 0.5 mL / g, greater than 0.8 mL / g, greater than 1 mL / g, greater than 1.2 mL / g, greater than 1.5 mL / g, or greater than 1.8 mL / g). In some embodiments, the volume of the pores is from 0.1 to 5 mL / g (e.g., from 0.1 to 4.5 mL / g, 0.1 to 4 mL / g, 0.1 to 3 mL / g, 0.1 to 3.5 mL / g, 0.1 to 3 mL / g, 0.1 to 2.5 mL / g, 0.1 to 2 mL / g, 0.1 to 1.5 mL / g, 0.1 to 1.2 mL / g, 0.1 to 1 mL / g, 0.5 to 5 mL / g, 0.5 to 4.5 mL / g, 0.5 to 4 mL / g, 0.5 to 3.5 mL / g, 0.5 to 3 mL / g, 0.5 to 2.5 mL / g, 0.5 to 2 mL / g, 0.5 to 1.5 mL / g, 0.5 to 1 mL / g, 1 to 5 mL / g, 1 to 4.5 mL / g, 1 to 4 mL / g, 1 to 3.5 mL / g, 1 to 3 mL / g, 1 to 2.5 mL / g, 1 to 2 mL / g, 1.5 to 5 mL / g, 1.5 to 4.5 mL / g, 2.5 to 5 mL / g, 2.5 to 4.5 mL / g, 3.5 to 5 mL / g, 3.5 to 4.5 mL / g, 1.5 to 3.5 mL / g, 1 to 3 mL / g, 1 to 1.5 mL / g, 1 to 1.2 mL / g, or 1.5 to 2.5 mL / g). Without wishing to be limited theory, increased total volume of the pores could allow more amine moieties to be grafted or into the pores and, thus increase the adsorption potential of the functionalized material.

[0150] Total surface area can be used to characterize the substrate. The total surface area of the substrate includes the surface area of not only the outer surface but also the surface area within the pores. In some embodiments, the total surface area is greater than 100 m2 per dry gram (m2 / g) of substrate. In some implementations, the total surface area is greater than 300 m2 / g (e.g., greater than 200 m2 / g, 400 m2 / g, 500 m2 / g, or 800 m2 / g). In some implementations, the total surface area is greater than 1200 m2 / g (e.g., greater than 200 m2 / g, 400 m2 / g, 500 m2 / g, or 800 m2 / g). In some implementations, the total surface area is greater than 2000 m2 / g (e.g., greater than 2500 m2 / g, 3000 m2 / g, 4000 m2 / g, 5000 m2 / g, or 6000 m2 / g). In some examples, the total surface area is in a range from 100 to 1200 m2 / g (e.g., from 200 to 1200 m2 / g, 400 to 1200 m2 / g, 500 to 1200 m2 / g, 700 to 1200 m2 / g, 800 to 1200 m2 / g, 1000 to 1200 m2 / g, 100 to 1000 m2 / g, 100 to 800 m2 / g, 100 to 500 m2 / g, 100 to 400 m2 / g, 100 to 900 m2 / g, 200 to 900 m2 / g, 400 to 900 m2 / g, 500 to 1000 m2 / g, or 500 to 800 m2 / g). In some examples, the total surface area is in a range from 1000 to 12000 m2 / g (e.g., from 1000 to 11000 m2 / g, 1000 to 10000 m2 / g, 1000 to 9000 m2 / g, 1000 to 8000 m2 / g, 1000 to 7000 m2 / g, 1000 to 6000 m2 / g, 1000 to 5000 m2 / g, 1000 to 4000 m2 / g, 2000 to 12000 m2 / g, 2000 to 11000 m2 / g, 2000 to 10000 m2 / g, 2000 to 9000 m2 / g, 2000 to 8000 m2 / g, 2000 to 7000 m2 / g, 2000 to 6000 m2 / g, 2000 to 5000 m2 / g, 2000 to 4000 m2 / g, 3000 to 12000 m2 / g, 3000 to 11000 m2 / g, 3000 to 10000 m2 / g, 3000 to 9000 m2 / g, 3000 to 8000 m2 / g, 3000 to 7000 m2 / g, 3000 to 6000 m2 / g, 3000 to 5000 m2 / g, 3000 to 4000 m2 / g, 4000 to 12000 m2 / g, 4000 to 11000 m2 / g, 4000 to 10000 m2 / g, 4000 to 9000 m2 / g, 4000 to 8000 m2 / g, 4000 to 7000 m2 / g, 4000 to 6000 m2 / g, or 4000 to 5000 m2 / g). In some examples, the total surface area is in a range from 100 to 12000 m2 / g (e.g., including ranges therebetween, such as any described herein).

[0151] Without wishing to be limited by theory, higher total surface area could increase the available area for functionalization (e.g., by way of interactions between a silane moiety and a surface of the substrate) and / or increase the adsorption potential of the functionalized material. Surface area can be determined in any useful manner, e.g, by using the BET model or other methodologies described herein.

[0152] Any useful combination of features may be present in a substrate. In some embodiments, the substrate comprises a greatest dimension (e.g., an average greatest dimension) of at least 70 pm and a plurality of pores, where the plurality of pores is characterized by a volume that is greater than 0.8 mL / g and by a size (e.g., an average size) of at least 90 A. In some embodiments, the substrate comprises a greatest dimension (e.g., an average greatest dimension) in a range from 0.5 to 2 mm and a plurality of pores, where the plurality of pores is characterized by a volume greater than 0.5 ml / g and a size in a range from 20 to 1000 A. Other combinations of features are possible.

[0153] a. Silica

[0154] In some embodiments, the substrate comprises silica (e.g., silicon dioxide). Any methods or compounds herein can be used to functionalize a silica substrate to provide a functionalized silica. For example and without limitation, in some embodiments the functionalized silica has amine moi eties that are bound to the silica surface (e.g., by way of siloxane bonds, other covalent bonds, or even non-covalent bonds).

[0155] In some embodiments the silica is in any useful form, such as beads (e.g., microbeads, nanobeads, or combinations thereof), powders (e.g., micropowders, nanopowders, or combinations thereof; or from micrometer size to millimeter size), particles (e.g., microparticles, nanoparticles, or combinations thereof), and the like. Furthermore, in some embodiments the silica includes any useful type, such as amorphous or non-crystalline silica (e.g., precipitated, sol-gel, fumed, calcined, agglomerated, or other forms of silica) or silicates (e.g., calcium silicate, sodium aluminosilicate, and the like). In some embodiments, the silica includes one or more pores (e.g., as in porous silica). Furthermore, within such a substrate, pores can have any useful shape, configuration, distribution, and arrangement (e.g., hexagonal arrangement of pores in MCM-41, which in turn can be spherical or any other shape). In some embodiments, the substrate can be bead-shaped, though this is not limiting. Silica can be obtained or provided in any useful manner, such as by employing synthetic methods or by sourcing from standard industrial sources.

[0156] In some non-limiting embodiments, the substrate 102A, 102B, 102C is a silica substrate. In some non-limiting embodiments, the substrate 102A, 102B, 102C is composed of amorphous silica, e.g., non-crystalline silica.

[0157] b. Metal-organic framework (MOF)

[0158] Metal organic frameworks (MOFs) are a class of compounds including metal ions or clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures (e.g., porous three-dimensional structures). Various kinds of MOF are synthesized with different combinations of metal ions and organic ligands (e.g., as described herein) and all such MOFs are within the scope of the present disclosure. In some embodiments, MOF substrates are used as a porous structure for functionalization to achieve carbon capture.

[0159] In some embodiments, the substrate comprises a MOF. Any methods or compounds herein are used to functionalize a MOF substrate to provide a functionalized MOF. Without wishing to be limited by theory, a functionalized MOF features surface areas larger than alternative substrates (e.g., zeolite, silica, etc.) for increased functionalization (e.g., > 2000 m2 / g). For example and without limitation, in some embodiments a functionalized MOF features amine moieties that are bound to hydroxy functional side groups present on the surface, thereby allowing for CO2 uptake. The amine moiety is provided by any compound described herein (e.g., an aminosilane compound) for increased carbon capture (e.g., > 2 mol CO2 / kg).

[0160] In some embodiments MOFs are provided in any useful manner. In some embodiments, MOFs are produced using reactor-based, solvothermal (e.g., hydrothermal) synthesis methods in which a metal source (e.g., a metallic substrate or a metal-containing salt), an organic ligand, and an optional competing agent / additive are reacted together to produce MOF crystals of 10 pm to 1 mm in size (e.g., in diameter), including ranges therebetween (e.g., from 10 to 500 pm, 10 to 300 pm, 50 to 300 pm, or 50 to 100 pm in size). In some embodiments, the crystals are extruded, pelletized, and functionalized with adsorbing moieties to provide a functional group disposed on a surface of the MOF, thereby providing a functionalized MOF.

[0161] In some embodiments, MOFs are synthesized by providing a metal source and an organic ligand. Under certain conditions, metal-containing centers form nodes, and organic ligands form bridges between the nodes to provide self-assembled, networked structures. By selecting certain metals and ligands with certain reaction conditions, various structural characteristics (e.g., topology, pore structure, pore size, and the like) of the MOF material are controlled in some embodiments.

[0162] Any useful metal source can be employed. Non-limiting examples include metal sources comprising aluminum (Al), chromium (Cr), copper (Cu), iron (Fe), titanium (Ti), vanadium (V), zinc (Zn), zirconium (Zr), as well as salts thereof (e.g., halide salts, nitrate salts, or others described herein), combinations thereof, and mixtures thereof. In some embodiments, the metal source is an aluminum-based metal source, an iron-based metal source, a titanium-based metal source, a zinc-based metal source, or a zirconium-based metal source. In some embodiments, the metal ions selected for the MOF substrate include an economical, commercially available, cost-effective metal ion source, such as aluminum (Al), iron (Fe), titanium (Ti), zinc (Zn) (e.g., zinc nitrate (ZnNOs)), zirconium (Zr) (e.g., zirconium tetrachloride (ZrCh)).

[0163] Any useful organic ligand is employed in some embodiments. Non-limiting ligands include, e.g., 3,3’,5,5’-azobenzenetetracarboxylate (ABTC4 ); 1,4-benzenedicarboxylate (BDC2 ); (X)-BDC2 or (X)2-BDC2 , where each X is, independently, alkyl, halo, hydroxy, nitro, amino, carboxyl, alkoxy, cycloalkoxy, aryloxy, or benzyloxy (e.g., 2-amino-1,4-benzenedicarboxylate (NH2-BDC2 ), 2-hydroxy-1,4-benzenedicarboxylate (OH-BDC2 ), 2,5-diamino-l,4-benzenedicarboxylate ((NH2)2-BDC2 ), 2,5-dihydroxy-1,4-benzenedicarboxylate ((OH)2-BDC2 or DHBDC2 ), 2,3-dihydroxy-l,4-benzenedicarboxylate, or 2,6-dihydroxy-1,4-benzenedicarboxylate); l,l’-biphenyl-4,4’-dicarboxylate (BPDC2 ); (X)-BPDC2 or (X)2-BPDC2 , where each X is, independently, alkyl, halo, hydroxy, nitro, amino, carboxyl, alkoxy, cycloalkoxy, aryloxy, or benzyloxy (e.g., 2-amino-1,1’-biphenyl-4,4’-dicarboxylate (NH2-BPDC2 ), 2-hydroxy-1,1’-biphenyl-4,4’-dicarboxylate (OH-BPDC2 ), 2,2’-diamino-1,1’-biphenyl-4,4’-dicarboxylate ((NH2)2-BPDC2 ), or 2,2’-dihydroxy-1,1’-biphenyl-4,4’-dicarboxylate ((OH)2-BPDC2 )); 1,3,5-benzenetri carb oxy late or 1,2,4-benzenetricarboxylate (BTC’3 ); 2,5-dihydroxy-l,4-benzenedicarboxylate (DHBDC2 ); 2,5-dioxido-1,4-benzenedicarboxylate (DOBDC4 ); 4,4’,4”-s-triazine-2,4,6-triyl-tribenzoate (TATB3 ); l,3,6,8-tetrakis(p-benzoate)pyrene (TBAPy4 ); l,l’-triphenyl-4,4’-dicarboxylate (TPDC2 ); and (X)2-TPDC2 or (X)4-TPDC2-, where each X is, independently, alkyl, halo, hydroxy, nitro, amino, carboxyl, alkoxy, cycloalkoxy, aryloxy, or benzyloxy (e.g., 2,2’-dihydroxy-l,r-triphenyl-4,4’-dicarboxylate (di-OH-TPDC) or 2,2’,6,6’-tetrahydroxy-l,r-triphenyl-4,4’-dicarboxylate (tetra-OH-TPDC)). In some embodiments, such ligands are provided as a compound in its protonated form to the metal source. In some embodiments, the ligand optionally includes one or more counterions (e.g., one or more counteranions or countercations), as well as a cation thereof, an anion thereof, a protonated form thereof, a salt thereof, or an ester thereof.

[0164] In some embodiments, the ligand includes hydroxy functional side groups. Without wishing to be limited by theory or mechanism, the presence of hydroxy functional side groups may facilitate post-synthetic functionalization of the MOF surface with adsorbing moi eties (e.g., amine moi eties).

[0165] In some embodiments, the hydroxy reacts with a silane moiety of an aminosilane compound to covalently bond the silane moiety to the hydroxy group of the organic ligand, while increasing the density of amine moieties on a surface of the MOF substrate, thereby increasing the CO2 capture capacity of the MOF substrate. Non-limiting examples of aminosilanes suitable for bonding with the MOF substrate for carbon capture include methoxysilanes, chlorosilanes, ethoxysilanes, as well as others described herein.

[0166] In some embodiments, the organic ligand is provided by a compound that is l,4-di-(4-carboxy-2,6-dihydroxyphenyl)benzene. Within the MOF, this compound provide sa 2,2’,6,6’-tetrahydroxy-l,r-triphenyl-4,4’-dicarboxylate (tetra-OH-TPDC) ligand. In some embodiments, this compound is employed with a metal source that includes Zn(NO3)2 6H2O.

[0167] In some embodiments, the organic ligand is 2-hydroxyterephthalic acid (e.g., to provide a 2-hydroxy-BDC ligand), 2,5-dihydroxyterephthalic acid (e.g., to provide a 2,5-dihydroxy-BDC ligand), 2,3-dihydroxyterephthalic acid (e.g., to provide a 2,3-dihydroxy-BDC ligand), 2,6-dihydroxyterephthalic acid (e.g., to provide a 2,6-dihydroxy-BDC ligand), or 2-boronobenzene-l,4-dicarboxylic acid (e.g., to provide a 2-borono-BDC ligand).

[0168] Any useful MOF can be employed. Non-limiting examples of MOF include, e.g., HCC-1 [Zn4O(di-OH-TPDC)3]; HCC-2 [Zn4O(tetra-OH-TPDC)3], HKUST-1 [Cu3(BTC)2 or Cu3(BTC)3(H2O)3], IRMOF-1 orMOF-5 [Zn4O(BDC)3], IRMOF-3 [Zn4O(NH2-BDC)3], IRMOF-10 [Zn4O(BPDC)3], IRMOF-16 [Zn4O(TPDC)3], MIL-47 [VO(BDC)], MIL-101-Cr [Cr3O(BDC)3(H2O)2F or Cr3O(BDC)3(H2O)3], MIL-101-Fe [Fe3O(BDC)3(H2O)2X or Fe3O(BDC)3X, where X is a monoanion, such as OH' or Cl’], NH2-MIL-101-Fe [Fe3O(NH2-BDC)3(H2O)2X or Fe3O(NH2-BDC)3X, where X is a monoanion, such as OH' or Cl ], NH2-MIL- 101-Al [A13O(NH2-BDC)6X3 or A13O(NH2-BDC)3(H2O)2X, where X is a monoanion, such as OH' or Ch], MIL-125 [Ti8O8(OH)4 (BDC)6], NH2-MIL-125 [Ti8O8(OH)4(NH2-BDC)6], MOF-2 [Zn2(BDC)2], MOF-74 [Zn2(DHBDC)], MOF-808 [Zr6O4(n3-OH)4(OH)6(H2O)6(BTC)2],NU-1000 [Zr6(n3-O)4(n3-OH)4(OH)4(H2O)4(TBAPy)2], PCN-250 [Fe3O(ABTC)6 or (Fe3O)2(ABTC)3 or (Fe3O)2(ABTC)3—(OH)2(H2O)4], PCN-777 [Zr6O4(p3-OH)4(TATB)2(OH)6(H2O)6 or Zr3O4(OH)(TATB)(H2O)6], UiO-66 [Zr6(O)4(OH)4(BDC)i2], UiO-66 [Zr6O4(OH)4(BDC)6], UiO-66-DOBDC [Zr6O4(OH)4(DOBC)6], UiO-66-NH2 [Zr6O4(OH)4(NH2-BDC)6], UiO-66-OH [Zr6O4(OH)4(OH-BDC)6], orUiO-67 [Zr6O4(OH)4(BPDC)6]. In some embodiments, any of these is modified to include one or more hydroxy groups or additional hydroxy groups (e.g., if a hydroxy group is already present). In some embodiments, the hydroxy group is provided on the organic ligand.

[0169] In some embodiments, MOFs are provided in any useful form, e.g., particles, crystals, powders, and the like. In some embodiments, the MOF particles include MIL-101-Fe, MIL-101-A1, MIL-125-Ti, PCN-250, UiO-66, UiO-67, or any combination or mixture thereof. In some embodiments, the MOF particles are water-stable.

[0170] In some embodiments MOF substrates are processed under a variety of synthetic conditions to yield different pore sizes and porosities. In some embodiments, the MOF substrate is a mesoporous or a macroporous MOF material. In general and without wishing to be bound by theory, higher pore opening size facilitate increased surface area, increasing the number of exposed active sites on which post-synthetic modification can occur. Increased exposed active sites facilitates higher concentrations of the adsorbing moiety on the MOF substrate, which in turn enables higher CO2 capture capacity in some embodiments.

[0171] In some embodiments, the MOF substrate includes pores, which are openings that extend into the interior volume of the MOF substrate. The pores increase the surface area of the MOF substrate. The dimensions of the pores vary, and can vary within an individual pore. Mesoporous and macroporous MOF materials allow for a large volume of adsorbing moieties (e.g., amines moieties) to be incorporated into the porous matrix. In some embodiments, a mesoporous material includes pores having a greatest opening dimension (e.g., a diameter) in a range from 2 nanometers (nm) and 50 nm, and a macroporous material includes pores having a greatest opening dimension greater than 50 nm. In some embodiments, for a MOF substrate, pore dimension, pore volume, and / or total surface area are any described herein (e.g., a pore dimension from a range from 30 to 400 A or greater than 90 A; a pore volume from 0.5 to 5 mL / g; and / or a total surface area greater than 100 m2 / g).

[0172] In some embodiments the MOF substrate is functionalized to provide a functional portion having an adsorbing moiety. In some embodiments, the adsorbing moiety is an amine moiety (e.g., a primary, secondary, or tertiary amine group, as described herein). In some embodiments, the amine moieties bind to the surface of the MOF from which the hydroxy functional side groups extend. In this example, the interaction moiety includes any that reacts with hydroxy groups present on the surface of the MOF. Non-limiting interaction moieties can be, e.g., a silane moiety (e.g., any described herein). By forming interactions between the interaction moiety and the surface, amine bonding stability and / or lifetime of the sorbent is improved in some embodiments. The functionalization methods herein can be applicable to all form factors of the MOF substrates.

[0173] In some embodiments, an aminosilane is on the MOF surface. In some embodiments, this aminosilane includes a silane moiety (e.g., a trimethoxysilane moiety, a triethoxysilane moiety, a dimethoxyethoxysilane moiety, a diethoxymethoxysilane moiety, and the like) and an amine moiety. In some embodiments, the aminosilane includes one, two, or three amine moieties (e.g., any described herein for RA). In some embodiments, the aminosilane has a structure having formula [RA]sSiX, where each RA is, independently, an amine moiety comprising at least one amine group (e.g., any described herein) and X is a side group, a reactive group, or a leaving group (e.g., any described herein). In some embodiments, the aminosilane includes a structure having formula [RN1RN2N]sSiX, where each of RN1 and RN2 is, independently, any described herein (e.g., optionally substituted aliphatic, alkyl, aromatic, or aryl); and X is a side group, a reactive group, or a leaving group (e.g., any described herein, such as halo, hydroxy, and the like). In some embodiments, the aminosilane is or includes tris(ethylmethylamino)chlorosilane. Other examples of aminosilanes include any described herein (e.g., an aminosilane including a structure having formula I).

[0174] In some embodiments, the aminosilane is on the surface of the MOF, where the aminosilane interacts with a hydroxy group present on an organic ligand within the MOF. In some embodiments, the organic ligand interacts with (e.g., binds to) the metal center within the MOF, and the hydroxy group is unbound from the metal center. In particular embodiments, the silane moiety of the aminosilane interacts with (e.g., binds to or / reacts with) the hydroxy group present on the organic ligand.

[0175] In some non-limiting embodiments, the substrate 102A, 102B, 102C is a MOF substrate, and the pores 104A-a,b, 104B-a,b, 104C-a,b, represent pores provide by the MOF structure. In some non-limiting embodiments, the substrate 102A, 102B, 102C is composed of crystalline, nanoporous MOF.

[0176] c. Resin

[0177] Ion-exchange resins generally possess a porous structure that can provide a large surface area for the exchange of ionic compounds. In some embodiments, to provide a functionalized resin, functional portion-containing compounds are adsorbed within the pores and interact with reactive moieties present within such pores. Such interactions include ionic bonding interactions, hydrogen bonding interactions, and / or van der Waals force interactions, and the like. In some embodiments, this process is conducted with multiple types of ion-exchange resin having various types of reactive sites, such as polystyrene sulfonate (e.g., in which the sulfonic acid in the ion-exchange resin includes an acidic reactive site that forms ionic bonds with various amines through ionic bonding). In some embodiments, resin substrates are used as a porous structure for functionalization to achieve carbon capture. In particular embodiments, reactive sites present in the resin are employed during functionalization.

[0178] In some embodiments, the substrate comprises a resin (e.g., an ion-exchange resin). Any methods or compounds herein are used to functionalize a resin substrate to provide a functionalized resin. For example and without limitation, in some embodiments a functionalized resin features amine moieties that are bound to acidic reactive sites present on the surface, thereby allowing for CO2 uptake. In some embodiments the amine moiety is provided by any compound described herein (e.g., a polyamine) for increased carbon capture (e.g., > 1 mol CO2 / kg or from 1 to 3 mol CO2 / kg).

[0179] In some embodiments, the substrate comprises an ion-exchange resin (e.g., ion-exchange resin particles). In some embodiments, the ion-exchange resin is sufficiently cross-linked to retain porosity sufficient to facilitate gas diffusion and adsorption when dry.

[0180] In general, a resin substrate is a portion of an ion-exchange resin that is sourced from standard industrial sources. Non-limiting types of ion-exchange resins include a “weak base” functionalized resin, an “acid” functionalized resin such as those with carboxylic or sulfonic acid groups, and a neutral resin with no chemical functionalization.

[0181] In these types, different molecular interactions are used to retain the introduced amine moieties. In weak base resins, amine moieties are present in the resin and serve as reactive sites. In turn, these reactive sites interact (e.g., by way of hydrogen bonding) with adsorbing moieties that are introduced during functionalization (e.g., by introducing a polyamine, a monoamine, an aminosilane, and the like). In acidic resins, acidic moieties are present as reactive sites in the resin. In some embodiments, introduction of an amine (e.g., a polyamine, a monoamine, an aminosilane, etc.) to this resin results in acid-base reactions, which can form ionic bonds between the reactive sites and the amine. In neutral resins, van der Waals forces and entrapment of larger amines within resin pores are the primary interactions. Without wishing to be limited by theory, in some embodiments ionic bonding interactions with an acidic resin provides the highest bonding strength, relative to the other bonding modes; hydrogen bonding with a weak base rein has less strength than the ionic bonding; and van der Waals forces with neutral resins have the lowest bonding strength, relative to the other two bonding modes.

[0182] Ion-exchange resins are a class of porous polymers that includes polystyrene (e.g., optionally crosslinked with divinylbenzene), polyacrylate, polymethacrylate (e.g., optionally crosslinked with divinylbenzene), polyphenols / phenol-aldehyde resins (e.g., phenol-formaldehyde), melamine resins, agarose, cellulose, polyacrylamides, poly carbohydrates (e.g., dextrans), polyolefins, or similar resins and thermosets, as well as crosslinked forms of any of these or copolymers of any of these.

[0183] In some embodiments, resins include ionizable, chelating, ionic, acidic, or basic functional groups, which can interact with ions. In some embodiments, these functional groups include, but are not limited to, carboxylic acids, phosphonic acids, sulfonic acids, sulfoalkyl acids, thiols, iminodiacetic acid, thiourea, aminophosphonic acids, pyridines, phenols, picolylamines, primary amines, secondary amines, tertiary amines, quaternary amines, and alcohol amines.

[0184] Any useful resin is employed in some embodiments. Non-limiting examples of resin include a base-functionalized resin, an acid-functionalized resin, or a neutral resin including no chemical functionalization. In some embodiments, the acid-functionalized resin include carboxylic and / or sulfonic acid groups. In some embodiments, the resin is a porous polystyrene, polyacrylamide, or phenol-formaldehyde resin that retains its porosity when dry combined with a molecular alkyl amine. Non-limiting examples of porous ion-exchange resins include, but are not limited to, PUROLITE® Al 10 (polystyrenic macroporous, weak base anion resin, free base form, having a primary amine as a functional group), PUROLITE® Al05 (polystyrenic macroporous, weak base anion resin, free base form, having a tertiary amine as a functional group), PUROLITE® C145H (polystyrenic macroporous, strong acid cation resin, hydrogen form, having sulfonic acid as a functional group), PUROLITE® C160H (polystyrenic macroporous, strong acid cation resin, hydrogen form, having sulfonic acid as a functional group), PUROLITE® MACRONET™ MN502 (hyper-crosslinked polystyrenic macroporous, adsorbent resin, strong acid functionality, hydrogen form, having sulfonic acid as a functional group), PUROLITE® C104Plus (polyacrylic porous, weak acid cation resin, hydrogen form, having carboxylic acid as a functional group), PUROSORB™ PAD900 (polydivinylbenzene macroporous, adsorbent resin, non-ionic form), AMBERLITE® IRA-402 (strongly basic anion exchanger, Cl’ form, having quaternary ammonium as a functional group), or DOWEX® 50W-X8 (strongly acidic cation exchanger, H+ form, having sulfonic acid as a functional group). Resins can be provided in any useful form, e.g, beads, granules, powders, membranes, fibers, particles, crystals, and the like.

[0185] In some embodiments, resins are sufficiently porous to facilitate diffusion of gaseous ions into and out of the polymeric matrices. Some resins are highly crosslinked and rigid and retain porosity in a dry state (e.g., a hydration of < 15% (wt / wt) of water). The term “(wt / wt)” is in reference to a ratio of the weight (wt) of a first component to the weight of a second component. For example, 1 gram of a first substance and 10 grams of a second substance defines a 10% (wt / wt) ratio of the first substance to the second substance.

[0186] In some embodiments, the resin substrate is porous in the dry state. Without wishing to be limited by mechanism, such substrates can facilitate diffusion of gas containing CO2 into the polymeric matrix for CO2 capture. Ion-exchange resins can be polymerized under a variety of synthetic conditions to yield different pore sizes and porosities. Larger meso- and macro-pores can allow for a large volume of adsorbing groups to be incorporated into the porous matrices. In some embodiments, a mesoporous resin includes pores having a greatest opening dimension (e.g., diameter) in a range from 2 to 50 nm; and a macroporous resin includes pores having a greatest opening dimension greater than 50 nm.

[0187] In general and without wishing to be bound by theory, proper pore size (e.g, as in a sorbent with pores in any range herein) can be characterized by high surface areas, pore volumes, and channels for gas diffusion that allows for a stable coating or surface functionalization layer, relatively higher concentrations of adsorbing moieties (e.g, active amines), and / or fast gas kinetics. This, in turn, could enable higher CO2 capture capacity. In some embodiments, higher porosity can reduce the adsorption process energy cost for a fluidization process.

[0188] In some embodiments, the resin substrate includes pores, which are openings that extend into the interior volume of the resin substrate. In some embodiments, the pores increase the surface area of the resin substrate. For a resin substrate, pore dimension, pore volume, and / or total surface area is any described herein (e.g., a pore dimension greater than 90 A or in a range from 60 to 400 A or 1 to 200 nm; an average pore size in a range from 30 to 80 nm; a pore volume greater than 0.5 mL / g or in a range from 0.1 to 5 mL / g, 0.1 to 4 mL / g, or 0.1 to 1.5 mL / g; and / or a total surface area greater than 100 m2 / g, greater than 1200 m2 / g, or in a range from a range from 100 to 1200 m2 / g).

[0189] In some embodiments, the resin substrate is functionalized to provide a functional portion having an adsorbing moiety. In some embodiments, the adsorbing moiety is an amine moiety (e.g., a primary, secondary, or tertiary amine group, as described herein). In some embodiments, the amine moieties bind to the reactive sites of the resin. In some embodiments, the interaction moiety includes any that reacts with reactive sites present on the surface of the resin. Non-limiting interaction moieties are, e.g., an amine moiety (e.g., any described herein). In some embodiments, the resin includes a first amine moiety, and the reaction introduces a second amine moiety bonded to the first. By forming interactions between the interaction moiety and the surface, amine bonding stability and / or lifetime of the sorbent is improved in some embodiments. The functionalization methods herein can be applicable to all form factors of the ion-exchange resins.

[0190] ii. Functional portion

[0191] In some embodiments, the functional portion includes any combination of moieties, groups, or compounds to facilitate adsorption of desired gases by the sorbent. In some embodiments, the functional portion includes an adsorbing moiety and an interaction moiety. Whereas the adsorbing moiety is configured to adsorb a desired gas, the interaction moiety is configured to attach (directly or indirectly) the adsorbing moiety to the substrate surface. Optionally, the interaction moiety is further configured to stabilize the functional portion, such as by forming bonds with the adsorbing moiety and / or the substrate surface. In another optional embodiment, the interaction moiety further provides an additional adsorbing moiety to enhance adsorption of the sorbent. In some embodiments, the functional portion includes any useful combination of one or more adsorbing moieties (e.g., one or more amine moieties) with one or more interaction moieties (e.g., one or more silane moieties). In some embodiments, when a plurality of amine moieties is present (e.g., when a first amine moiety and a second amine moiety are present), such moieties react with or bind to carbon dioxide.

[0192] As seen in FIGS. 1A-1C, in some embodiments the surface 103A-C of the substrate 102A-C is functionalized to provide a functional portion 106A-C. In some embodiments (e.g., as in FIG. 1A), the functional portion 106A includes an interaction moiety 108A bonded to an adsorbing moiety 110A. In some embodiments (e.g., as in FIG. IC), the functional portion 106B includes an interaction moiety 108B bonded to a first adsorbing moiety HOB and includes a second adsorbing moiety 112B associated with the interaction moiety 108B and / or the first adsorbing moiety HOB. In some embodiments (e.g., as in FIG. IC), the functional portion 106C includes an adsorbing moiety.

[0193] In some embodiments, the functional portion includes an adsorbing moiety. In some embodiments, the adsorbing moiety includes one, two, three, or more amine moieties (e.g., any described herein). In some embodiments, the amine moiety includes one or more of the following: a primary amine (e.g., -NH2), a secondary amine (e.g., -NHRn1, in which RN1 can be any described herein that is not hydrogen), a tertiary amine (e.g., -NRN1RN2, in which each of RN1 and RN2 can be any described herein that is not hydrogen), an aminoalkyl group (e.g., -Ak-NRN1RN2), a terminal amine group (e.g., - NRN1RN2), an internal amine group (e.g., -NRN3-, such as -NH-), a linked group (e.g., - N(-L1-NRn1RN2)-; -N(-L2-NRN3-Lj-NRn1RN2)-; -N[-L2-N(-L1-NRn1RN2)2]-; -L1-NRn1 RN2; .nrns.li.^ni^.                 -NR^-P-NR^-lA-NR^n2; or -L3-NRN4'L2'NRN3-L1-NRn1RN2), an aminoalkylamino group (e.g., -NRN3-Ak-NRN1RN2), an aminoalkylaminoalkyl group (e.g., -Ak-NRN3-Ak-NRN1RN2 or -Ak-N(-Ak-NRN1RN2)2), a linked group including amino and silane groups (e.g., -Ll-SiRslRS2-NRxlRX2, -L2-SiR^R^-LkNR^^, and -L3-SiRslRS2-L2-NRN3-L1-NRN1RN2), a nitrogen-containing heterocyclyl (e.g., optionally substituted piperazinyl, such as unsubstituted piperazinyl or piperazinyl substituted with optionally substituted alkyl, aminoalkyl, hydroxyalkyl, amino, etc.), and the like.

[0194] In other embodiments, the adsorbing moiety includes one or more RA moieties described herein. In some embodiments, RA is or includes -NH-, -NRn1-, -N(-L'-NRxi RX2)-, -N(-L2-NRN3-L1-NRn1RN2)-, -N[-L2-N(-L1-NRn1RN2)2]-, -nh2, -NRn1RN2, -L'-NRXIRX2, -N RN3-L1-NRn1RN2, -L2-NRN3-L1-NRn1RN2, or -NRN4-L2-NRN3-Lj-NRn1RN2.

[0195] The amine moiety includes any combination of linkers and RA moieties. In some implementations, the amine moiety includes one or more of the following: -L^tR^-L^ni-R^; -NRN1-[L1-NRN2]ni-L2-NRN3RN4; -NH-[L-NH]n-H; -N[L-NH2] 2; - NH[CH2CH2NH]nH; -[CH2CH2NH]nRN1; -[CH2CH2NH]n-; -[CH2CH2NRA]nRN1; -[CH2C H2NRA]n-; and the like.

[0196] In some non-limiting embodiments for any amine moiety herein, each of RA, RA1, or Ra2 is or includes any described herein for RA; each of RN1 and RN2 is any described herein; each of RN3, RN4, and RN5 is any described herein for RN1 and RN2; each of RS1 and RS2 can be any described herein; each of L, L1, L2, or L3 is independently a linker; each Ak is independently optionally substituted alkylene; and each of n and nl is independently an integer (e.g., an integer of 1 or more, such as from 1-25000, 1-24000, 1-23000, 1-22000, 1-21000, 1-20000, 1-19000, 1-18000, 1-17000, 1-16000, 1-15000, 1-14000, 1-13000, 1-12000, 1-11000, 1-10000, 1-7500, 1-5000, 1-4000, 1-3000, 1-2000, 1-1000, 1-500, 1-100, 1-50, 1-20, 1-10, 1-5, 2-25000, 2-24000, 2-23000, 2-22000, 2-21000, 2-20000, 2-19000, 2-18000, 2-17000, 2-16000, 2-15000, 2-14000, 2-13000, 2-12000, 2-11000, 2-10000, 2-7500, 2-5000, 2-4000, 2-3000, 2-2000, 2-1000, 2-500, 2-100, 2-50, 2-20, 2-10, 2-5, 5-25000, 5-24000, 5-23000, 5-22000, 5-21000, 5-20000, 5-19000, 5-18000, 5-17000, 5-16000, 5-15000, 5-14000, 5-13000, 5-12000, 5-11000, 5-10000, 5-7500, 5-5000, 5-4000, 5-3000, 5-2000, 5-1000, 5-500, 5-100, 5-50, 5-20, 5-10, as well as ranges therebetween).

[0197] In some embodiments, RA, RA1, or RA2 is or includes -NH-, -NRn1-, -N(-Lj-NRn1RN2)-, -N(-L2-NRN3-Lj-NRn1RN2)-, -N[-L2-N(-Lj-NRn1R N2)2]-, -NH2, -NRn1RN2, -L'-NRXIRX2, -NRN3-L1-NRn1RN2, -l2-nrN3-l1-nrn1rN2, or -NRN4-L2-NRN3-L1-NRN1RN2.

[0198] In some embodiments, each of RN1, RN2, RN3, RN4, and RN5 is, independently, hydrogen (H), halo (e.g., F, Cl, Br, or I), hydroxy (e.g., -OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxy (e.g., -OR, in which R is an optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, in which R is an optionally substituted aryl), trialkylsilyloxy (e.g., -OSiRs, in which each R is independently an optionally substituted alkyl), or trialkoxylsilyloxy (e.g., -OSi[OR]3, in which each R is independently an optionally substituted alkyl. In some embodiments, each of RN1, RN2, RN3, RN4, RN5, and R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0199] In some embodiments, each of RS1 and RS2 is, independently, a side group (e.g., any described herein), a leaving group (e.g., halo, acyl, acyloxy, and the like), a reactive group (e.g., hydroxy, halo, alkoxy, and the like), hydrogen (H), optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted amine, or an Ra moiety (e.g., any described herein); or RS1 and RS2, taken together with the silicon atom to which each are attached, form a heterocyclyl group. In some embodiments, each of RS1 and RS2 is independently hydrogen (H), optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0200] In some embodiments, the linker includes, for example, a covalent bond, an atom (e.g., carbonyl, oxy, thio, imino, and the like), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene.

[0201] In some embodiments, the functional portion includes an interaction moiety. In some embodiments, the interaction moiety includes one, two, three, or more silane moieties (e.g., any described herein). In some embodiments, the interaction moiety comprises one or more Si-0 bonds.

[0202] In some embodiments, the silane moiety includes an alkoxysilane group (e.g., -Si(OAk)d(X)3-d or -Si(OAk)di(X)2-di- or -Si(OAk)d(X)2-dRA); a trialkoxysilane group (e.g., -SiRslRS2RS3, in which each of RS1, RS2, and RS3 is, independently, alkoxy; such as trimethoxysilane or triethoxysilane); a dialkoxysilane group (e.g., e.g., -SiRslRS2RS3 or -SiRslRS2-, in which each of RS1 and RS2 is, independently, alkoxy, and a R3 is a side group, a leaving group, a reactive group, or any described herein); a monoalkoxysilane group (e.g, -SiRslRS2RS3 or -SiRslRS2-, in which RS1 is alkoxy, and each of RS2 and RS3 is independently a side group, a leaving group, a reactive group, or any described herein); a dialkoxysilanol group (e.g, -Si(OR)2OH, in which each R is independently alkyl); a monoalkoxysilanol group (e.g., -Si(OR)(Rsl)OH, in which each R is independently alkyl and RS1 is a side group, a leaving group, a reactive group, or any described herein); a hydrosilane group (e.g., -SiHs or -SiH2-); a monoalkylsilane group (e.g., -SiRslRS2RS3 or -SiRslRS2-, in which RS1 is alkyl, and each of RS2 and RS3 is independently a side group, a leaving group, a reactive group, or any described herein; in which non-limiting examples of monoalkylsilane is alkyldialkoxy silane or alkyldihalosilane); a dialkylsilane group (e.g., -SiRslRS2RS3 or -SiRslRS2-, in which each of RS1 and RS2 is independently alkyl, and RS3 is a side group, a leaving group, a reactive group, or any described herein; in which non-limiting examples of dialkylsilane includes dialkylalkoxysilane or dialkylhalosilane); a trihalosilane group (e.g., -SiZs, in which each Z is independently halo, such as trichlorosilane); a dihalosilane group (e.g., -SiZ2Rsl, in which each Z is independently halo and each of RS1 is a side group, a leaving group, a reactive group, or any described herein); a monohalosilane group (e.g., -SiZRslRS2, in which Z is halo and each of RS1 and RS2 is independently a side group, a leaving group, a reactive group, or any described herein); a silanetriol group (e.g., -Si(OH)3); or a hydroxysilane group (e.g., -Si(OH)Rsl-, -Si(OH)2-, or -Si(OH)3).

[0203] In some non-limiting embodiments for any silane moiety herein, Ak is optionally substituted aliphatic, alkyl, or alkylene; each X is, independently, a side group, a reactive group, or a leaving group, as any described herein; d is an integer of 1, 2, or 3; and dl is an integer of 1 or 2. In some embodiments, each of RS1, RS2, and RS3 is, independently, a side group (e.g., any described herein), a leaving group (e.g., halo, acyl, acyloxy, and the like), a reactive group (e.g., hydroxy, halo, alkoxy, and the like), hydrogen (H), optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted amine, or an RA moiety (e.g., any described herein); or RS1 and RS2, taken together with the silicon atom to which each are attached, form a heterocyclyl group. In some embodiments, each of RS1 and RS2 is independently hydrogen (H), optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0204] In some embodiments, any useful combination of moieties is present. For example, in some embodiments, the functional portion includes a combination of one or more adsorbing moieties, a combination of one or more interaction moieties, a combination of an adsorbing moiety with an interaction moiety, and a combination of one or more adsorbing moieties with one or more interaction moieties.

[0205] In some embodiments, the functional portion is provided in any useful manner. For example, in some embodiments, a compound having both the adsorbing moiety and the interaction moiety is provided to a substrate. A non-limiting example of such a compound includes an aminosilane comprising an amino moiety (e.g., as the adsorbing moiety) and a silane moiety (e.g., as the interaction moiety). In some embodiments, the compound has a long-chain multi-amine containing moiety. In some embodiments, the compound has a silane moiety, which is chemically bonded to a surface of each of the particles (e.g., porous silica particles) serving as the substrate.

[0206] In another example, a plurality of compounds is used to provide the one or more adsorbing moieties and one or more interaction moieties. For instance, in some embodiments, a first compound includes both an adsorbing moiety and an interaction moiety, and a second compound includes one or more adsorbing moieties. A non-limiting example includes a first compound that is an aminosilane comprising an amino moiety (e.g., as the adsorbing moiety) and a silane moiety (e.g., as the interaction moiety) that is used in combination with a second compound that is a polyamine comprising a plurality of amino moieties (e.g., as the adsorbing moieties). In some embodiments, the first compound is attached to a surface of the substrate (e.g., by way of one or more covalent bonds or non-covalent bonds), and the second compound is or is not attached to the substrate. In some embodiments, the second compound interacts with the first compound (or a portion thereof). In some embodiments, the second compound interacts with the first compound (or a portion thereof) and with the substrate surface. In some embodiments, such attachments and interactions include covalent and / or non-covalent bonding interactions. Non-covalent bonding interactions include, without limitation, hydrogen bonding, ionic interactions, halogen bonding, electrostatic interactions, r| bond interactions, hydrophobic interactions, inclusion complexes, clathration, van der Waals interactions, and combinations thereof.

[0207] Upon providing one or more compounds to a substrate, reactions can occur to provide covalent and / or non-covalent bonding interactions, thereby providing a functional portion disposed on the substrate surface. Non-limiting examples of compounds for providing a functional portion include amines, aminosilanes, polymers, polyamines, as well as others described herein.

[0208] a. Aminosilanes

[0209] In some embodiments, the compound is an aminosilane. For example and without limitation, the substrate surface (e.g, a silica substrate surface) is functionalized with an aminosilane compound including a silane moiety bonded to an amine moiety. In turn, in some embodiments, the surface includes a functional group having the silane moiety and the amine moiety. As used herein, such moi eties also include reacted forms of these moi eties (e.g, a reacted form of a silane moiety upon reacting with a surface of the substrate) that may be present upon forming one or more bonds, as would be understood by a skilled artisan.

[0210] In some embodiments, the aminosilane include at least one silane moiety (e.g., one, two, three, or more silane moi eties) and at least one amine moiety (e.g., one, two, three, or more amine moieties). Non-limiting examples of aminosilane compounds, silane moieties, and amine moieties are described herein.

[0211] In some embodiments, the aminosilane compound includes one, two, three, or more silane moieties. In some embodiments, the silane moiety includes a trialkoxysilane (e.g., -SiRslRS2RS3, in which each of RS1, RS2, and RS3 is, independently, alkoxy; such as trimethoxysilane or triethoxysilane), a dialkoxysilane (e.g., -SiRslRS2RS3, in which each of RS1 and RS2 is, independently, alkoxy, and RS3 is a leaving group or a reactive group, such as any described herein), a dialkoxysilanol group (e.g., -Si(OR)2OH, in which each R is independently alkyl), a hydrosilane group (e.g., -SiHs), a monoalkylsilane group (e.g., -SiRslRS2RS3, in which RS1 is alkyl, and each of RS2 and RS3 is independently a leaving group or a reactive group, such as any described herein; in which non-limiting examples of monoalkylsilane is alkyldialkoxysilane or alkyldihalosilane), a dialkylsilane group (e.g., -SiRslRS2RS3, in which each of RS1 and RS2 is independently alkyl, and RS3 is a reactive group or a leaving group, such as any described herein; in which non-limiting examples of dialkylsilane includes dialkylalkoxysilane or dialkylhalosilane), a trihalosilane group (e.g., -SiZs, in which each Z is independently halo, such as trichlorosilane), or a silanetriol (e.g., -Si(OH)3). In some embodiments, higher numbers (e.g., three or more) of silane moieties in the aminosilane compound increase the covalent bond stability with the substrate as higher numbers of siloxane bonds between the silane moieties and the substrate surface can increase. Additionally, in some embodiments, a silane group forms up to three siloxane bonds (Si-O-Si) to the surface, which increases stability. In some embodiments, the number of siloxane bonds that are formed by silane moiety depends on the composition of the side groups (e.g., one or more of X1, X2, and / or X3) capable of forming siloxane bonds (e.g., -OMe, -OEt, -Cl, -OH, or a combination of any of these).

[0212] In some embodiments, the aminosilane compound includes one, two, three, or more amine moieties. In some embodiments, the amine moiety includes a primary amine (e.g., -NH2), a secondary amine (e.g., -NHRn1, in which RN1 is any RS1 described herein that is not hydrogen), a tertiary amine (e.g., -NRN1RN2, in which each of RN1 and RN2 is respectively any RS1 and RS2 described herein that is not hydrogen), or an aminoalkyl group (e.g., -Ak-NRN1RN2, in which Ak is optionally substituted alkylene and each of RN1 and RN2 is respectively any RS1 and RS2 described herein). In some embodiments, each of RN1 and RN2 is, independently, hydrogen (H), halo (e.g., F, Cl, Br, or I), hydroxy (e.g., -OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxy (e.g., -OR, in which R is an optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, in which R is an optionally substituted aryl), trialkylsilyloxy (e.g., -OSiRs, in which each R is independently an optionally substituted alkyl), or trialkoxylsilyloxy (e.g., -OSi[OR]3, in which each R is independently an optionally substituted alkyl. In some embodiments, each of RN1, RN2, and R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0213] In some embodiments, the amine moiety includes more than one amine group connected through various linkers (e.g., any described herein for L). For instance, in some embodiments, the amine moiety includes a terminal amine group (e.g., -NRN1RN2), one or more internal amine groups (e.g., -NRN3-), and a linker (e.g., -L-) disposed between the terminal and internal amine groups, where RN1, RN2, and RN3 are respectively any RS1, RS2, and RS3 described herein. Non-limiting examples of amine moieties include an aminoalkylamino group (e.g., -NRN3-Ak-NRN1RN2, in which Ak is optionally substituted alkylene and each of RN1, RN2, and RN3 is respectively any RS1, RS2, and RS3 described herein) or an aminoalkylaminoalkyl group (e.g., -Ak-NRN3-Ak-NRN1RN2, in which each Ak is independently optionally substituted alkylene and each of RN1, RN2, and RN3 is respectively any RS1, RS2, and RS3 described herein described herein). In some embodiments, each of RN1, RN2, and RN3 is, independently, hydrogen (H), halo (e.g., F, Cl, Br, or I), hydroxy (e.g., -OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxy (e.g., -OR, in which R is an optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, in which R is an optionally substituted aryl), trialkylsilyloxy (e.g., -OSiR3, in which each R is independently an optionally substituted alkyl), or trialkoxylsilyloxy (e.g., -OSi[OR]3, in which each R is independently an optionally substituted alkyl. In some embodiments, each of RN1, RN2, RN3, and R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0214] In some embodiments, higher numbers (e.g., three or more) of amine moi eties in the aminosilane compound increase the adsorption ability of a sorbent. In some embodiments, amine moieties interact with other moieties and groups to stabilize stability of the functional group.

[0215] In some embodiments, an amine moiety (e.g., amine groups) of one aminosilane interacts with a neighboring aminosilane (e.g., with silane moieties or side groups within a silane moiety of the neighboring aminosilane). Alternatively, an amine moiety of one aminosilane does not interact with a neighboring aminosilane (e.g., does not interact with silane moieties or side groups within a silane moiety of the neighboring aminosilane). In yet another embodiment, an amine moiety of one aminosilane interacts with other groups, moieties, or compounds (e.g., present in another compound, such as a polyamine or another type of aminosilane). In some embodiments, an amine moiety (e.g., which can be an amine group) of the aminosilane interacts with a polyamine (e.g., an amine moiety of a polyamine).

[0216] In some embodiments, the aminosilane compound has any useful structure. In one non-limiting example, the aminosilane includes a structure having formula (I): [RA]aSi[X]4-a (I), where each RA is, independently, an amine moiety comprising at least one amine group, each X is, independently, a side group, a reactive group, or a leaving group, and a is an integer from 1 to 4.

[0217] In some embodiments, the amine moiety (e.g., RA) includes one or more amine groups. In one instance, the amine group is -NRN1RN2 or -NRn1-, in which each of RN1 and RN2 is, independently, hydrogen (H), halo (e.g., F, Cl, Br, or I), hydroxy (e.g., -OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxy (e.g., -OR, in which R is an optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, in which R is an optionally substituted aryl), trialkylsilyloxy (e.g., -OSiR3, in which each R is independently an optionally substituted alkyl), or trialkoxylsilyloxy (e.g., -OSi[OR]3, in which each R is independently an optionally substituted alkyl). In some embodiments, each of RN1, RN2, and R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0218] In some embodiments, the amine moiety (e.g., RA) includes one, two, three, or more amine groups. In other embodiments, the amine moiety includes a terminal amine group (e.g., as -NRN1RN2) and / or an internal amine group (e.g., as -NRn1-).

[0219] Non-limiting examples of amine moieties (e.g., RA) include -NRN1RN2, -L-NRn1RN2, -NRN3-L-NRn1RN2, -L2-NRN3-L1-NRn1RN2, -L3-NRN4-L2-NR N3-L1-NRn1RN2, -L2-SiRslRS2-L1-NRN1RN2, and -L3-SiRslRS2-L2-NRN3-L1-NRN1RN2, in which each of Rn1, RN2, Rs1, and RS2 are described herein; in which each of RN3 and RN4 are described herein for RN1 and RN2; and in which each L, L1, L2, or L3 is independently a linker. Non-limiting examples of linkers include, e.g., a covalent bond, an atom (e.g., carbonyl, oxy, thio, imino, and the like), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene. In some non-limiting embodiments, each of RN1, RN2, RN3, RN4, RS1, and RS2 is, independently, H, optionally substituted aliphatic, or optionally substituted alkyl. Other examples of RN1, RN2, and RN3 are described herein.

[0220] In some embodiments, the aminosilane includes a reactive group, a leaving group, or another group (e.g., X). Non-limiting examples of such groups include H, halo (e.g., F, Cl, Br, or I), hydroxy (e.g., -OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxy (e.g., -OR, in which R is an optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, in which R is an optionally substituted aryl), or optionally substituted alkanoyloxy. In some embodiments, X is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0221] In one non-limiting example, the aminosilane includes a structure having formula (la): RA1SiXxX2X3 (la), where RA1 is an amine moiety comprising at least one amine group; and each of X1, X2, and X3 is, independently, a side group, a reactive group, or a leaving group. Each of RA1, X1, X2, and X3 is any described herein for RA and X, respectively. An example of formula IA is shown in Figure 2A (where the terms RA1 and RA are interchangeable).

[0222] In another non-limiting example, the aminosilane includes a structure having formula lb, Ic, Id, or Ie: RA1-L1-SiX1X2X3           (lb), RNlRN2N_Ll_SiXlX2X33           (k), RA1-L1-RA2.L2_sixiX2X3           (Id), or RNiRN2N-Li-N(RN3)-L2-SiXiX2X3         (Ie)5 where N stands for Nitrogen, each RA1 or RA2 is, independently, an amine moiety comprising at least one amine group, each of RN1, RN2, and RN3 is any described herein, each of X1, X2, and X3 is, independently, a side group, a reactive group, or a leaving group, and each of L1 and L2 is a linker. In some embodiments, each of RA1, R^, X1, X2, X3, L1, and L2 is any described herein for RA, X, and L, respectively. In some embodiments, each of X1, X2, and X3 is, independently, H, halo, optionally substituted alkyl (e.g., optionally substituted C1-3 alkyl), or optionally substituted alkoxy (e.g., optionally substituted C1-3 alkoxy). In other embodiments, each of X1, X2, and X3 is, independently, optionally substituted alkoxy (e.g., optionally substituted C1-3 alkoxy). In yet other embodiments, L is optionally substituted alkylene (e.g., optionally substituted C1-12, C1-10, C1-8, or C1-6 alkylene).

[0223] In yet another non-limiting example, the aminosilane has the structure of formula If: RAlRA2RA3sixl             (If), where each RA1, RA2, or RA3 is, independently, an amine moiety comprising at least one amine group; and X1 is a side group, a reactive group, or a leaving group. In some embodiments, each of RA1, RA2, RA3, and X1 is any described herein for RA and X, respectively.

[0224] In some embodiments, the aminosilane has the structure of formula II: [RB]bN[Y]3-b (II), where each RB is, independently, a silane moiety comprising at least one silane group, N is nitrogen, each Y is, independently, H, optionally substituted alkyl, or optionally substituted aryl, and b is an integer from 1 to 3. In some embodiments, each Y is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. One example of formula II is illustrated in Figure 2F. Another example of formula II is illustrated in Figure 2G.

[0225] In some embodiments, the silane moiety (e.g., RB) includes one or more silane groups. In some embodiments, the silane group is -SiRslRS2RS3 or -SiRslRS2-, in which each of RS1, RS2, and RS3 is, independently, hydrogen (H), halo (e.g., F, Cl, Br, or I), hydroxy (e.g., -OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxy (e.g., -OR, in which R is an optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, in which R is an optionally substituted aryl), trialkylsilyloxy (e.g., -OSiR3, in which each R is independently an optionally substituted alkyl), or trialkoxylsilyloxy (e.g., -OSi[OR]3, in which each R is independently an optionally substituted alkyl). In some embodiments, each of RS1, RS2, RS3, and R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0226] In some embodiments, the silane moiety (e.g., RB) includes one, two, three, or more silane groups. In other embodiments, the silane moiety includes a terminal silane group (e.g., as -SiRslRS2RS3) and an internal silane group (e.g., as -SiRslRS2-).

[0227] Non-limiting examples of silane moi eties (e.g., RB) include -SiRslRS2RS3, -Si(ORsl)(RS2)(RS3), -Si(ORsl)(ORS2)(RS3), -Si(ORsl)(ORS2)(ORS3), -L-SiRslRS2RS3, -L-Si(O Rsi)(Rs2yRs3^ -L-Si(ORsl)(ORS2)(RS3), -L-Si(ORsl)(ORS2)(ORS3), -SiRS4RS5-L-SiRslRS2RS3 , and -SiRslRS2-NRN1RN2, in which each of RS1, RS2, RS3, RN1, and RN2 is any described herein, in which each of RS4 and RS5 is any described herein for RS1, RS2, and RS3; and in which L is a linker. Examples of linkers include, e.g., a covalent bond, an atom (e.g., carbonyl, oxy, thio, imino, and the like), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene. In some non-limiting embodiments, each of RS1, RS2, RS3, RS4, RS5, RN1, and RN2 is, independently, H, optionally substituted aliphatic, or optionally substituted alkyl.

[0228] In one non-limiting example, the aminosilane has the structure of formula Ila: rbiNY'Y2          (Ila), where N is nitrogen, RB1 is a silane moiety comprising at least one silane group (e.g., any described herein for RB) and each of Y1 and Y2 is any described herein for Y (e.g., a side group, a reactive group, or a leaving group).

[0229] In another non-limiting example, the aminosilane has the structure of formula lib, lie, or lid: RB1RB2NY1         (Hb), [RsiRs2Rs3Si_Li_]NYiY2           (lie), or [RsiRs2Rs3SiLi_jNYi|-_L2_siRsiRs2Rs3]           (lid), where N is nitrogen, each RB1 or RB2 is, independently, a silane moiety comprising at least one silane group, each of Y1 and Y2 is, independently, a side group, a reactive group, or a leaving group, each of RS1, RS2, and RS3 is any described herein; and each of L1 and L2 is a linker. Each of RB1, RB2, Y1, Y2, L1, and L2 is any described herein for RB, Y, and L, respectively.

[0230] FIGS. 2A-2C depict an examples of an aminosilane 206 having an amine moiety 210 (denoted as RA) and a non-limiting silane moiety 208 having three potential interaction sites or side groups (denoted as X1, X2, and X3). Side groups X^X3 are occupied by functional groups which include, but are not limited to, a methoxy group (-OMe), an ethoxy group (-OEt), a chloro (-C1), a hydroxy group (-OH), a hydrogen (-H), or an alkyl group (e.g., a linear alkyl group such as -(CH2)n(CH3), in which n is an integer from 0-10; or a branched alkyl group). Yet other examples of functional groups can include any reactive or leaving group described herein. Non-limiting examples of functional groups for X can include halo, as well as optionally substituted aliphatic, alkyl, alkoxy, alkanoyloxy, heteroaliphatic, heteroalkyl, aromatic, aryl, aryloxy, and the like.

[0231] In some embodiments, the amine moi eties 210 (e.g., which can be amine groups) of one aminosilane interact with one or more of the side groups 208 of a neighboring aminosilane. In alternative embodiments, amine moi eties 210 do not interact with other side groups. In yet other embodiments, the amine moi eties 210 interact with other groups, moi eties, or compounds (e.g., present in another compound, such as a polyamine or another type of aminosilane). In some embodiments, the amine moi eties 210 (e.g., which can be amine groups) of aminosilane 208 interact with a polyamine.

[0232] Optionally, a further linker is present between the amine moiety and the silane moiety of the aminosilane compound. For example, in some embodiments a linker is present between the amine moiety 210 and the silane moiety 208. In some embodiments, the aminosilane includes RA-L-SiX1X2X3, in which RA is an amine moiety (e.g., any described herein), L is a linker (e.g., any described herein), and each of X1, X2, and X3 is a side group, a reactive group, or a leaving group (e.g., any described herein).

[0233] In some embodiments, an aminosilane 206 has any combination of these functional groups, e.g., amine moiety 210 and side groups 208 (e.g., which can include side group X1, side group X2, or side group X3), and must have at least one amine moiety 210 and at least one side group 208 (e.g., -OMe, -OEt, -Cl, -OH, -H, alkyl, or others described herein) capable of forming a siloxane bond (e.g., an Si-0 or Si-O-Si linkage). FIG. 2B is a non-limiting example of a 3-aminopropyl group which, in some examples, serves as one or more side groups 208 (e.g., one or more of X1, X2, and X3) or amine moiety 210. FIG. 2C is an example of an N-(2-aminoethyl)-3-aminopropyl group which, in some examples, serves as one or more amine moi eties 210.

[0234] As non-limiting examples, FIGS. 2D-2G indicate examples of aminosilanes having side groups and amine moieties. In some embodiments, the aminosilane is an alkylalkoxyaminosilane having a formula of RA(Ak)cSi(OAk)d, in which each of c and d is 1 or 2; Ra is an amine moiety (e.g., any described herein); and each of Ak is, independently, an optionally substituted alkyl. Non-limiting examples of alkylalkoxyaminosilane include 3-aminopropyl(diethoxy)methylsilane (FIG. 2D) and 3-(ethoxydimethylsilyl)propylamine (FIG. 2E).

[0235] In some embodiments, the aminosilane is an aminosilanetriol having the formula (HO)3SiRA, in which RA is an amine moiety (e.g., any described herein). A non-limiting example of aminosilanetriol is (3-((2-aminoethyl)amino)propyl)silanetriol (FIG. 2F).

[0236] In some embodiments, the aminosilane is a haloaminosilane having the formula (RA)sSiX, in which each RA is, independently, an amine moiety (e.g., any described herein) and X is halo (e.g., any described herein). Non-limiting examples of haloaminosilane include tris(dimethylamino)chlorosilane (FIG. 2G), tris(ethylmethylamino)chlorosilane, and the like.

[0237] In some embodiments, the aminosilane 108 has the structure of formula Illa:

[0238] In formula Illa, Q is -(CP2)n- where n is 2, 3, 4, or 5, and each P is independently a hydrogen, hydroxy, or halogen. In one embodiment, each P is halogen and n is 3: -CH2-CH2-CH2- (e.g., compounds 1302, 1304, 1306, 1308, 1310, 1312, 1314, 1322, 1324, and 1326 of Figure 14).

[0239] In formula Illa, each Ri, R2, and R3 is independently hydrogen, alkyl, a substituted alkyl, an alkylene, or a substituted alkylene. In some embodiments, each Ri, R2, and R3 is -CH3, -CH2-CH3, or -CH2-CH2-CH3. In one embodiment, each Ri, R2, and R3 is hydrogen (e.g., compounds 1308, 1312 and 1314 of Figure 13). In one embodiment, each Ri, R2, and R3 is -CH2-CH3 (e.g., compound 1304 of Figure 13). In one embodiment, each Ri, R2, and R3 is - -CH3 (e.g., compounds 1302, 1306, 1322, 1324, 1326, and 1328 of Figure 13).

[0240] In formula Illa, each R4 and Rs is independently hydrogen, a substituted alkane, a substituted alkylene, an aryl, or a substituted aryl.

[0241] In some embodiments R4 and Rs are each methyl (e.g., compound 1328 of Figure 13).

[0242] In one embodiment one of R4 and Rs is -(CH2)m-NH(Rs), where m is 1, 2, 3, 4 or 5, and Rs is hydrogen or a substituted alkane, while the other of R4 and Rs is hydrogen.

[0243] In one embodiment R4 is -(CH2)m-NH(Re), where m is 1, 2, 3, 4 or 5, and Re is hydrogen or a substituted alkane, and R4 is hydrogen. In some such embodiments, m is 2 and Re is hydrogen: -CH2-CH2-NH2 (e.g., compounds 1306 and 1308 of Figure 13). In other embodiments, Re is -(CH2)P-NH(R?), where p is m is 1, 2, 3, 4 or 5, and R7 is hydrogen or a substituted alkane. In one embodiment, R7 is -(CH2)-(CH2)-NH2 (e.g., compound 1314 of Figure 13).

[0244] In some embodiments, the aminosilane 108 has the structure of formula Illb:

[0245] In formula Illb, Q is -(CP2)n- where n is 2, 3, 4, or 5, and each P is independently a hydrogen, hydroxy, or halogen. In one embodiment, each P is halogen and n is 3: -CH2-CH2-CH2- (e.g, compounds 1302, 1304, 1306, 1308, 1310, 1312, 1314, 1320, 1322, 1324, and 1326 of Figure 13).

[0246] In formula Illb, each Ri, R2, and R3 is independently hydrogen, alkyl, a substituted alkyl, an alkylene, a substituted alkylene, an alkoxy, or a substituted alkoxy. In some embodiments, Ri and R2 are each -OCH2-CH3, and R3 is -CH3 (e.g., compound 1320 of Figure 13).

[0247] In formula Illa, each R4 and Rs is independently hydrogen, a substituted alkane, a substituted alkylene, an aryl, or a substituted aryl.

[0248] In some embodiments R4 and Rs are each methyl (e.g., compound 1328 of Figure 13).

[0249] In some embodiments R4 and Rs are each hydrogen (e.g., compound 1320 of Figure 13).

[0250] In some embodiments, one of R4 and Rs is -(CH2)m-NH(Rs), where m is 1, 2, 3, 4 or 5, and Rs is hydrogen or a substituted alkane, while the other of R4 and Rs is hydrogen.

[0251] In some embodiments, R4 is -(CH2)m-NH(Re), where m is 1, 2, 3, 4 or 5, and Re is hydrogen or a substituted alkane, and Rs is hydrogen. In some such embodiments, m is 2 and Re is hydrogen: -CH2-CH2-NH2 (e.g., compounds 1306 and 1308 of Figure 13). In other embodiments, Re is -(CH2)P-NH(R?), where p is m is 1, 2, 3, 4 or 5, and R7 is hydrogen or a substituted alkane. In one embodiment, R7 is -(CH2)-(CH2)-NH2 (e.g., compound 1314 of Figure 13).

[0252] In some embodiments, the aminosilane 108 has the structure of formula IV: (IV)

[0253] In formula IV, each Ri, R2, R3, R4, Rs, and Re is independently hydrogen, alkyl, a substituted alkyl, an alkylene, or a substituted alkylene. In one embodiment, each Ri, R2, R3, R4, Rs, and Re is -CH3 (e.g., compound 1318 of Figure 13). In one embodiment, each Ri, R2, R3, R4, Rs, and Re is -CH3 or -CH2CH3 (e.g., compound 1413 of Figure 13). In formula IV, X is halogen. In one embodiment, X is Cl (e.g., compounds 1413 and 1413 of Figure 13).

[0254] In some embodiments, the amine moi eties of the aminosilane 108 interact with one or more of the X^X3 sites of neighboring aminosilanes 108 or interact with polymeric amines 110. In some embodiments, the amine moiety is or includes an amine group such as the amine groups of FIGS. 2B and 2C, which depict example aminopropyl, and N-(2-aminoethyl)-3-aminopropyl groups, respectively. In some implementations, the amine moiety is a primary, secondary, or tertiary amine. For example, in some embodiments, the amine moiety includes one or more aminopropyl or diethylenetriamine groups. In some implementations, the amine moiety includes more than one amine group connected through various alkyl groups. For instance, in some embodiments, the amine moiety includes a terminal amine group, an internal amine group, and a linker disposed between the terminal and internal amine group.

[0255] Optionally, in some embodiments, a further linker is present between the amine moiety and the silane moiety of the aminosilane compound.

[0256] Other non-limiting examples of aminosilanes include (3-aminopropyl) trimethoxysilane (compound 1302 in Figure 13), (3-aminopropyl)tri ethoxy silane (compound 1304 in Figure 13), [3-(2-aminoethylamino)propyl]trimethoxysilane (compound 1306 in Figure 13), N-(2-aminoethyl)-3-aminopropyl silanetriol (compound 1308 in Figure 13), N1-(3-trimethoxysilylpropyl) diethylenetriamine (compound 1310 in Figure 13), 3-aminopropylsilanetriol (compound 1312 in Figure 13), N-(2aminoethyl)-3-aminopropylsilanetriol (compound 1314 in Figure 14), tris(ethylmethylamino)chlorosilane (compound 1316 in Figure 14), tris(dimethylamino)chlorosilane (compound 1318 in Figure 13), an aminosilane oligomer (e.g., such as VPS SIVO 280, a modified organofunctional polysiloxane from Evonik Industries AG, Essen, Germany), 3-aminopropyl(diethoxy)methylsilane (compound 1320 in Figure 13), N-[3-(trimethoxysilyl)propyl]ethylenediamine (compound 1322 in Figure 13), bis(3-(methylamino)propyl)-trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine (compound 1324 in Figure 13), N-[3-(trimethoxysilyl)propyl]aniline (compound 1326 in Figure 13), or (N,N-dimethylamino propyl)trimethoxysilane (compound 1328 in Figure 13).

[0257] b. Silanes

[0258] In some embodiments, a silane compound includes any compound having a -SiRslRS2RS3 moiety or a -SiRslRS2- moiety, in which each of RS1, RS2, and RS3 is any described herein. In some embodiments, each of RS1, RS2, and RS3 is, independently, H, optionally substituted aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, aryl, amine, or others described herein; or RS1 and RS2, taken together with the silicon atom to which each are attached, form a heterocyclyl group. In some embodiments, each of RS1, RS2, and RS3 is, independently, hydrogen (H), halo (e.g., F, Cl, Br, or I), hydroxy (e.g., -OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxy (e.g., -OR, in which R is an optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, in which R is an optionally substituted aryl), trialkylsilyloxy (e.g., -OSiR3, in which each R is independently an optionally substituted alkyl), or trialkoxylsilyloxy (e.g., -OSi[OR]3, in which each R is independently an optionally substituted alkyl).

[0259] In some embodiments, the silane includes one or more amino moieties, such as in an aminosilane compound (e.g., any described herein).

[0260] In some embodiments, the silane does not include an amino moiety. In one non-limiting example, the silane has formula (V): [RC1]aSi[X]4-a (V), where each RC1 does not comprise amino; each X is, independently, a side group, a reactive group, or a leaving group (e.g., any described herein); and a is an integer from 1 to 4.

[0261] In some embodiments, RC1 is optionally substituted aliphatic, heteroaliphatic, alkyl, aromatic, heteroaromatic, or aryl, where the optional substituent is not amino (e.g., as defined herein). In some embodiments, RC1 is a branched, optionally substituted aliphatic, heteroaliphatic, alkyl, aromatic, heteroaromatic, or aryl. In some embodiments, RC1 is a hydrophobic group (e.g., optionally substituted C4-30 aliphatic, heteroaliphatic, alkyl, perfluoroalkyl, cycloalkyl, aromatic, heteroaromatic, or aryl). Non-limiting examples of hydrophobic groups include optionally substituted C4-24, C6-24, Cs-24, C4-18, Ce-18, Cs-18 alkyl, haloalkyl, perfluoroalkyl, cycloalkyl, and the like (e.g., hexyl, octyl, nonyl, decyl, dodecyl, perfluorohexyl, perfluorooctyl, cyclohexyl, and cyclopentyl).

[0262] In some embodiments, the silane has formula (Va): [X]3Si-L-Si[X]3             (Va), where L is a linker (e.g., any described herein) and each X is, independently, a side group, a reactive group, or a leaving group (e.g., any described herein).

[0263] Examples of linkers include, e.g., a covalent bond, an atom (e.g., carbonyl, oxy, thio, imino, and the like), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene. Other examples of linkers include any described herein (e.g., described herein for L, L1, L2, and L3).

[0264] In some embodiments, the silane includes a reactive group, a leaving group, or another group (e.g., X). Non-limiting examples of such groups include hydrogen (H), halo (e.g., F, Cl, Br, or I), hydroxy (e.g., -OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxy (e.g., -OR, in which R is an optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, in which R is an optionally substituted aryl), optionally substituted alkanoyloxy, trialkylsilyloxy (e.g., -OSiR3, in which each R is independently an optionally substituted alkyl), or trialkoxylsilyloxy (e.g., -OSi[OR]3, in which each R is independently an optionally substituted alkyl). In some embodiments, X is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0265] In some embodiments, a silane is employed as a crosslinker or as an additive for any composition or use herein (e.g., for any coating, surface functionalization layer, functionalization mixture, pre-functionalization mixture, and the like). Non-limiting examples of silanes include l,2-bis(triethoxysilyl)ethane (BTESE) and l,2-bis(trimethoxysilyl)ethane (BTME).

[0266] c. Polyamines

[0267] As described herein, in some embodiments the functional portion is provided by any useful compound or combination of compounds. In some embodiments, the compound is a polyamine. In some embodiments, the polyamine includes any compound or moiety having two or more amine moieties. In some embodiments, the polyamine is a non-polymeric compound, in which the polyamine does not include repeating units. In some embodiments, the polyamine is a polymeric compound (e.g., as in a polymeric polyamine). In other embodiments, the polyamine is an oligomeric compound (e.g., as in an oligomeric polyamine). Unless otherwise specified, discussion related to “polymeric” and “oligomeric” forms of compounds is applied interchangeably. In some embodiments, the polyamine includes dimeric, trimeric, tetrameric, pentameric, hexameric, and higher order amines. In some embodiments, the polyamine is a small molecule polyamine (e.g., having a molecular weight between 100 g / mol and 800 g / mol). In some embodiments, the polyamine is a large molecule polyamine (e.g., having a MW greater than 800 g / mol).

[0268] In some embodiments, a polyamine is used alone or with other compounds (e.g., any described herein, such as an aminosilane and the like). In some embodiments, the polyamine is used in the presence of aminosilane. In some embodiments, a first polyamine (e.g., having a high MW, such as any described herein) is used in the presence of a second polyamine (e.g., having a low MW, such as any described herein).

[0269] In some embodiments, a high molecular weight includes a weight-average molecular weight (Mw) or number-average molecular weight (Mn) of greater than 300 daltons (Da), 400 Da, 500 Da, or 600 Da or from a range of 300 to 1,000,000 Da (e.g., 300 to 900000 Da, 300 to 800000 Da, 300 to 700000 Da, 300 to 600000 Da, 300 to 500000 Da, 300 to 400000 Da, 300 to 300000 Da, 300 to 200000 Da, 300 to 100000 Da, 300 to 90000 Da, 300 to 80000 Da, 300 to 70000 Da, 300 to 60000 Da, 300 to 50000 Da, 300 to 40000 Da, 300 to 30000 Da, 300 to 20000 Da, 300 to 10000 Da, 300 to 9000 Da, 300 to 8000 Da, 300 to 7000 Da, 300 to 6000 Da, 300 to 5000 Da, 300 to 4000 Da, 300 to 3000 Da, 300 to 2000 Da, 300 to 1000 Da, 500 to 1000000 Da, 500 to 900000 Da, 500 to 800000 Da, 500 to 700000 Da, 500 to 600000 Da, 500 to 500000 Da, 500 to 400000 Da, 500 to 300000 Da, 500 to 200000 Da, 500 to 100000 Da, 500 to 90000 Da, 500 to 80000 Da, 500 to 70000 Da, 500 to 60000 Da, 500 to 50000 Da, 500 to 40000 Da, 500 to 30000 Da, 500 to 20000 Da, 500 to 10000 Da, 500 to 9000 Da, 500 to 8000 Da, 500 to 7000 Da, 500 to 6000 Da, 500 to 5000 Da, 500 to 4000 Da, 500 to 3000 Da, 500 to 2000 Da, 500 to 1000 Da, 700 to 1000000 Da, 700 to 900000 Da, 700 to 800000 Da, 700 to 700000 Da, 700 to 600000 Da, 700 to 500000 Da, 700 to 400000 Da, 700 to 300000 Da, 700 to 200000 Da, 700 to 100000 Da, 700 to 90000 Da, 700 to 80000 Da, 700 to 70000 Da, 700 to 60000 Da, 700 to 50000 Da, 700 to 40000 Da, 700 to 30000 Da, 700 to 20000 Da, 700 to 10000 Da, 700 to 9000 Da, 700 to 8000 Da, 700 to 7000 Da, 700 to 6000 Da, 700 to 5000 Da, 700 to 4000 Da, 700 to 3000 Da, 700 to 2000 Da, 700 to 1000 Da, 800 to 1000000 Da, 800 to 900000 Da, 800 to 800000 Da, 800 to 700000 Da, 800 to 600000 Da, 800 to 500000 Da, 800 to 400000 Da, 800 to 300000 Da, 800 to 200000 Da, 800 to 100000 Da, 800 to 90000 Da, 800 to 80000 Da, 800 to 70000 Da, 800 to 60000 Da, 800 to 50000 Da, 800 to 40000 Da, 800 to 30000 Da, 800 to 20000 Da, 800 to 10000 Da, 800 to 9000 Da, 800 to 8000 Da, 800 to 7000 Da, 800 to 6000 Da, 800 to 5000 Da, 800 to 4000 Da, 800 to 3000 Da, 800 to 2000 Da, or 800 to 1000 Da). In some embodiments, the high MW polyamine includes linear or branched forms. In some embodiments, the high MW polyamine includes a plurality of primary amine moieties and / or a plurality of secondary amine moieties. In some embodiments, the high molecular weight polyamine is provided in polymeric form.

[0270] In some embodiments, the low molecular weight includes a weight-average molecular weight (Mw) or number-average molecular weight (Mn) of less than 300 Da, from a range of 30 to 300 Da, from a range of 100 to 800 Da, or ranges therebetween (e.g., 30 Da to 800 Da, 30 Da to 700 Da, 30 Da to 500 Da, 30 Da to 200 Da, 30 Da to 100 Da, 50 Da to 800 Da, 50 Da to 700 Da, 50 Da to 600 Da, 50 Da to 500 Da, 100 Da to 700 Da, 100 Da to 600 Da, 100 Da to 500 Da, 100 Da to 400 Da, 100 Da to 300 Da, 150 Da to 800 Da, 150 Da to 700 Da, 150 Da to 600 Da, 150 Da to 500 Da, 150 Da to 400 Da, 150 Da to 300 Da, 200 Da to 800 Da, and 300 Da to 800 Da). In some embodiments, the low molecular weight polyamine (e.g., which can be considered to be an oligomeric amine) includes linear or branched forms. In some embodiments, the low MW polyamine includes a plurality of primary amine moieties and / or a plurality of secondary amine moieties. In some embodiments, the low molecular weight polyamine is provided in oligomeric form.

[0271] Without wishing to be limited by mechanism, in some embodiments high molecular weight (MW) amines are useful for their lower volatility (e.g., as compared to low MW amines). In some embodiments, higher MW polyamines are characterized by a higher viscosity, which makes handling more difficult. Higher MW polyamines are generally more expensive. In some non-limiting embodiments, polyamines with high relative concentrations of primary and secondary amine moieties are employed. In some non-limiting embodiments, tertiary amine moieties are characterized by lower performance for DAC applications and are less desired. Secondary amines have higher oxidation resistance equating to longer operational lifetimes. Primary amines have higher reactivity equating to higher performance at low CO2 concentrations (DAC conditions).

[0272] The polyamine can have any useful structure. In one non-limiting example, the polyamine has the structure of any one of formula (Via) to (Vli): RA^tL^R^Jnl-L2^ (Via) (VIb) (Vic) (Vid) RNlRN2N_|-Ll_NRN3]nl_L2_NRN4RN5 (VIf) where N is nitrogen, each RA, RA1, R^, and RA3 is, independently, an amine moiety comprising at least one amine group, each L, L1, or L2 is, independently, a linker, each of rm rn2 rn3 r\4 anc[ rn5 js any describec[ herein, optionally where RN1 and RN2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein or optionally where RN4 and RN5, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein; Rc is hydrogen (H), halo, hydroxy, amino (e.g., -NRN1RN2), optionally substituted aliphatic, heteroaliphatic, alkyl, hydroxyalkyl, aromatic, heteroaromatic, or aryl; n is an integer greater than 1 (e.g, from 1-25000, 1-24000, 1-23000, 1-22000, 1-21000, 1-20000, 1-19000, 1-18000, 1-17000, 1-16000, 1-15000, 1-14000, 1-13000, 1-12000, 1-11000, 1-10000, 1-7500, 1-5000, 1-4000, 1-3000, 1-2000, 1-1000, 1-500, 1-100, 1-50, 1-20, 1-10, 1-5, 2-25000, 2-24000, 2-23000, 2-22000, 2-21000, 2-20000, 2-19000, 2-18000, 2-17000, 2-16000, 2-15000, 2-14000, 2-13000, 2-12000, 2-11000, 2-10000, 2-7500, 2-5000, 2-4000, 2-3000, 2-2000, 2-1000, 2-500, 2-100, 2-50, 2-20, 2-10, 2-5, 5-25000, 5-24000, 5-23000, 5-22000, 5-21000, 5-20000, 5-19000, 5-18000, 5-17000, 5-16000, 5-15000, 5-14000, 5-13000, 5-12000, 5-11000, 5-10000, 5-7500, 5-5000, 5-4000, 5-3000, 5-2000, 5-1000, 5-500, 5-100, 5-50, 5-20, 5-10, as well as ranges therebetween); and nl is an integer of 1 or more (e.g., from 1-1000, 1-100, 1-50, 1-20, 1-10, 5-1000, 5-100, 5-50, 5-20, 5-10, as well as ranges therebetween). In some embodiments, RA, RA1, and RA2 is any amine moiety described herein, L, L1, and L2 is any linker described herein, and each of RN1, RN2, RN3, RN4, and RN5 is any described herein for RN1 orRN2.

[0273] In some embodiments, RA, RA1, RA2, or RA3 is or includes -NH-, -NRn1-, -N(-Lj-NRn1RN2)-, -N(-L2-NRN3-L1-NRn1RN2)-, -N[-L2-N(-L1-NRn1RN2)2]-, -nh2, -NRn1Rn 2, -L'-NRXIRX2, -NRX3-L'-NRXIRN2, -L2-NRN3-Lj-NRn1RN2, or -NRN4-L2-NRN3-L1-NRN1RN2, in which each of RN1 and RN2 is any described herein, each of RN3 and RN4 is any described herein for RN1 and RN2; and each of L1 or L2 is independently a linker.

[0274] Examples of linkers (e.g., for L1, L2, or L) include, e.g., a covalent bond, an atom (e.g., carbonyl, oxy, thio, imino, and the like), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene. In some embodiments, the linker is a monomer or a polymer, which can be employed as a backbone to which an amine moiety RA is attached. Alternatively, the backbone of the polymer itself can also include an amine moiety. Non-limiting examples of monomers include a saccharide (e.g., glucosamine, N-acetyl-glucosamine, glucose, and the like), an amino acid (e.g., lysine), an alkylene, an alkenylene, an arylene, and the like. Non-limiting examples of polymers include a polysaccharide (e.g., chitosan, chitin, and the like), a polypeptide (e.g., poly(lysine)), a vinyl polymer, and the like.

[0275] Further non-limiting examples of polyamines include poly(lysine) (e.g., poly(L-lysine), poly(D-lysine), or poly(LD-lysine)), poly(ethyleneimine), poly(propyleneimine), poly(vinylamine), poly(N-methylvinylamine), poly(allylamine), poly(N-isopropyl acrylamide), poly(4-aminostyrene), chitosan, spermidine, spermine, norspermine, putrescine, cadaverine, tetraethylenepentamine (TEPA), triethylenetetramine (TETA), an ethylene amine / oligomeric mix (e.g., Amix 1000 having CAS No. 68910-05-4), diethylenetriamine (DETA), 2-(2-aminoethylamino)ethanol, ethylenediamine, piperazine, 2-piperazin-l-ylethylamine, 2-piperazin-l-ylethanol, pentaethylenehexamine, tetramethylethylenediamine, as well as salts thereof and / or copolymers thereof and / or mixtures thereof. In some embodiments, the polyamine includes spermidine, spermine, norspermine, putrescine, cadaverine, tetraethylenepentamine (TEPA), triethylenetetramine (TETA), ethanolamine, di ethylenetriamine (DETA), piperazine, 2-piperazin-l-ylethylamine, 2-piperazin-l-ylethanol, pentaethylenehexamine, tetramethylethylenediamine, as well as polymeric forms thereof. In some embodiments, the ethylene amine / oligomeric mix includes one or more of the following: 2-(2-aminoethylamino)ethanol, trientine or TETA, 2,2’-iminodi(ethylamine) or DETA, 2-aminoethanol, ethylenediamine, piperazine, 2-piperazin-l-ylethylamine, and 2-piperazin-l-ylethanol.

[0276] In some embodiments, the polyamine is or includes H2N[CH2CH2NH]nH, in which n is an integer of 1 or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more). In some embodiments, the polyamine is or includes H2N[-L-NH-]nH or N[-L-NH2]3, in which each L is independently a linker (e.g., any described herein, such as optionally substituted alkylene) and n is an integer of 1 or more. In some embodiments, the polyamine is or includes H2N[CH2CH2CH2NH]nH, in which n is an integer of 1 or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more).

[0277] In some embodiments, the polyamine is or includes oligomeric or polymeric forms of ethyleneimine. In some embodiments, the polyamine is or includes -[CH2CH2NH]n-, in which n is an integer of 1 or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more). In some embodiments, the polyamine is or includes -[CH2CH2NRA]n-, in which RA is an amine moiety (e.g., any described herein) and n is an integer of 1 or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more). In some non-limiting embodiments, RA is -Ak-NRN1RN2 or -Ak-N(-Ak-NRN1RN2)2 or -Ak-NRN1-Ak-NRN2RN3, in which N is nitrogen, Ak is optionally substituted alkylene and each of Rn1, RN2, and RN3 is any described herein.

[0278] FIGS. 2H-2K provide non-limiting, general examples of polyamine chains that can serve as a poly amine of the present disclosure. The poly amines of FIGS. 2H and 21 include repeating units composed of amine groups (e.g., -NH-, -NRn1-, -NH2, or -NRN1RN2) and linkers. In some examples, the linker is a carbon aliphatic -(CH2)n- spacer groups, in which n is an integer greater than one (e.g., an integer from 1 to 20, 1 to 10, 1 to 12, 1 to 6, etc.). FIG. 2H shows an n-propylene (-CH2CH2CH2-) (CsHe) spacer group. FIG. 21 shows an ethylene (-CH2CH2-) (C2H4) spacer group. The polyamine has a repeating chain portion (bracketed) having a length of n active groups in the chain portion of the polymer (e.g., if n = 2, there are two repeating groups in the chain portion). Other linkers can be used, such as any described herein (e.g., optionally substituted alkylene, as described herein), as well as linkers having peptidic bonds (e.g., -C(O)NH-) or glycosidic linkages. Linkers can include peptides, polysaccharides, and the like. Furthermore, in some embodiments the polyamine includes linear or branched structures, such as those present in linear polymers, branched polymers, block polymers, or dendrimers.

[0279] FIGS. 2H-2I depict a polyamine having a length of n active groups in the repeating chain portion. FIGS. 2H-2I also depict the repeating chain portion including two non-limiting amine groups (-N(X)-), separated by either C3 (FIG. 2H) or C2 (FIG. 21) spacer groups. In NX, X is any side group, reactive group, leaving group, or other group described herein. For example, in some emboidments X is H, optionally substituted aliphatic, heteroaliphatic, aromatic, and the like. Furthermore, in some embodiments X further includes an amine groups. Thus, in some non-limiting embodiments, X is any RA group described herein (e.g., an aminoalkyl group, an alkylaminoalkyl group, and the like). FIG. 21 depicts the amine groups extending in different orientations from the carbon chain, whereas FIG. 2H depicts the amine groups extending in similar orientations.

[0280] In some embodiments the polyamine is derived from natural polymers having amine moieties. For example, FIG. 2J is an example of a poly(lysine), and FIG. 2K is an example of a natural chitosan.

[0281] In some embodiments, the amine moieties present in a polyamine interact with other moieties, groups, or compounds present in proximity to the substrate surface. In some embodiments, amine moieties of the polyamine interact with silane moieties (e.g., silanol groups or other groups) present in an aminosilane. In other embodiments, amine moieties of the polyamine interact with moieties of other polyamines, aminosilanes, or other groups present in proximity to the surface. Such interactions include covalent or non-covalent interactions (e.g., hydrogen bonding, ionic interactions, and / or others described herein) to form a network over the surface of the substrate.

[0282] In some embodiments, the polyamine is a polymeric / oligomeric amine or a mixture including polymeric / oligomeric amine, such as poly(ethyleneimine) (PEI), poly(propyleneimine) (PPI), or a multiple amine mixture (e.g., a mixture including a plurality of amines (e.g., polyamines and / or monoamines), such as Amix 1000, CAS No. 68910-05-4, as produced by BASF SE, Ludwigshafen, Germany). In some embodiments, the polyamine is a small molecule including amine moieties (e.g., small molecule amines), an oligomer including amine moieties (e.g., an oligomeric amine), or an oligomeric including ethylene amine moieties (e.g., an oligomeric ethylene amine), such as tetraethylenepentamine (TEPA), triethylenetetramine (TETA), diethylenetriamine (DETA), ethylenediamine, polymers or oligomers of monoethanolamine, polymers or oligomers of diethanolamine, polymers or oligomers of triethanolamine, 2-(2-aminoethylamino)ethanol, piperazine, 2-piperazin-l-ylethylamine, 2-piperazin-l-ylethanol, pentaethylenehexamine, tetramethylethylenediamine, or others described herein.

[0283] In some embodiments, the polyamine is a small molecule polyamine. In some embodiments, the small molecule polyamine is characterized by a boiling point being sufficiently high that the compounds are not lost due to a high volatility. In some embodiments, the small molecule polyamine has a boiling point of at least 170 °C. In some examples, these compounds have reduced compound cost compared to alternatives.

[0284] In some embodiments, a mixture of one or more amines described herein (e.g., an aminosilane, a polyamine such as a high molecular weight polyamine or a small molecule polyamine, and / or a monoamine) is employed, in which the presence of such amines provides a polymer or an oligomer. In some embodiments, the mixture further includes an alcohol (e.g., ROH, in which R is optionally substituted aliphatic, alkyl, hydroxyalkyl, heteroaliphatic, heteroalkyl, aromatic, or aryl).

[0285] d. Monoamines

[0286] As described herein, the functional portion can be provided by any useful compound or combination of compounds. In some embodiments, the compound is a monoamine. In some embodiments the monoamine is any compound or moiety having one amine group (e.g, -NRN1RN2, in which RN1 and RN2 can be any described herein). In some embodiments the amine group is attached to a linker (c.g, any described herein).

[0287] In certain embodiments, the monoamine is provided to the substrate to act as an interaction moiety or an adsorbing moiety.

[0288] In some embodiments, the monoamine includes an aminosilane having one amine group. Other examples of monoamine compounds include an alkanolamine (e.g., HO-Ak-NRN1RN2, in which N is nitrogen, Ak is optionally substituted alkylene and each of RN1 and RN2 is any described herein, such as monoethanolamine) or an alkylamine (e.g., Ak-NRN1RN2, in which Ak is optionally substituted alkyl and each of RN1 and RN2 is any described herein, such as ethylamine or hexylamine), and the like. In some embodiments, the monoamine is a compound having a structure of formula Rc1Nr1RN2, in which each of RN1 and RN2 is any described herein and RC1 is optionally substituted aliphatic, heteroaliphatic, alkyl, aromatic, heteroaromatic, or aryl, where the optional substituent is not amino, as defined herein, or where RC1 does not comprise amino, as defined herein.

[0289] e. Crosslinking Agent

[0290] As described herein, the functional portion can be provided by any useful compound or combination of compounds. In some embodiments, the compound is a crosslinking agent. The crosslinking agent forms interactions between functional groups to form a three-dimensional network of connected molecules. In the embodiments described herein, the crosslinking agent forms interactions between one or more of the adsorbing moieties, the interaction moieties, the substrate, or a combination thereof.

[0291] In some embodiments, the structure of crosslinking agent is given by formula (VII): Rxl-L-[RXn]n (VII), where each RX1 and RXn is, independently, a reactive group (e.g., any described herein), L is a linking moiety (e.g., any linker described herein, such as terephthalaldehyde), and n is an integer from 0 to 5. Upon reacting the reactive moieties with one or more amine groups in a functional material, a linking moiety L is provided within the functional material. In some embodiments, one or more amine groups are present in the surface modification layer, and one or more linking moieties are bound (e.g., covalently bound) to at least one of the one or more amine groups.

[0292] Non-limiting examples of reactive groups include hydrogen (H), formyl (-C(O)H), halo (e.g., F, Cl, Br, or I), hydroxyl (e.g., -OH), carboxyl (e.g., -CO2H), isocyanato (e.g., -NCO), optionally substituted alkanoyl, optionally substituted halocarbonyl, optionally substituted oxiranyl, optionally substituted heterocyclyl, optionally substituted cyclic anhydride, optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted hydroxyalkyl, optionally substituted alkoxy (e.g., -OR, in which R is an optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, in which R is an optionally substituted aryl), optionally substituted alkanoyloxy, trialkylsilyloxy (e.g., -OSiR3, in which each R is independently an optionally substituted alkyl), or trialkoxylsilyloxy (e.g., -OSi[OR]3, in which each R is independently an optionally substituted alkyl).

[0293] In some embodiments, each of RX1 and RXn is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0294] Examples of linking moieties include e.g., a covalent bond, an atom (e.g., methylene, carbonyl, oxy, thio, imino, and the like), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene. Other examples of linking moi eties include any described herein (e.g., described herein for L, L1, L2, and L3). The linker can be flexible or rigid.

[0295] In some embodiments, L is optionally substituted aliphatic, heteroaliphatic, alkyl, aromatic, heteroaromatic, or aryl.

[0296] In some embodiments, n is 2. In other embodiments, n is 3. In yet other embodiments, n is 4.

[0297] In some embodiments, RX1 and RXn are the same. In some embodiments, RX1 and RXn are different.

[0298] In some embodiments, each of RX1 and RXn is formyl; and n is 2, 3, or 4.

[0299] In some embodiments, each of RX1 and RXn is halo; and n is 2, 3, or 4.

[0300] In some embodiments, each of RX1 and RXn is isocyanato; and n is 2, 3, or 4.

[0301] In some embodiments, each of RX1 and RXn is optionally substituted halocarbonyl (e.g., in which X is Cl); and n is 2, 3, or 4.

[0302] In some embodiments, each of RX1 and RXn is optionally substituted oxiranyl; and n is 2, 3, or 4.

[0303] In some embodiments, each of RX1 and RXn is optionally substituted heterocyclyl; and n is 2, 3, or 4.

[0304] In some embodiments, each of RX1 and RXn is optionally substituted cyclic anhydride; and n is 2, 3, or 4.

[0305] An example of the crosslinking agent is a dialdehyde. A dialdehyde is an organic chemical compound with two aldehyde groups. In some embodiments, the dialdehyde includes a structure having the formula (Vila) or (Vllb): HC(O)-L-C(O)H          (Vila) or HC(O)-La-Rnl (Vllb), where L is any described herein, Rnl is any described herein; and La is optionally substituted with a formyl group. In some embodiments, La is optionally substituted with one or more formyl groups. Non-limiting examples of aldehyde groups include formaldehyde, terephthalaldehyde, glutaraldehyde, and glyoxal.

[0306] Examples of dialdehyde include 2,5-diformylfuran: glutaraldehyde: glyoxal: hexanedial: 1,3-phenylenediacetaldehyde: and terephthalaldehyde (TALD; 1,4-benzenedicarbaldehyde):

[0307] Examples of the use of TALD as a crosslinking agent are described in Examples 5 and 6.

[0308] Another example of the crosslinking agent is a diisocyanate. A diisocyanate is an organic chemical compound with two isocyanate groups. In some embodiments, the diisocyanate includes a structure having the formula (Vile) or (Vlld): O=C=N-L-N=C=O        (Vile) or OCN-La-Rnl         (Vlld), where L is any described herein; Rnl is any described herein; and La is optionally substituted with an isocyanato group. In some embodiments, La is optionally substituted with one or more isocyanato groups. Non-limiting examples of diisocyanates include 2,4-diisocyanatotoluene (TDI): 2,6-diisocyanatotoluene (TDI): methylene diphenyl diisocyanate (4,4'-diisocyanatodiphenylmethane) (MDI): hexamethylene diisocyanate (HDI): isophorone diisocyanate: a trimethylhexamethylene diisocyanate such as: cyclohexane diisocyanate: and xylylene diisocyanate (meta-xylylene diisocyanate):

[0309] Additional examples of isocynanates are Trixene BI 7960 and Trixene Bl 7961 (Baxenden Chemicals Ltd., Lancashire, United Kingdom) described in Example 9.

[0310] Another example of the crosslinking agent is a dihaloalkane. A dihaloalkane is an organic chemical compound with two haloalkane groups. In some embodiments, the halo groups are provided at the terminus of the alkylene moiety. In some embodiments, the dihaloalkane includes a structure having the formula (Vile) or (Vllf): X-L-X             (Vile) or X-La-Rnl             (Vllf), where L is any described herein, each X is, independently, halo (e.g., fluorine, chlorine, bromine, or iodine); Rnl is any described herein; and La is optionally substituted with a halo groups. In some embodiments, La is optionally substituted with one or more halo groups. In some embodiments, L or La is optionally substituted alkylene. In some embodiments, L is unsubstituted alkylene. Non-limiting examples of dihaloalkanes include 1,4-dibromobutane: 1,2-dibromoethane: and 1,5-dibromopentane:

[0311] FIG. 2L depicts a non-limiting example of a dihaloalkane having two potential reactive groups (denoted as X) and two potential substituents (denoted as R1 and R2).

[0312] Additional examples of dihaloalkanes are of the formula: where Xi and X2 are each, independently, F, Cl, Br, I, and n is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Example 11 illustrates the use the alkyl bromide alpha alpha' dibromo-xylene (1,2- bis(bromomethyl)benzene) as a cross-linker:

[0313] Another example of the crosslinking agent is an epoxide, or a compound containing an optionally substituted oxiranyl functional group. An epoxide is a reactive cyclic ether. In some embodiments, the epoxide includes a structure having the formula (Vllg): R1R2C[O]CR3R4           (Vllg), where each of R1, R2, R3, and R4 is, independently, any functional group described herein. In some embodiments, each of R1, R2, R3, and R4 is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0314] Another example of the crosslinking agent is a diepoxide, or a compound containing two optionally substituted oxiranyl functional groups. In some embodiments, the di epoxide includes a structure having the formula (Vllh) or (Vlli): RX1-L-RX2          (Vllh) or RXl_La_Rnl where L is any described herein, each RX1 and RX2 is, optionally substituted oxiranyl, Rnl is any R described herein; and La is optionally substituted with an optionally substituted oxiranyl group. In some embodiments, La is optionally substituted with one or more optionally substituted oxiranyl groups. Non-limiting examples of epoxides include 1,2-propylene oxide, epichlorohydrin, and bisphenol A. Non-limiting examples of di epoxides in accordance with the present disclosure include diglycidyl ether: ethylene glycol diglycidyl ether: 3,4-epoxycy cl ohexylmethyl-3,4-epoxy cyclohexane carboxylate (and cis-isomers, transisomers, and mixed stereochemistry thereof): neopentyl glycol diglycidyl ether: and l,4-bis(oxiran-2-ylmethyl)butane (1,4-butanediglycidyl) :

[0315] Example 8 illustrates the use of various epoxy (diexpoxy) crosslinking agents.

[0316] FIG. 2M depicts an example of an epoxide 220 having four potential reactive groups 222 (denoted as R^R4).

[0317] Another example of the crosslinking agent is a dianhydride. A dianhydride is an organic chemical compound with two anhydride groups. In some embodiments, each anhydride group includes two acyl groups bonded to the same oxygen atom. An example of a dianhydride is ethylenediaminetetraacetic (EDTA) dianhydride. In some embodiments, the dianhydride includes a structure having the formula (Vllj) or (Vllk): RX1-L-RX2           (Vllj) or RXl_La_Rnl where L is any described herein; each RX1 and RX2 is, an optionally substituted cyclic anhydride group; Rnl is any described herein, and La is optionally substituted with an optionally substituted cyclic anhydride group. In some embodiments, La is optionally substituted with one or more optionally substituted cyclic anhydride groups. Non-limiting examples of anhydrides include glutaric anhydride, succinic anhydride, and ethyl enedi aminetetraaceti c di anhydri de.

[0318] Nonlimiting examples of dianhydrides in accordance with the present disclosure include methylene dianhydride (MD A; 2,2'-oxy dioxy diethanone): benzophenone-3,3',4,4'-tetracarboxylic dianhydride (2,2'-(4-oxocyclohexa-2,5-dien-l-ylidene)bi s(benzenecarboxylic acid): 3,3',4,4'-biphenyl dianhydride (2,2'-dicarboxy-4,4'-dioxo-[l,l'-biphenyl]-3,3'-dicarboxylic acid anhydride): 4,4'-oxy diphthalic anhydride: and 1,2,3,4-cyclohexane tetracarboxylic dianhydride such as:

[0319] Example 12 illustrates the use of the dianhydride 3,3',4,4'-biphenyltetracarboxylic dianhydride as a crosslinker.

[0320] Another example of the crosslinking agent is a diacid chloride. A diacid chloride is an organic chemical compound with two chlorocarbonyl functional groups. In some embodiments, the diacid chloride includes a structure having the formula (VIII) or (Vllm): C1C(O)-L-C(O)C1    (VIII) or ClC(O)-La-Rnl       (Vllm), where L is any described herein, Rnl is any described herein; and La is optionally substituted with a chlorocarbonyl group (e.g., -C(O)C1). In some embodiments, La is optionally substituted with one or more optionally substituted chlorocarbonyl groups. Non-limiting examples of diacid chlorides include succinyl chloride: glutaryl chloride: adipoyl chloride: sebacoyl chloride: and terephthaloyl chloride:

[0321] Example 10 illustrates the use of an diacid chloride (acid chloride) as a crosslinker.

[0322] Another example of the crosslinking agent is a diacrylate. An example of a diacrylate is 1,6-hexanediol diacrylate:

[0323] Additional examples of diacrylates used as crosslinking agents are provided in Example 7.

[0324] Hi. Interaction of moieties, groups, or compounds

[0325] Any combination of moieties, groups, or compounds can be used to provide a functional portion. In some embodiments, the functional portion is provided as a coating or a surface modification layer, which in turn can be formed from a complex network of interactions between one or more silanes, aminosilanes, polymeric / oligomeric amines, monoamines, and / or surfaces of the substrate (e.g., a silica substrate).

[0326] In some embodiments, interactions form between a surface of a substrate and a silane moiety (e.g., present in any silane, aminosilane, polymeric silane, or polymeric aminosilane described herein). In instances when the silane moiety is provided by a (poly)aminosilane, the silanol moieties on a silica surface may react with the silane moiety to form siloxane linkages, which are non-limiting examples of covalent bonds. In some embodiments, such silanol moieties are acidic and are deprotonated by basic amine moieties of the (poly)aminosilane to form an acid-base pair, which is a non-limiting example of an ionic interaction. In some embodiments, silanol moieties (on silica) and silanol and amine moi eties (on (poly)aminosilanes) form a variety of hydrogen bonding interactions (e.g., by way of hydrogen bonding). In the case of large polymeric silanes, the sum of these interactions is significant in some embodiments. In some embodiments the silica and (poly)silanes are polar and possess weak dipole-dipole interactions. In the case of large polymeric silanes, the sum of these interactions is significant in some embodiments.

[0327] In some embodiments, interactions form between the substrate surface and an amine moiety (e.g., present in any aminosilane, polyamine, or a monoamine described herein). In instances when the amine moiety is provided by a polyamine, silanol moieties on the silica surface are acidic and are deprotonated by the basic amine moieties of the polyamine to form acid-base pairs, which are non-limiting examples of ionic interactions. Silanol moieties (on silica) and amine moieties (on polyamines) form a variety of hydrogen bonding interactions in some embodiments. In some embodiments the silica and polyamines are polar and possess weak dipole-dipole interactions. Due to the large branching shape of some non-limiting polyamines, the sum of these weak interactions is significant when the polyamine adheres to or otherwise interacts with the silica surface in some embodiments.

[0328] In some embodiments, interactions form between substrate surfaces (e.g., a first surface and a second surface of a silica substrate). In instances when the substrate comprises silica, silica-silica interactions contribute to the formation and strength of the silica substrate in some embodiments. In some embodiments, silica substrates are composed of a single polymeric silica-dioxide molecule. In the case of precipitated silica, the silica substrate is e composed of a great number of small nucleites that are entangled into larger aggregates and finally agglomerated into the full particle and held together by physical interactions in some embodiments. In some embodiments silicon dioxide forms siloxane (-Si-O-Si-) linkages between individual silicon atoms, in which such siloxane linkages are non-limiting examples of covalent bonds. In some embodiments silica nucleites and aggregates are physically entangled and agglomerated to form substrate particles, in which such entanglement and agglomeration interactions are non-limiting examples of physical interactions. The surface of silica nucleites and aggregates include silanol moieties that form many hydrogen bonding interactions that promote cohesion in some embodiments. In some embodiments such silica nucleites and aggregates are polar and form cohesive dipole-dipole interactions.

[0329] In some embodiments, interactions form between silane moieties (e.g., present in any silane, aminosilane, or polymeric aminosilane described herein). In instances when the silane moieties are provided by alkoxysilane groups or silanol groups, the silane moieties react with each other to form siloxane condensation bonds in some embodiments. Both a silica surface and silanes can include silanol moieties that can condense to form siloxane bonds in some embodiments. This process is repeated many times to form branching polysilane networks having covalent bonds in some embodiments. In some embodiments silanols or polysilanes include acidic silanol moieties that are deprotonated by basic amine moieties (e.g., present in aminosilane) to form acid-base interactions, which are non-limiting examples of ionic interactions. In some embodiments the silanols or poly silanes of the present disclosure have silanol and amino moieties that form a variety of hydrogen bonding interactions. In some embodiments large branching polysilanes become physically entangled with each other. In some embodiments silanols and polysilanes are polar molecules and possess weak dipole-dipole interactions with each other. In the case of large branching poly silanes, the sum of these weak interactions is significant in some embodiments.

[0330] In some embodiments, interactions form between amine moieties (e.g., present in any amine, polyamine, aminosilane, or polymeric aminosilane). In instances when the amine moieties are provided by polyamines, polyamines have a variety of amine moieties that can donate and accept hydrogen bonds in some embodiments. Since polyamines are polymers, a higher number of these intermolecular interactions are possible (e.g., by way of hydrogen bonding) in some embodiments. Large polyamines become physically entangled with each other in some embodiments. In some embodiments polyamines are polar molecules and possess some weak dipole-dipole interactions with each other. In the case of large branching shapes present in some poly amines, the sum of these interactions can be significant in some embodiments.

[0331] In some embodiments, interactions form between an amino moiety (e.g., present in any amine, polyamine, aminosilane, or polymeric aminosilane), and a silane moiety (e.g., present in any silane, polymeric silane, aminosilane, or polymeric aminosilane). In instances when the amine moieties are provided by polyamines, polyamines have a plurality of basic amine moieties, which can deprotonate acidic silanol moieties (in (poly)silane) to form acid-base interactions in some embodiments. In the case of large polyamines interacting with large polysilanes, the sum of these interactions is even more significant (e.g., by way of ionic interactions) in some embodiments. In some embodiments, polyamines have many amine moieties, that form a variety of hydrogen bonding interactions with silanol moieties (in (poly)silane) and amine moieties. In the case of large polyamines interacting with large poly silanes, the sum of these interactions is even more significant (hydrogen bonding) in some embodiments. In some embodiments, polyamines and (poly)silanes are polar molecules and possess some weak dipole-dipole interactions with each other. In the case of large polyamines interacting with large poly silanes, the sum of these interactions is significant in some embodiments.

[0332] iv. Additives

[0333] In some embodiments the compositions of the present disclosure further include additives. Such additives include any described herein, including one or more chelating agents, antioxidants, and the like.

[0334] In some embodiments, additives are included in the functionalization mixtures to extend the operational lifetime of the functionalized material. For example, the addition of bis[3-(trimethoxysilyl)propyl]amine (BTMSPA) to the mixture increases the operational lifetime of the functionalized material of the present disclosure in some embodiments. BTMSPA is an aminosilane having two ends, in which each end has a trimethoxysilyl reactive group. The BTMSPA bonds on the substrate with six binding points, as contrasted with the three binding points for an aminosilane with a single reactive group, such as would be present in a compound having a methoxydialkylsilyl reactive group. The increased number of binding points increases binding stability with the silica substrate in some embodiments. The BTMSPA forms a network with other aminosilanes and polyamines on the surface that increases binding stability of the overall network in some embodiments.

[0335] Other examples of additives include a polyamine (e.g., any described herein). Yet other examples of additives include l,2-bis(triethoxysilyl)ethane (BTESE), other bisaminosilane compounds (e.g., X1X2X3Si-L1-NRN-L2-SiX4X5X6, in which each of X1, X2, X3, X4, X5, and X6 is any described herein for X; each of L1 and L2 is any described herein for L; and RN is any described herein for RN1), or other bissilane compounds (e.g., X1X2X3Si-L1-SiX4X5X6, in which each of X1, X2, X3, X4, X5, and X6 is any described herein for X and L1 is any described herein for L).

[0336] In some embodiments, the functionalized material includes antioxidant additives. Without wishing to be limited by theory, an additive prevents the degradation of the amine moieties by atmospheric oxygen and / or extends the cycling lifetime of the functionalized material of the present disclosure in some embodiments. For example, in some embodiments the antioxidant additives are organic sulfur-containing compounds, such as 2,2-thiodiethanol, 2-hydroxyethyl disulfide, and 3,3’-dithiodipropionic acid. In some embodiments, the organic sulfur-containing compound has the formula R’SR” or R’SSR” or R’S-L-SR”, in which each ofR’ andR” is, independently, aliphatic, alkyl, hydroxyalkyl, carboxyalkyl, aromatic, aryl, hydroxyaryl, or carboxyaryl (e.g., as defined herein), in which each of these is optionally substituted; and L is a linker (e.g., any described herein).

[0337] Another example of antioxidant additives is a metal catalyst chelator. Without wishing to be limited by theory or mechanism, transition metal impurities (e.g., such as iron or copper) increase the oxidation rate of amine moieties, which in turn reduces the lifetime of the sorbent. In some embodiments, a catalyst chelator includes, e.g., a phosphate or phosphonate alkali salt (e.g., a phosphate or phosphonate sodium salt), an aminopoly carboxylic acid or a salt thereof (e.g., ethylenediaminetetraacetic acid tetrasodium salt dihydrate or di ethylenetriaminepentaacetic acid), a phosphonic acid or a salt thereof (e.g., 1-hydroxyethane 1,1-diphosphonic acid monohydrate or ethylenediamine tetramethylene phosphonic acid), a mercapto acid (e.g., meso-2,3-dimercaptosuccinic acid, and the like. In some embodiments, one or more catalyst chelators is used to reduce the oxidation rate and improve sorbent lifetime.

[0338] In general, the amount of antioxidant additives in the functionalized material is 5% (wt / wt) to the substrate (e.g., 3%, 4%, 6%, or 8% (wt / wt)). In some embodiments the antioxidant additives is added during any useful step (e.g., during formation of the suspension mixture or the functionalization mixture) of the following synthesis procedure or afterward (e.g., through dissolving in a solvent, such as an alcohol like methanol, and then soaking the functionalized material in the additive / solvent mixture for 1 hour).

[0339] In some embodiments, the functionalized material includes, or is functionalized with, other hydrophobic compounds including hydrophobic silanes or hydrophobic polymer coatings. In some embodiments, the hydrophobic silane includes one, two, or three alkyl chains. In particular embodiments, the hydrophobic silane includes R'R2R3SiX' or [R^aSifX1]^, in which each of R1, R2, and R3 is independently an optionally substituted aliphatic, alkyl, aromatic, or aryl; X1 is a side group, a reactive group, or a leaving group (e.g., any described herein for X); and a is 1, 2, or 3. Without wishing to be limited by theory, alkyl chains on the silane molecule increases the hydrophobicity of the silane molecule in some embodiments. When the silane molecule is bonded to the substrate, it increases the hydrophobicity of the functionalized material as well in some embodiments. Thus, the water adsorption capacity of the functionalized material is reduced, which is beneficial for some cases such as when using the sorbent in high humidity conditions in some embodiments. For the same purpose of increasing the hydrophobicity of the functionalized material, additional hydrophobic polymer coatings are used in some embodiments. Polydimethylsiloxane (PDMS), silicone oil, polyethylene, polypropylene, poly(tetrafluorethylene), and polyurethane are examples of hydrophobic polymers that re used to coat the outer surface of the functionalized silica to reduce water adsorption for high humidity applications in some embodiments.

[0340] v. Characteristics

[0341] In some embodiments the functionalized material of the present disclosure is used as a sorbent, which in turn can has any useful characteristics (e.g., any described herein).

[0342] In some embodiments, the crosslinked sorbent adsorbs CO2 at concentrations similar to non-enhanced sorbents, enabling efficient capture at levels present in atmospheric conditions using stronger, longer-lasting products.

[0343] In some embodiments, the crosslinked sorbent has increased mechanical durability compared to non-enhanced sorbents such as increased crush strength and resistance to abrasion, thus increasing the useful lifespan of the sorbent and reducing the production of fines and sorbent particulates.

[0344] In some embodiments, crosslinking sorbent amines reduces amine volatility thereby reducing amines lost during vacuum desorption of adsorbed CO2 from the functionalized material.

[0345] In some embodiments, crosslinking sorbent amines enhances sorbent oxidation resistance which improves operational lifetimes of the functionalized material thereby increasing adsorption / desorption cycle counts for the functionalized sorbent.

[0346] In some embodiments, crosslinking sorbent amines reduces amine leaching thereby reducing environmental release of free amines and reducing the environmental impact of the functionalized material.

[0347] In some embodiments, the functionalized material adsorbs CO2 at low concentrations enabling increased capture at levels present in atmospheric conditions. Capturing CO2 from atmospheric conditions can facilitate employing the functionalized material in a large number of applications.

[0348] In some embodiments, CO2 is desorbed from the functionalized material at laboratory temperatures. This can reduce the energy required to remove captured CO2, increase the applicability of the functionalized material to more industries and environments, and / or increase the speed at which the CO2 is desorbed.

[0349] In some embodiments, the functionalized material achieves high adsorption / desorption counts, which reduces operational costs in carbon capture systems. In some embodiments the functionalized material is enabled for repeated use of the substrate.

[0350] In some embodiments, the functionalized material is produced using industrially available components, reducing the cost of and increasing the scalability of production.

[0351] In some embodiments, the functionalized material includes polymeric, oligomeric, or molecular sources with high densities of amine functionality that increase uptake of CO2 per weight of dry sorbent.

[0352] In some embodiments, functionalizing the substrate with an aminosilane compound increases the binding stability of the polymeric, oligomeric, or high density amine source, thereby increasing the useful lifespan of the functionalized material.

[0353] In some embodiments, functionalizing the substrate with a polyamine (e.g., a high molecular weight polyamine) increases the binding stability, as compared to short chain amine functionalization (e.g., employing an oligomeric amine or a small molecular weight amine having at least two amine moi eties and having a molecular weight from 100 to 800 g / mol).

[0354] In some embodiments, functionalizing the substrate with a small molecule polyamine (e.g., an oligomeric amine, an oligomeric ethylene amine, or an ethylene amine / oligomer mixture compound) decreases the cost of the functionalized substrate and facilitates large-scale functionalization of the substrate.

[0355] In some embodiments, polyamine sources have an increased amine density and are commercially available which increases cost effectiveness of the use of polyamine functionalized materials as sorbents.

[0356] In some embodiments, the functionalized material is produced in a single-pot reaction in short time scales to reduce the cost of production, reduce reliance on industrial solvents, and / or reduce the environmental impact of the product.

[0357] In some embodiments, the functionalized material is produced in a single-pot reaction in short time scales and using only water as a solvent to reduce the cost of production, reduce reliance on industrial solvents, and / or reduce the environmental impact of the product.

[0358] In some embodiments, the functionalized material is produced in a water-based, single-pot reaction at ambient pressures and temperatures in short time scales (e.g., using a dip-coating process) to reduce the cost of production, reduce reliance on industrial solvents, and / or reduce the environmental impact of the product.

[0359] In some embodiments, the compositions of the present disclosure adsorb atmospheric CO2 (e.g., to an adsorbing moiety, such as an amine moiety) in a first temperature range and can desorb previously adsorbed CO2 (e.g., from an adsorbing moiety, such as an amine moiety) in a second temperature range higher than the first temperature range. The second temperature range can be between 65 °C and 90 °C.

[0360] In some embodiments, the compositions of the present disclosure adsorb atmospheric CO2 (e.g., to an adsorbing moiety, such as an amine moiety) at a first gas pressure for CO2 and desorb previously adsorbed CO2 (e.g., from an adsorbing moiety, such as an amine moiety) at a second gas pressure for CO2 that is lower than the first gas pressure. In some embodiments, the second gas pressure is below 1.5 psi (e.g., for functionalized silica or other functionalized material described herein). In some embodiments, the second gas pressure is below 0.3 psi (e.g., for functionalized MOF or other functionalized material described herein). The first and second gas pressure relate to the pressure for CO2. Thus, when other gases are present in proximity of the sorbent, the first gas pressure and the second gas pressure relate to the partial pressure for CO2.

[0361] In some embodiments, the composition adsorbs atmospheric CO2 (e.g., to an adsorbing moiety, such as an amine moiety) at a first CO2 concentration and desorbs previously adsorbed CO2 (e.g., from an adsorbing moiety, such as an amine moiety) at a second CO2 concentration lower than the first CO2 concentration. In some embodiments the first CO2 concentration is below 420 ppm or below 400 ppm.

[0362] In some embodiments, the composition comprises or consists essentially of porous silica particles as a substrate. In some embodiments the porous silica particles include a plurality of pores. In some embodiments the plurality of pores have a dimension (e.g., a diameter) in the range between 60 A and 400 A or between 20 A and 1000 A. In some embodiments the pores have a size in the range between 100 A and 150 A. In some embodiments the plurality of pores can have a volume that is greater than 0.5 mL / g. In some embodiments the porous silica particles have a total surface area greater than 100 m2 per dry gram. In some embodiments the porous silica particles have an average diameter in the range between 25 pm asnd 3 mm or between 25 pm and 4 mm.

[0363] In some embodiments, the porous silica particles have a greatest dimension in the range between 70 pm and 80 pm. In some embodiments the porous silica particles include a plurality of pores, and the plurality of pores have volume greater than 0.8 mL / g and a size of at least 90 A.

[0364] In some embodiments, the compositions of the present disclosure comprise or consist essentially of MOF particles as a substrate. In some embodiments the MOF particles include a plurality of pores. In some embodiments the plurality of pores have a dimension (e.g., a diameter) in the range between 30 A and 400 A. In some embodiments the plurality of pores have a volume greater than 0.5 mL / g. In some embodiments the MOF particles have a total surface area greater than 100 m2 per dry gram. In some embodiments MOF particles have an average diameter in the range between 10 pm and 1 mm or between 50 and 100 pm.

[0365] In some embodiments, the compositions of the present disclosure comprise or consist essentially of resin as a substrate. In some embodiments the resin includes a plurality of pores. In some embodiments the plurality of pores have a dimension (e.g., a diameter) in the range between 1 nm and 200 nm. In some embodiments the plurality of pores have a volume greater than 0.5 mL / g. In some embodiments the resin has a total surface area greater than 100 m2 per dry gram. In some embodiments the resin has an average diameter in the range between 25 pm and 4 mm.

[0366] In some embodiments, the compositions of the present disclosure adsorb between 0.5 mol and 2.5 mol of CO2 per dry kilogram (mol CO2 / kg), between 0.5 mol CO2 / kg and 2 mol CO2 / kg, or between 1 mol CO2 / kg and 2 mol CO2 / kg. In some embodiments the compositions of the present disclosure adsorb CO2 at a relative humidity in the range between 0% relative humidity (RH) and 100% RH, between 5% RH and 95% RH, or between 5% RH and 90% RH (e.g., for functionalized silica or other functionalized material described herein) or between 0% RH and 100% RH or between 5% and 60% RH (e.g., for functionalized MOF, functionalized resin, or other functionalized material described herein).

[0367] In some embodiments, a sorbent of the present disclosure is reused through the desorption process. For example, in some embodiments any of the sorbents of the present disclosure is reused 100 times or more (e.g., 1000 times or more, 10000 times or more). For the desorption process, in some embodiments the sample (sorbent of the present disclosure) is heated to 70 °C under vacuum for 30 minutes or another duration (e.g., the duration is change based on temperature and / or vacuum level). This facilitates the CO2 captured during the adsorption process to be released, in which released CO2 is collected for further sequestration, described with reference to the systems for direct air capture herein. A non-limiting aspect of the desorption process of the present disclosure includes maintaining the sorbent to be heated under a water vapor filled vacuum environment (e.g., > 10% RH) in some embodiments. In some non-limiting embodiments, this reduces sorbent degradation.

[0368] When exposed to a gaseous mixture including CO2, the amine moiety (or other adsorbing moiety) of the sorbents of the present disclosure react with the CO2 to bond the CO2 to the functional portion. This thereby functionally adsorbs the CO2 to the substrate, in which the interaction moiety bonds the adsorbing moiety to substrate surface by way of covalent or non-covalent bonding interactions. Without wishing to be bound by theory, the total surface area, volume of the pores, and number of adsorbing moieties determines the adsorption capacity of the functionalized material of the present disclosure in some embodiments. The adsorption capacity (e.g., uptake) of the functionalized material of the present disclosure is in a range between 0.1 mol CO2 / kg and 2.5 mol CO2 / kg of functionalized material (e.g., between 0.1 mol CO2 / kg and 2 mol CO2 / kg, 0.1 mol CO2 / kg and 1.8 mol CO2 / kg, 0.1 mol CO2 / kg and 1.5 mol CO2 / kg, 0.1 mol CO2 / kg and 1.2 mol CO2 / kg, 0.1 mol CO2 / kg and 1.0 mol CO2 / kg, 0.1 mol CO2 / kg and 0.5 mol C02 / kg, 0.2 mol C02 / kg and 2 mol C02 / kg, 0.2 mol C02 / kg and 1.0 mol C02 / kg, 0.2 mol C02 / kg and 0.8 mol C02 / kg, 0.5 mol C02 / kg and 2.5 mol C02 / kg, 0.5 mol C02 / kg and 2.2 mol C02 / kg, 0.5 mol C02 / kg and 2 mol C02 / kg, 0.5 mol C02 / kg and 1.8 mol C02 / kg, 0.5 mol C02 / kg and 1.5 mol C02 / kg, 0.5 mol C02 / kg and 0.8 mol C02 / kg, 0.8 mol C02 / kg and 2.5 mol C02 / kg, 0.8 mol C02 / kg and 2.2 mol C02 / kg, 0.8 mol C02 / kg and 2 mol C02 / kg, 0.8 mol C02 / kg and 1.8 mol C02 / kg, 0.8 mol C02 / kg and 1.5 mol C02 / kg, 1 mol C02 / kg and 2 mol C02 / kg, 1 mol C02 / kg and 1.4 mol C02 / kg, 1 mol C02 / kg and 1.5 mol C02 / kg, 1.2 mol C02 / kg and 2.0 mol C02 / kg, 1.2 mol C02 / kg and 1.8 mol C02 / kg, 1.5 mol C02 / kg and 2.5 mol C02 / kg, 1.5 mol C02 / kg and 2 mol C02 / kg, or 2 mol C02 / kg and 2.5 mol C02 / kg). In some embodiments, the range is greater than 0.5, 1, 1.5, 2, or 2.5 mol C02 / kg. In some implementations, the functionalized material of the present disclosure achieves CO2 adsorption capacity up to 1 mol C02 / kg or up to 2 mol C02 / kg at 420 ppm CO2 in ambient air conditions.

[0369] In some implementations, the functionalized material (e.g., functionalized substrate including polyamine) achieves CO2 adsorption capacity in a range from 0.8 to 2.5 mol C02 / kg or 0.5 to 2.2 mol C02 / kg (e.g, from 1 to 2 mol C02 / kg, 1 to 1.5 mol C02 / kg, 1.5 to 2 mol C02 / kg, 1.5 to 2.5 mol C02 / kg, or 2 to 2.5 mol C02 / kg). In some implementations, the functionalized substrate achieves CO2 adsorption capacity up to 2 mol C02 / kg at 420 ppm CO2 in ambient air conditions.

[0370] In some implementations, the functionalized material (e.g., functionalized substrate including ethylene amine, oligomeric ethylene amine, or mixtures thereof) achieves CO2 adsorption capacity in a range from 0.5 to 1.8 mol C02 / kg or 0.5 to 2 mol C02 / kg (e.g., from 1.5 to 2 mol C02 / kg, 1.5 to 1.8 mol C02 / kg, 1 to 1.5 mol C02 / kg, or 1.2 to 1.8 mol C02 / kg). In some implementations, the functionalized substrate achieves CO2 adsorption capacity up to 2 mol C02 / kg at 420 ppm CO2 in ambient air conditions.

[0371] In some implementations, the functionalized material (e.g., functionalized substrate prepared by way of a dip-coating process) achieves CO2 adsorption capacity in a range from 1 to 2 mol CO2 / kg. In some implementations, the functionalized substrate achieves CO2 adsorption capacity up to 2 mol C02 / kg at 420 ppm CO2 in ambient air conditions.

[0372] In some implementations, the functionalized material (e.g., functionalized MOF) achieves CO2 adsorption capacity in a range from 0.8 to 2.5 mol CO2 / kg or 0.1 to 1 mol CO2 / kg (e.g., from 0.2 to 0.8 mol CO2 / kg). In some implementations, the functionalized MOF substrate achieves CO2 adsorption capacity up to 2 mol CO2 / kg at 420 ppm CO2 in ambient air conditions.

[0373] In some implementations, the functionalized material (e.g., functionalized resin) achieves CO2 adsorption capacity in a range from 0.8 to 2.5 mol CO2 / kg, 0.8 to 3 mol CO2 / kg, or 0.1 to 2.0 mol CO2 / kg (e.g, from 0.1 to 1.8 mol CO2 / kg, 0.1 to 1.5 mol CO2 / kg, 0.1 to 1.2 mol CO2 / kg, 0.1 to 1.0 mol CO2 / kg, 0.1 to 0.5 mol CO2 / kg, 0.2 to 1.0 mol CO2 / kg, 0.2 to 0.8 mol CO2 / kg, 0.5 to 2.0 mol CO2 / kg, 0.5 to 1.5 mol CO2 / kg, 0.5 to 0.8 mol CO2 / kg, 1.2 to 2.0 mol CO2 / kg, 1.2 to 1.8 mol CO2 / kg, or any ranges described herein). In some implementations, the functionalized resin achieves CO2 adsorption capacity up to 2 mol CO2 / kg at 420 ppm CO2 in ambient air conditions.

[0374] In environmental conditions, the atmosphere includes a concentration of water vapor (e.g., humidity). The functionalized material of the present disclosure is used to capture CO2 from atmospheric conditions in a range of RH levels in some embodiments. For example, in some embodiments of the present disclosure the functionalized material captures CO2 from atmospheric conditions in the range between 0% RH and 100% RH, such as for example between 5% RH and 95% RH (e.g., between 15% RH and 50% RH, between 25% RH and 40% RH, between 10% RH and 60% RH, between 5% RH and 90% RH, between 10% RH and 90% RH, or between 20% RH and 80% RH). In some embodiments, the functionalized material captures CO2 from atmospheric conditions having greater than 60% RH, greater than 75% RH, greater than 90% RH, or greater than 95% RH.

[0375] Described herein are functionalized materials, as well as methods of forming and using such materials (e.g., as a sorbent). In some embodiments, methods include forming or using a functionalized material including a porous structure that allows gas to diffuse through the material and that provides a large surface area for gas to be captured or “adsorbed.” Also described herein are systems for employing such materials in various capture processes. In some embodiments, systems include sample holder, reactors, adsorbers, desorbers, and the like that employ a functionalized material (e.g., any described herein) to adsorb carbon dioxide and / or that regenerate a functionalized material (e.g., any described herein) having adsorbed carbon dioxide.

[0376] Yet other functionalized material, methods, systems, and the like are provided in Int. Appl. No. PCT / US23 / 26724, filed June 30, 2023, which is incorporated herein by reference in its entirety.

[0377] vi. Chemical definitions

[0378] Unless otherwise specified, the term “material” is used to encompass compounds, molecules, structures (e.g., substrates or particles), or combinations thereof (e.g., a functionalized substrate).

[0379] As used herein, the term “moiety” is used to describe characteristic parts of organic molecules, compounds, or materials. For example, an amine moiety is a molecule, compound, or portion of a compound containing an amine group (e.g., - NRN1RN2, as described herein), whereas a silane moiety is a molecule, compound, or portion of a compound containing a silane group (e.g., -SiRslRS2RS3, as described herein). In one non-limiting instance, an amine moiety is an aminoalkyl group (e.g., -Ak-NRN1RN2, as described herein), as may be present in an aminosilane compound or a polyamine compound. In another non-limiting instance, an amine moiety includes an amino group alone (e.g., -NRN1RN2, as described herein). The term moiety is used to describe both larger molecules containing the group, or may be used to describe the group itself.

[0380] As used herein, “interact” is used to describe covalent or non-covalent interactions between chemicals, such as by way of physical adsorption or ionic interactions.

[0381] By “acyl” or “alkanoyl,” as used interchangeably herein, is meant an aliphatic or alkyl group, as defined herein, attached to the parent molecular group through a carbonyl group. In particular embodiments, the alkanoyl is -C(O)-Ak, in which Ak is an aliphatic or alkyl group, as defined herein. In some embodiments, an unsubstituted alkanoyl is a C2-7 alkanoyl group. Non-limiting examples of alkanoyl groups include acetyl.

[0382] By “acyloxy” or “alkanoyloxy,” as used interchangeably herein, is meant an acyl or alkanoyl group, as defined herein, attached to the parent molecular group through an oxy group. In particular embodiments, the alkanoyloxy is -O-C(O)-Ak, in which Ak is an aliphatic or alkyl group, as defined herein. In some embodiments, an unsubstituted alkanoyloxy is a C2-7 alkanoyloxy group. Non-limiting examples of alkanoyloxy groups include acetoxy.

[0383] By “acyl halide” is meant -C(O)X, where X is a halogen, such as Br, F, I, or Cl.

[0384] By “aliphatic” is meant a hydrocarbon group having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (C1-10), and which includes alkanes (or alkyl, e.g, as described herein), alkenes (or alkenyl), alkynes (or alkynyl), including cyclic versions thereof, and further including straight- and branched-chain arrangements, and all stereo and position isomers as well. Such a hydrocarbon can be unsubstituted or substituted with one or more groups, such as groups described herein for an alkyl group.

[0385] By “aliphatic-aryl” is meant an aryl group that is or can be coupled to a compound disclosed herein, where the aryl group is or becomes coupled through an aliphatic group, as defined herein. In some embodiments, the aliphatic-aryl group is -L-R, in which L is an aliphatic group, as defined herein, and R is an aryl group, as defined herein.

[0386] By “aliphatic-heteroaryl” is meant a heteroaryl group that is or can be coupled to a compound disclosed herein, where the heteroaryl group is or becomes coupled through an aliphatic group, as defined herein. In some embodiments, the aliphatic-heteroaryl group is -L-R, in which L is an aliphatic group, as defined herein, and Risa heteroaryl group, as defined herein.

[0387] By “alkenyl” is meant an optionally substituted C2-24 alkyl group having one or more double bonds. The alkenyl group can be cyclic (e.g., C3-24 cycloalkenyl) or acyclic. The alkenyl group can also be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting unsubstituted alkenyl groups include allyl and vinyl. In some embodiments, the unsubstituted alkenyl group is a C2-6, C2-8, C2-10, C2-12, C2-16, C2-18, C2-20, C2-24, C3-8, C3-10, C3-12, C3-16, C3-18, C3-20, or C3-24 alkenyl group. Non-limiting examples of alkenyl groups include vinyl or ethenyl (-CH=CH2), 1-propenyl (-CH=CHCH3), allyl or2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CH=CHCH3), 3-butenyl (-CH2CH2CH=CH2), 2-butenylidene (=CH- CH=CHCH3), and the like.

[0388] By “alkenylene” is meant a multivalent (e.g., bivalent) form of an alkenyl group, which is an optionally substituted C2-24 alkyl group having one or more double bonds. The alkenylene group can be cyclic (e.g., C3-24 cycloalkenyl) or acyclic. The alkenylene group can be substituted or unsubstituted. For example, the alkenylene group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting examples of alkenylene include -CH=CH- or -CH=CHCH2-.

[0389] By “alkoxy” is meant -OR, where R is an optionally substituted aliphatic or alkyl group, as described herein. Non-limiting examples of alkoxy groups include methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy, such as trifluoromethoxy, etc. The alkoxy group can be substituted or unsubstituted. For example, the alkoxy group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting examples of unsubstituted alkoxy include C1-3, C1-6, C1-12, C1-16, Ci-is, C1-20, or Ci-24 alkoxy groups.

[0390] By “alkoxyalkyl” is meant an alkyl group, as defined herein, which is substituted with an alkoxy group, as defined herein. Non-limiting examples of unsubstituted alkoxyalkyl groups include between 2 to 12 carbons (C2-12 alkoxyalkyl), as well as those having an alkyl group with 1 to 6 carbons and an alkoxy group with 1 to 6 carbons (i.e., C1-6 alkoxy-Ci-6 alkyl). In some embodiments, the alkoxyalkyl group is -L-O-R, in which L is an alkylene group, as defined herein, and R is an alkyl group, as defined herein.

[0391] By “alkyl” and the prefix “alk” is meant a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (i-Pr), cyclopropyl, n-butyl (n-Bu), isobutyl (i-Bu), s-butyl (s-Bu), t-butyl (t-Bu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. In some embodiments, the alkyl group is cyclic (e.g., C3-24 cycloalkyl) or acyclic. In some embodiments, the alkyl group is branched or unbranched. In some embodiments, the alkyl group is also substituted or unsubstituted. For example, in some embodiments, the alkyl group is substituted with one or more alkenyl, alkoxy, alkynyl, amino, aryl, carboxyaldehyde (e.g., -C(O)H), carboxyl (e.g., -CO2H), cyano (e.g., -CN), halo, nitro (e.g., -NO2), oxo (e.g., =0), and the like. In some embodiments, the alkyl group is substituted with one, two, three or, in the case of alkyl groups of two carbons or more, four substituents independently selected from the group consisting of: (1) C1-6 alkoxy (e.g., -O-R, in which R is C1-6 alkyl); (2) C1-6 alkylsulfinyl (e.g., -S(O)-R, in which R is C1-6 alkyl); (3) C1-6 alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (4) amine (e.g., -C(O)NR'R2 or -NHCOR1, where each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein); (5) aryl (e.g., C4-18 aryl); (6) arylalkoxy (e.g., -O-L-R, in which L is C1-6 alkylene and R is C4-18 aryl); (7) aryloyl (e.g., -C(O)-R, in which R is C4-18 aryl); (8) azido (e.g., - N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C3-8 cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6- or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -O-R, in which R is heterocyclyl, as defined herein); (15) heterocyclyloyl (e.g., -C(O)-R, in which R is heterocyclyl, as defined herein); (16) hydroxy (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =0); (20) C1-6 thioalkoxy (e.g., -S-R, in which R is alkyl); (21) thiol (e.g., -SH); (22) -CO2R1, where R1 is selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-i8 aryl (e.g., - L-R, in which L is C1-6 alkylene and R is C4-18 aryl); (23) -C(O)NR'R2, where each of R1 and R2 is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkylene and R is C4-18 aryl); (24) -SO2R1, where R1 is selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkylene and R is C4-18 aryl); (25) -SO2NR'R2, where each of R1 and R2 is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkylene and R is C4-18 aryl); and (26) -NR'R2, where each of R1 and R2 is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkylene and R is C4-18 aryl), (h) C3-8 cycloalkyl, and (i) C1-6 alkyl-C3-8 cycloalkyl (e.g., -L-R, in which L is C1-6 alkylene and R is C3-8 cycloalkyl), where in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group.

[0392] In some embodiments, the alkyl group is a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is a C1-3, Ci-4, C1-6, C1-8, C1-10, C1-12, Ci-16, Ci-18, C1-20, Ci-24, C2-6, C2-8, C2-10, C2-12, C2-16, C2-18, C2-20, C2-24, C3-8, C3-10, C3-12, C3-16, C3-18, C3-20, or C3-24 alkyl group. Unless stated otherwise specifically in the specification, an alkyl group is optionally substituted by one or more of substituents that are independently heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra)2, -C(O)Ra, -C(O)ORa, -0C(0)N(Ra)2, -C(0)N(Ra)2, -N(Ra)C(0)0Ra, -N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, -N(Ra)C(NRa)N(Ra)2, -N(Ra)S(O)tRa (where t is 1 or 2), -S(O)tRa (where t is 1 or 2), -S(O)tORa (where t is 1 or 2), -S(O)tN(Ra)2 (where t is 1 or 2), or PO3(Ra)2 where each Ra is independently hydrogen, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0393] By “alkylene” is meant a multivalent (e.g., bivalent) form of an aliphatic or alkyl group, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene group is a C1-3, C1-4, C1-6, C1-12, Ci-16, Ci-18, C1-20, Ci-24, C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24 alkylene group. In some embodiments, the alkylene group is branched or unbranched. The alkylene group is also substituted or unsubstituted. For example, in some embodiments, the alkylene group is substituted with one or more substitution groups, as described herein for alkyl.

[0394] The term “alkoxy” refers to the group -O-alkyl, including from 1 to 24 carbon atoms of a straight, branched, cyclic configuration and combinations thereof attached to the parent structure through an oxygen. Exemplary alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, butoxy, cyclohexyloxy, and trihaloalkoxy, such as trifluoromethoxy, etc. In some embodiments, the alkoxy group is substituted or unsubstituted. For example, in some embodiments, the alkoxy group is substituted with one or more substitution groups, as described herein for alkyl. Exemplary unsubstituted alkoxy groups include Ci-3, Ci-6, C1-12, Ci-16, Ci-18, C1-20, or C1-24 alkoxy groups.

[0395] The term “substituted alkoxy” refers to alkoxy where the alkyl constituent is substituted (e.g., -O-(substituted alkyl)). Unless stated otherwise specifically in the specification, the alkyl moiety of an alkoxy group is optionally substituted by one or more substituents the independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra)2, -C(O)Ra, -C(O)ORa, -OC(O)N(Ra)2, -C(O)N(Ra)2, -N(Ra)C(0)0Ra, -N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, -N(Ra)C(NRa)N(Ra)2, -N(Ra)S(O)tRa (where t is 1 or 2), -S(O)tRa (where t is 1 or 2), -S(O)tORa (where t is 1 or 2), -S(O)tN(Ra)2 (where t is 1 or 2), or POs(Ra)2, where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0396] The term “alkylsilyl,” as used herein, refers to -SiR1 R2R3 group, where R1 is an optionally substituted alkyl, and where each of R2 and R3 is independently selected from H and an optionally substituted alkyl. Alkylsilyls include mono, bis, and tris alkylsilyls. Examples of alkylsilyls include trimethyl silyl, dimethylsilyl, methylsilyl, triethylsilyl, diethylsilyl, ethylsilyl, and the like.

[0397] By “alkylsulfinyl” is meant an alkyl group, as defined herein, attached to the parent molecular group through an -S(O)- group. In some embodiments, the unsubstituted alkylsulfinyl group is a C1-6 or C1-12 alkylsulfinyl group. In other embodiments, the alkylsulfinyl group is -S(O)-R, in which R is an alkyl group, as defined herein.

[0398] By “alkylsulfinylalkyl” is meant an alkyl group, as defined herein, substituted by an alkylsulfinyl group. In some embodiments, the unsubstituted alkylsulfinylalkyl group is a C2-12 or C2-24 alkylsulfinylalkyl group (e.g., C1-6 alkylsulfinyl-Ci-6 alkyl or C1-12 alkylsulfinyl-Ci-12 alkyl). In other embodiments, the alkylsulfinylalkyl group is -L-S(O)-R, in which L is alkylene, as defined herein, and R is an alkyl group, as defined herein.

[0399] By “alkylsulfonyl” is meant an alkyl group, as defined herein, attached to the parent molecular group through an -SO2- group. In some embodiments, the unsubstituted alkylsulfonyl group is a C1-6 or C1-12 alkylsulfonyl group. In other embodiments, the alkylsulfonyl group is -SO2-R, where R is an optionally substituted alkyl (e.g., as described herein, including optionally substituted C1-12 alkyl, haloalkyl, or perfluoroalkyl).

[0400] By “alkylsulfonylalkyl” is meant an alkyl group, as defined herein, substituted by an alkylsulfonyl group. In some embodiments, the unsubstituted alkylsulfonylalkyl group is a C2-12 or C2-24 alkylsulfonylalkyl group (e.g., C1-6 alkylsulfonyl-Ci-6 alkyl or C1-12 alkylsulfonyl-Ci-12 alkyl). In other embodiments, the alkylsulfonylalkyl group is -L-SO2-R, in which L is alkylene, as defined herein, and R is an alkyl group, as defined herein.

[0401] By “alkynyl” is meant an optionally substituted C2-24 alkyl group having one or more triple bonds. The alkynyl group can be cyclic or acyclic and is exemplified by ethynyl, 1-propynyl, and the like. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting unsubstituted alkynyl groups include C2-8 alkynyl, C2-6 alkynyl, C2-5 alkynyl, C2-4 alkynyl, or C2-3 alkynyl. Non-limiting examples of alkynyl groups include ethynyl (-C=CH), 1-propynyl (-C=CCH3), 2-propynyl or propargyl (-CH2C=CH), 1-butynyl (-C=CCH2CH3), 2-butynyl (-CH2C=CCH3), 3-butynyl (-CH2CH2OCH ), and the like. In some embodiments, the unsubstituted alkynyl group is a C2-6, C2-8, C2-10, C2-12, C2-16, C2-18, C2-20, C2-24, C3-8, C3-10, C3-12, C3-16, C3-18, C3-20, or C3-24 alkynyl group.

[0402] By “alkynylene” is meant a multivalent (e.g., bivalent) form of an alkynyl group, which is an optionally substituted C2-24 alkyl group having one or more triple bonds. The alkynylene group can be cyclic or acyclic. The alkynylene group can be substituted or unsubstituted. For example, the alkynylene group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting examples of alkynylene groups include -C=C- or -C=CCH2-.

[0403] By “amido” is meant -C(O)NR'R2 or -NHCOR1, where each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or where R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein.

[0404] By “amine” or “amino” is meant a -NRN1RN2 group, a -NRn1- group, or a compound having such a group, where each of RN1 and RN2 is, independently, H, optionally substituted aliphatic, alkyl, hydroxyalkyl, heteroaliphatic, heteroalkyl, aromatic, or aryl; or where RN1 and RN2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In some embodiments an “amino” or “amino” is meant a -N(Ra)2 radical group, where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl, unless stated otherwise specifically in the specification. When a -N(Ra)2 group has two Ra substituents other than hydrogen, they can be combined with the nitrogen atom to form a 4-, 5-, 6- or 7-membered ring. For example, -N(Ra)2 is intended to include, but is not limited to, 1-pyrrolidinyl and 4-morpholinyl. Unless stated otherwise specifically in the specification, an amino group is optionally substituted by one or more substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -OC(O)-Ra, -N(Ra)2, -C(O)Ra, -C(O)ORa, -0C(0)N(Ra)2, C(0)N(Ra)2, -N(Ra)C(0)0Ra, - N(Ra)C(0)Ra, -N(Ra)C(0)N(Ra)2, -N(Ra)C(NRa)N(Ra)2, -N(Ra)S(O)tRa (where t is 1 or 2), -S(O)tRa (where t is 1 or 2), -S(O)tORa (where t is 1 or 2), -S(O)tN(Ra)2 (where t is 1 or 2), or -POs(Ra)2, where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0405] The term “substituted amino” also refers to N-oxides of the groups -NHRa, and NRaRa each as described above. N-oxides can be prepared by treatment of the corresponding amino group with, for example, hydrogen peroxide or m-chloroperoxybenzoic acid.

[0406] By “aminoalkyl” is meant an aliphatic or alkyl group, as described herein, substituted with one, two, three, or more amine groups. In some embodiments the aminoalkyl includes internal amine groups or terminal amine groups. In some embodiments, the aminoalkyl group is further substituted. For example, in some embodiments, the aminoalkyl group is substituted with one or more substitution groups, as described herein for alkyl. Exemplary unsubstituted aminoalkyl groups include C1-3, Ci-6, C1-12, Ci-16, Ci-is, C1-20, or Ci-24 aminoalkyl groups. In some embodiments, the aminoalkyl group is -L-NR1 R2, in which L is an aliphatic or alkylene group, as defined herein, and each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof; or R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein. In other embodiments, the aminoalkyl group is -L-C(NR1R2)(R3)-R4, in which Lisa covalent bond, an aliphatic group, or an alkylene group, as defined herein; each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof; or R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein; and each of R3 and R4 is, independently, H or alkyl, as defined herein.

[0407] By “aminoaryl” is meant an aromatic or aryl group, as defined herein, substituted by an amino group, as defined herein.

[0408] By “aromatic” is meant a cyclic, conjugated group or moiety of, unless specified otherwise, from 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple condensed rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring, and optionally multiple condensed rings, have a continuous, delocalized 7t- electron system. Typically, the number of out of plane 7t-electrons corresponds to the Huckel rule (4n+2). The point of attachment to the parent structure typically is through an aromatic portion of the condensed ring system.

[0409] By “aryl” is meant an aromatic carbocyclic group comprising at least five carbon atoms to 15 carbon atoms (C5-15), such as five to ten carbon atoms (C5-10), having a single ring or multiple condensed rings, which condensed rings can or may not be aromatic provided that the point of attachment to a remaining position of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. Aryl groups may be substituted with one or more groups other than hydrogen, such as alkyl, as well as any substitution groups described herein for alkyl. Non-limiting examples of aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl, which is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl, which is also included in the term aryl, defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group can be substituted with one, two, three, four, or five substituents provided herein for alkyl. In particular embodiments, an unsubstituted aryl group is a C4-18, C4-14, C4-12, C4-10, Ce-18, Ce-14, C6-12, or Ce-io aryl group. Aryl groups can have any suitable number of carbon ring atoms and any suitable number of rings. Aryl groups can include any suitable number of carbon ring atoms, such as Ce, C7, Cs, C9, C10, C11, C12, C13, C14, C15 or Ci6, as well as C6-12, Ce-io, or Ce-14. Bivalent radicals formed from substituted benzene derivatives and having the free valences at ring atoms are named as substituted phenylene radicals. Bivalent radicals derived from univalent polycyclic hydrocarbon radicals whose names end in “-yl” by removal of one hydrogen atom from the carbon atom with the free valence are named by adding “-idene” to the name of the corresponding univalent radical, e.g., a naphthyl group with two points of attachment is termed naphthylidene. Whenever it appears herein, a numerical range such as “6 to 10” (e.g., Ce-Cio aromatic or Ce-Cio aryl) refers to each integer in the given range; e.g., “6 to 10 ring atoms” means that the aryl group may consist of 6 ring atoms, 7 ring atoms, etc., up to and including 10 ring atoms. Aryl groups can be monocyclic, fused (i.e., rings which share adjacent pairs of ring atoms) to form bicyclic (e.g., benzocyclohexyl) or tricyclic groups or polycyclic groups, or linked by a bond to form a biaryl group. Representative aryl groups include phenyl, naphthyl and biphenyl. Other aryl groups include benzyl, having a methylene linking group. Unless stated otherwise specifically in the specification, an aryl moiety is optionally substituted by one or more substituents which are independently alkyl, heteroalkyl, acylsulfonamido, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, hydroxamate, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, -ORa, -SRa, -S(O)tRa- (where t is 1 or 2), -OC(O)-Ra, -N(Ra)2, C(O)Ra, C(O)ORa, -OC(O)N(Ra)2, C(O)N(Ra)2, -N(Ra)C(O)ORa, -N(Ra)C(O)Ra, N(Ra)C(0)N(Ra)2, N(Ra)C(NRa)N(Ra)2, N(Ra)S(O)tRa (where t is 1 or 2), -S(O)tRa (where t is 1 or 2), -S(O)tORa (where t is 1 or 2), S(O)tN(Ra)2 (where t is 1 or 2), or PO(ORa)2, where each Ra is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.

[0410] By “arylene” is meant a multivalent (e.g., bivalent) form of an aromatic or aryl group, as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is a C4-18, C4-14, C4-12, C4-10, Ce-18, Ce-14, C6-12, or Ce-10 arylene group. In some embodiments, the arylene group is branched or unbranched. In some embodiments, the arylene group is further substituted or unsubstituted. For example, In some embodiments, the arylene group is substituted with one or more substitution groups, as described herein for alkyl or aryl.

[0411] By “aryloxy” is meant -OR, where R is an optionally substituted aromatic or aryl group, as described herein. In some embodiments, an unsubstituted aryloxy group is a C4-18 or Ce-18 aryl oxy group.

[0412] By “arylalkoxy” is meant an alkyl-aryl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy group is -O-L-R, in which L is an alkylene group, as defined herein, and R is an aryl group, as defined herein.

[0413] By “aryloxycarbonyl” is meant an aryloxy group, as defined herein, that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloxycarbonyl group is a C5-19 aryloxycarbonyl group. In other embodiments, the aryloxycarbonyl group is -C(O)O-R, in which R is an aryl group, as defined herein.

[0414] By “aryloyl” is meant an aryl group that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloyl group is a C7-11 aryloyl or C5-19 aryloyl group. In other embodiments, the aryloyl group is -C(O)-R, in which R is an aryl group, as defined herein.

[0415] By “(aryl)(alkyl)ene” is meant a bivalent form including an arylene group, as described herein, attached to an alkylene or a heteroalkylene group, as described herein. In some embodiments, the (aryl)(alkyl)ene group is -L-Ar- or -L-Ar-L- or -Ar-L-, in which Ar is an aromatic or arylene group and each L is, independently, an optionally substituted aliphatic, alkylene group, heteroaliphatic, or heteroalkylene group.

[0416] By “borono” is meant a -B(OH)2 group.

[0417] By “carbonyl” is meant a -C(O)- group, which can also be represented as >C=O, or a -CO- group.

[0418] By “carboxyl” or “carboxylic acid” is meant a -CO2H group or a compound including such a group, including deprotonated and protonated forms thereof.

[0419] By “carboxyalkyl” is meant an alkyl group, as defined herein, substituted by one or more carboxyl groups, as defined herein.

[0420] By “carboxyaryl” is meant an aryl group, as defined herein, substituted by one or more carboxyl groups, as defined herein.

[0421] By “cyclic anhydride” is meant a 3-, 4-, 5-, 6- or 7-membered ring (e.g., a 5-, 6- or 7-membered ring), unless otherwise specified, having a -C(O)-O-C(O)- group within the ring. The term “cyclic anhydride” also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above rings is fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring. Exemplary cyclic anhydride groups include a radical formed from succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, isochroman-1,3-dione, oxepanedione, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, naphthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, etc., by removing one or more hydrogen. Other exemplary cyclic anhydride groups include dioxotetrahydrofuranyl, dioxodihydroisobenzofuranyl, etc. The cyclic anhydride group can also be substituted or unsubstituted. For example, the cyclic anhydride group can be substituted with one or more groups including those described herein for heterocyclyl.

[0422] By “cycloaliphatic” is meant an aliphatic group, as defined herein, that is cyclic.

[0423] By “cycloalkoxy” is meant a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -O-R, in which Risa cycloalkyl group, as defined herein.

[0424] By “cycloalkylalkoxy” is meant an alkyl-cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkylalkoxy group is -O-L-R, in which L is an alkylene group, as defined herein, and R is a cycloalkyl group, as defined herein.

[0425] By “cycloalkyl” is meant a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of from three to eight carbons, unless otherwise specified, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. The cycloalkyl group can also be substituted or unsubstituted. For example, the cycloalkyl group can be substituted with one or more groups including those described herein for alkyl.

[0426] By “cycloheteroaliphatic” is meant a heteroaliphatic group, as defined herein, that is cyclic.

[0427] By “disulfide” is meant -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof.

[0428] By “formyl” is meant a -C(O)H group.

[0429] By “halo” is meant F, Cl, Br, or I.

[0430] By “haloaliphatic” is meant an aliphatic group, as defined herein, substituted with one or more halo.

[0431] By “haloalkyl” is meant an alkyl group, as defined herein, substituted with one or more halo.

[0432] By “haloalkenyl” is meant an alkenyl group, as defined herein, substituted with one or more halo.

[0433] By “haloalkynyl” is meant an alkynyl group, as defined herein, substituted with one or more halo.

[0434] By “haloalkylene” is meant an alkylene group, as defined herein, substituted with one or more halo.

[0435] By “halocarbonyl” is meant a -C(O)X group, in which X is halo, as defined herein.

[0436] By “haloheteroaliphatic” is meant a heteroaliphatic, as defined herein, in which one or more hydrogen atoms, such as one to 10 hydrogen atoms, independently is replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0437] By “heteroaliphatic” is meant an aliphatic group, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to boron, halo, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and, if applicable, oxidized forms thereof within the group.

[0438] By “heteroalkyl,” “heteroalkenyl,” and “heteroalkynyl” is meant an alkyl, alkenyl, or alkynyl group (which can be branched, straight-chain, or cyclic), respectively, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to, boron, halo, nitrogen (e.g., as present in imino), oxygen, phosphorus, selenium, silicon, sulfur, and, if applicable, oxidized forms thereof within the group.

[0439] By “heteroalkylene” is meant a multivalent (e.g., bivalent) form of a heteroaliphatic or heteroalkyl group, as described herein. The heteroalkylene group can be substituted or unsubstituted. For example, in some embodiments the heteroalkylene group is substituted with one or more substitution groups, as described herein for alkyl.

[0440] By “heteroalkenylene” is meant a multivalent (e.g., bivalent) form of a heteroalkenyl group, which is an optionally substituted heteroalkyl group having one or more double bonds. The heteroalkenylene group can be cyclic or acyclic. The heteroalkenylene group can be substituted or unsubstituted. For example, the heteroalkenylene group can be substituted with one or more substitution groups, as described herein for alkyl.

[0441] By “heteroalkynylene” is meant a multivalent (e.g., bivalent) form of a heteroalkynyl group, which is an optionally substituted heteroalkyl group having one or more triple bonds. The heteroalkynylene group can be cyclic or acyclic. The heteroalkynylene group can be substituted or unsubstituted. For example, the heteroalkynylene group can be substituted with one or more substitution groups, as described herein for alkyl.

[0442] By “heteroaromatic” is meant an aromatic group, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to boron, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and oxidized forms thereof within the group.

[0443] By “heteroaryl” is meant an aryl group including at least one heteroatom to six heteroatoms, such as one to four heteroatoms, which can be selected from, but not limited to, boron, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and oxidized forms thereof within the ring. Such heteroaryl groups can have a single ring or multiple condensed rings, where the condensed rings may or may not be aromatic or may contain a heteroatom, provided that the point of attachment is through an atom of the aromatic heteroaryl group. Heteroaryl groups may be substituted with one or more groups other than hydrogen, such as alkyl, as well as any substitution groups described herein for alkyl. A non-limiting example of heteroaryl includes a subset of heterocyclyl groups, as defined herein, which are aromatic, e.g., they contain 4n+2 pi electrons within the mono- or multi cyclic ring system.

[0444] By “heteroarylene” is meant a multivalent (e.g., bivalent) form of a heteroaromatic or heteroaryl group, as described herein. Exemplary heteroarylene groups include pyridinylene and the like. In some embodiments, the heteroarylene group is a C4-18, C4-14, C4-12, C4-10, Ce-18, C6-14, C6-12, or Ce-io heteroarylene group. In some embodiments, the heteroarylene group is branched or unbranched. In some embodiments, the heteroarylene group is further substituted or unsubstituted. For example, in some embodiments, the heteroarylene group is substituted with one or more substitution groups, as described herein for alkyl or aryl.

[0445] By “heterocyclyl” is meant a 3-, 4-, 5-, 6- or 7-membered ring (e.g., a 5-, 6- or 7-membered ring), unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, selenium, silicon, or sulfur). The 3-membered ring has zero to one double bonds, the 4- and 5-membered ring has zero to two double bonds, and the 6-and 7-membered rings have zero to three double bonds. The term “heterocyclyl” also includes bicyclic, tricyclic, tetracyclic, or other multicyclic groups. Heterocyclics include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl, benzodioxocinyl, benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl, benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl, benzylsultimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., P- carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytdinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydroypyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, dioxiranyl, dioxenyl, dioxinyl, di oxobenzofuranyl, dioxolyl, dioxooxolanyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., IH-indazolyl), indolenyl, indolinyl, indolizinyl, indolyl (e.g., IH-indolyl or 3H- indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazoyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidiniyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthiridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl, naphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanonyl, oxetanyl, oxetyl, oxtenayl, oxindolyl, oxiranyl, oxobenzoisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxolanyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolizi dinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5- thiadiazinyl or 2H,6H-l,5,2-dithiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthenyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thietyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, uricyl, uridinyl, xanthenyl, xanthinyl, xanthionyl, and the like, as well as modified forms thereof (e.g., including one or more oxo and / or amino) and salts thereof. The heterocyclyl group can be substituted or unsubstituted. For example, the heterocyclyl group can be substituted with one or more substitution groups, as described herein for alkyl.

[0446] By “heterocyclyloxy” is meant a heterocyclyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the heterocyclyloxy group is -O-R, in which Risa heterocyclyl group, as defined herein.

[0447] By “heterocyclyloyl” is meant a heterocyclyl group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, the heterocyclyloyl group is -C(O)-R, in which Risa heterocyclyl group, as defined herein.

[0448] By “hydroxy” is meant -OH.

[0449] By “hydroxyalkyl” is meant an alkyl group, as defined herein, substituted by one to three hydroxy groups, with the proviso that no more than one hydroxy group may be attached to a single carbon atom of the alkyl group and is exemplified by hydroxymethyl, dihydroxypropyl, and the like.

[0450] By “hydroxyaryl” is meant an aryl group, as defined herein, substituted by one to three hydroxy groups, with the proviso that no more than one hydroxy group may be attached to a single carbon atom of the aryl group and is exemplified by hydroxyphenyl, dihydroxyphenyl, and the like.

[0451] By “imido” is meant a =NR group, where R is selected from H, aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, or aryl, as defined herein, or any combination thereof.

[0452] By “imino” is meant -NR-, in which R can be H, optionally substituted aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, or aryl.

[0453] By “isocyanato” is meant a -NCO griyo.

[0454] By “nitro” is meant an -NO2 group.

[0455] By “nitroalkyl” is meant an alkyl group, as defined herein, substituted by one to three nitro groups. In some embodiments, the nitroalkyl group is -L-NO, in which L is an alkylene group, as defined herein. In other embodiments, the nitroalkyl group is -L-C(NO)(R1)-R2, in which L is a covalent bond or an alkylene group, as defined herein, and each of R1 and R2 is, independently, H or alkyl, as defined herein. 0                O yy     y\

[0456] By “oxiranyl” is meant a         ( group or a                 group, in which one or more hydrogen atoms can be optionally substituted with another functional group (e.g., halo, alkyl, or any described herein as a substituent for alkyl).

[0457] By “oxo” or “oxide” is meant an =0 group.

[0458] By “oxy” is meant -O-.

[0459] By “phosphono” or “phosphonic acid” is meant a -P(O)(OH)2 group or a compound including such a group, including deprotonated and protonated forms thereof.

[0460] By “perfluoroalkyl” is meant an alkyl group, as defined herein, having each hydrogen atom substituted with a fluorine atom. Non-limiting examples of perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, etc. In some embodiments, the perfluoroalkyl group is -(CF2)nCF3, in which n is an integer from 0 to 20, 1 to 20, 1 to 18, 1 to 16, 1 to 14, 1 to 12, 1 to 10, 1 to 8, 2 to 20, 2 to 18, 2 to 16, 2 to 14, 2 to 12, 2 to 10, 2 to 8, and ranges therebetween.

[0461] By “perfluoroalkoxy” is meant an alkoxy group, as defined herein, having each hydrogen atom substituted with a fluorine atom. In some embodiments, the perfluoroalkoxy group is -O-R, in which Risa perfluoroalkyl group, as defined herein.

[0462] By “salt” is meant an ionic form of a compound or structure (e.g., any formulas, compounds, or compositions described herein), which includes a cation or anion compound to form an electrically neutral compound or structure. Salts are well known in the art. For example, non-toxic salts are described in Berge S. M. et al., “Pharmaceutical salts,” J. Pharm. Sci. 1977 January; 66(1): 1-19; and in “Handbook of Pharmaceutical Salts: Properties, Selection, and Use,” Wiley-VCH, April 2011 (2nd rev. ed., eds. P. H. Stahl and C. G. Wermuth. The salts can be prepared in situ during the final isolation and purification of the compounds of the invention or separately by reacting the free base group with a suitable organic acid (thereby producing an anionic salt) or by reacting the acid group with a suitable metal or organic salt (thereby producing a cationic salt). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methylbromide, methylnitrate, methyl sulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, theophyllinate, thiocyanate, triethiodide, toluenesulfonate, undecanoate, valerate salts, and the like. Representative cationic salts include metal salts, such as alkali or alkaline earth salts, e.g, barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and the like; other metal salts, such as aluminum, bismuth, iron, and zinc; as well as nontoxic ammonium, quaternary ammonium, and amine cations, including, but not limited to ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like. Other cationic salts include organic salts, such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine. Yet other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, etc., as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinum, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0463] By “silane” is meant -SiRslRS2RS3, -SiRslRS2-, or a compound having such groups, where each of RS1, RS2, and RS3 is, independently, H, optionally substituted aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, aryl, amine, or others described herein; or RS1 and RS2, taken together with the silicon atom to which each are attached, form a heterocyclyl group.

[0464] By “silyl ether” is meant a functional group including a silicon atom covalently bound to an alkoxy group, as defined herein. In some embodiments, the silyl ether is - Si-O-R or Si-O- R, in which R is an alkyl group, as defined herein.

[0465] By “sulfinyl” is meant an -S(O)- group.

[0466] By “sulfo” or “sulfonic acid” is meant an -S(O)2OH group or a compound including such a group, including deprotonated and protonated forms thereof.

[0467] By “sulfonyl” or “sulfonate” is meant an -S(O)2- group or a -SO2R, where R is selected from hydrogen, aliphatic, alkyl, heteroaliphatic, heteroalkyl, haloaliphatic, haloheteroaliphatic, aromatic, aryl, as defined herein, or any combination thereof.

[0468] By “thio” is meant -S-.

[0469] By “thiol” is meant an -SH group.

[0470] By “thioalkoxy” is meant an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Non-limiting examples of unsubstituted thioalkoxy groups include C1-6 thioalkoxy. In some embodiments, the thioalkoxy group is -S-R, in which R is an aliphatic or alkyl group, as defined herein.

[0471] By “thioalkoxyalkyl” is meant an alkyl group, as defined herein, which is substituted with a thioalkoxy group, as defined herein. Non-limiting examples of unsubstituted thioalkoxyalkyl groups include between 2 to 12 carbons (C2-12 thioalkoxyalkyl), as well as those having an alkyl group with 1 to 6 carbons and a thioalkoxy group with 1 to 6 carbons (i.e., C1-6 thioalkoxy-Ci-6 alkyl). In some embodiments, the thioalkoxyalkyl group is -L-S-R, in which L is alkylene, as defined herein, and R is an alkyl group, as defined herein.

[0472] II. Methods offorming a functionalized material

[0473] A functionalized material can be prepared in any useful manner. In some embodiments, a functionalization mixture is prepared, in which this mixture includes the substrate, a solvent, and one or more compounds to provide a functional portion. In some embodiments, at least one of the compounds includes an amine moiety, and at least one of the compounds includes a silane moiety. In particular embodiments, at least one compound includes both an amine moiety and a silane moiety. In other embodiments, at least one compound includes a crosslinking agent.

[0474] The polymer coating, chelating agent(s), and / or antioxidant(s) are introduced at any useful operation described herein. For example and without limitation, in some embodiments a polymer for the polymer coating is introduced to the substrate prior to, during, or after the functionalization mixture is provided to the substrate. In another example, the chelating agent(s) is introduced to the substrate prior to, during, or after the functionalization mixture is provided to the substrate. In yet another example, the antioxidant(s) is introduced to the substrate prior to, during, or after the functionalization mixture is provided to the substrate. Optionally, in some embodiments, the chelating agent(s) and / or antioxidant(s) is introduced with the polymer of the polymer coating. In another option, the chelating agent(s) and / or antioxidant(s) is introduced with the functionalization mixture.

[0475] In some embodiments the functionalization mixture is prepared in any useful manner. In one non-limiting example, a suspension mixture is prepared including the substrate and a solvent. To this suspension mixture, a compound (to provide a functional portion) is added to provide a functionalization mixture. Non-limiting examples of compounds include a silane coupling material, an aminosilane, a polyamine, or a combination of any of these compounds. In some embodiments, functionalization is conducted using solution-based reaction conditions.

[0476] In some embodiments A crosslinking agent (to provide a linking moiety) is added to provide a crosslinking mixture. In some embodiments, the crosslinking agent is added to the functionalization mixture to provide a crosslinking mixture.

[0477] Various methods are employed to provide the functionalized materials described herein. In some embodiments, the material is produced using solution-based reaction methods in which a silane-containing compound (e.g., an aminosilane compound with an amine moiety and a silane moiety) is solvated and a substrate (e.g., porous silica, MOF, or resin) is added. The silane moiety binds to the surface, and the amine moieties extend from the silane moiety. In some embodiments the resultant substrate is filtered from the solvent, washed, and dried. In some embodiments, such a material is further reacted with a polymeric / oligomeric amine compound. In some embodiments the mixture is stirred and then dried, thereby functionalizing the substrate with both the silane-containing compound and the polymeric / oligomeric amine.

[0478] In other embodiments, a functionalized material is produced using solvent-based reaction methods in which a polyamine (e.g., a compound with a plurality of amine moieties) or an oligomeric ethylene amine compound (e.g., a compound with a plurality of ethylene groups and amine moieties, as well as mixtures of such compounds, including any described herein) with an optional aminosilane compound (e.g., a compound with an amine moiety and a silane moiety) is solvated (e.g., water-based reaction methods when the aminosilane compound is absent), and a substrate (e.g., porous silica, MOF, or resin) is added. When polyamine is used alone, in some embodiments, the polyamine has an increased number of amine moieties for increased carbon capture (e.g., > 2 mol / kg) in the functionalized material. When both a polyamine and an aminosilane is employed, the polyamine and aminosilane compounds react to form a complex network, which in turn is bonded to a surface of the substrate. When the oligomeric ethylene amine compound or mixture thereof is used alone, in some embodiments, the oligomeric ethylene amine compound or a mixture thereof has an increased number of amine moieties for increased carbon capture (e.g., > 1 mol / kg) in the functionalized material. The resulting material is stirred, optionally filtered from the solvent, optionally washed, and dried in some embodiments.

[0479] Any method described herein (e.g., such as the process in FIGS. 3A-3E) provides any functionalized material described herein (e.g., a functionalized material 100A-100E in FIGS. 1A-1E).

[0480] FIGS. 3 A-3E are non-limiting flow chart diagrams showing examples of steps for producing a functionalized material. These diagrams are further described below.

[0481] In some embodiments, the synthesis of the functionalized material is done under industrially applicable reaction conditions, such as liquid application to particles undergoing tumbling or mixing motion. After synthesis, the adsorbent can be optionally purified, dried, and optionally activated before using it as a CO2 adsorbent, such as coated particle 100. FIGS. 3A-E collectively illustrate examples processes 300 for making functionalized material, in accordance with some embodiments of the present disclosure. For example, FIGS. 3 A-B collectively illustrate flow chart diagrams detailing a process 300 for making functionalized particles for use in a reversible adsorbent material, e.g., synthesizing a reversible CO2 adsorbent, such as coated particle 100.

[0482] Referring to FIG. 3A, in some implementations, the process 300A is performed at large scale, e.g., producing 1 kilogram or more of functionalized crosslinked particles in a single process. In some implementations, the process 300A produces 100 kilograms or more of functionalized crosslinked particles (e.g., up to 10,000 kg). To maintain the original particle size distribution and reduce further attrition, in some embodiments agitation methods in which the particles are subjected to comparatively low friction or stirring forces are preferred, such as overhead stirring, gentle tumbling, slow and periodic stirring, or vibration.

[0483] In some embodiments, the process produces at least 10, at least 20, at least 50, at least 100, at least 500, at least 1000, at least 2000, at least 5000, at least 10,000, or at least 100,000 kg of functionalized crosslinked particles. In some embodiments, the process produces no more than 500,000, no more than 100,000, no more than 10,000, no more than 5000, no more than 1000, no more than 500, no more than 100, or no more than 50 kg of functionalized crosslinked particles. In some embodiments, the process produces from 10 to 500, from 100 to 1000, from 500 to 2000, from 1000 to 10,000, from 5000 to 50,000, or from 50,000 to 500,000 kg of functionalized crosslinked particles. In some embodiments, the process produces another range of functionalized crosslinked particles starting no lower than 10 kg and ending no higher than 500,000 kg of functionalized crosslinked particles.

[0484] In some embodiments, the process 300A includes preparing a functionalization mixture with a crosslinking agent to form a crosslinked mixture (step 302A).

[0485] In some embodiments functionalizing the particles includes exposing the particles to a functionalization mixture. In some embodiments the functionalization mixture includes any compound(s) herein to provide a functional portion (e.g., one or more of amines, aminosilanes, polyamines, monoamines, or any combination of any of these), any compounds herein to provide a linking moiety (e.g., one or more crosslinking agents), any compound(s) herein to provide a polymer coating (e.g., one or more polymers, such as PVA), any chelating agent(s) herein, or any antioxidant(s) herein, as well as combinations of any of these.

[0486] In one non-limiting embodiment, creating the functionalization mixture includes introducing a first reagent including a polyamine and a second reagent comprising a silane moiety and an amine functional group (e.g., an aminosilane) into a solvent to form a functionalization mixture. The solvent is an organic solvent in some embodiments. For example, in some embodiments the solvent is selected such that the polymer used to coat the particles is not miscible in the solvent, thereby minimizing removal of the protective polymer coating from the coated particles while introducing the polyamine and aminosilane. As used herein, the terms “reagent” and “compound” are used interchangeably. In some embodiments the reagent includes one or more solvents, salts, or other compounds. While an example of a functionalization mixture includes a polyamine and an aminosilane, any useful combination of compounds can be employed (e.g., any combination of one or more of an aminosilane, a silane, a polyamine that can include non-polymeric or polymeric amines, a monoamine, and the like).

[0487] The first reagent, the second reagent, and the volume of solvent are dispensed and mixed. In some embodiments the first reagent is a polyamine (e.g., a polymeric amine), such as any polyamine described herein. In some embodiments the solvent is dispensed to fully suspend the polyamine, for example, by dispensing 20 mL / g of the solvent to polyamine (e.g., 10 mL / g, 15 mL / g, or 25 mL / g). In some embodiments the polyamine is added to the solvent in a range between 5% (wt / wt) and 60% (wt / wt) of the substrate to be functionalized in step 302A (e.g., 6% (wt / wt), 8% (wt / wt), 10% (wt / wt), 12% (wt / wt), 14% (wt / wt), 16% (wt / wt), or 18% (wt / wt), 20% (wt / wt), 30% (wt / wt), 40% (wt / wt), or 50% (wt / wt)).

[0488] Alternatively, the solvent is dispensed to entirely cover the substrate within the vessel, for example, by dispensing from 1 mL / g to 15 mL / g of the solvent to the substrate (e.g., 1 mL / g, 5 mL / g, 8 mL / g, 15 mL / g, 2 to 2 mL / g, 2 to 2.5 mL / g, or other ranges herein). The solvent is any described herein (e.g., a neutral aprotic organic solvent, such as toluene, hexane, cyclohexane, or tetrahydrofuran (THF), as well as combinations of any of these).

[0489] In some embodiments the second reagent is a silane coupling material, which can include a silane moiety (e.g., as in an amino silane or a silane, such as any described herein). In some embodiments the silane coupling material is dispensed in a range between 20% (wt / wt) to 80% (wt / wt) of a loading silane to the substrate to be functionalized in step 302A (e.g., 25% (wt / wt), 30% (wt / wt), 35% (wt / wt), 45% (wt / wt), 50% (wt / wt), or 60% (wt / wt)).

[0490] In some embodiments the second reagent is an adsorbing moiety material, which can include one or more adsorbing moi eties (e.g., one or more amine moieties, such as any described herein). In some embodiments the adsorbing moiety material is dispensed in a range between 20% (wt / wt) to 80% (wt / wt) of a loading silane to the substrate to be functionalized in step 302A (e.g., 25% (wt / wt), 30% (wt / wt), 35% (wt / wt), 45% (wt / wt), 50% (wt / wt), or 60% (wt / wt)).

[0491] In some embodiments the liquid mixture is stirred until the polyamine and the silane coupling material are fully suspended in the solvent. In some examples, mechanical stirring with a propeller, a magnetic stirrer, or sonication disperses the polyamine in a time range from about 5 minutes (min) to 60 min (e.g., from 10 min to 30 min, from 5 min to 30 min, from 10 min to 45 min).

[0492] In some implementations, one or more additives is included in the functionalization mixtures to extend the operational lifetime of the functionalized material. For example, in some embodiments the addition of bis[3-(trimethoxysilyl)propyl]amine) (BTMSPA) to the functionalization mixture increases the operational lifetime of the functionalized material. BTMSPA is an aminosilane having two ends, in which each end has a trimethoxysilyl reactive group. The BTMSPA bonds on the silica substrates with six binding points, as contrasted with the three binding points for an aminosilane with a single reactive group, such as would be present in a compound having a methoxy dialkylsilyl reactive group. The increased number of binding points increases binding stability with the silica substrate. The BTMSPA forms a network with other aminosilanes and polyamines on the surface that increases binding stability of the overall network in some embodiments. In some embodiments, the addition of a chelator to the polymer used during coating increases the operational lifetime of the functionalized material. In yet other embodimetns, the addition of an antioxidant with the polyamine and / or aminosilane used during functionalization increases the operational lifetime of the functionalized material.

[0493] Optionally, the functionalization mixture is agitated for a duration to allow hydrolysis of and fully dissolve the silane coupling material and polyamine. In some non-limiting examples, the first time period is in a range from 1 min to 10 min (e.g., 5 min). Optionally, the functionalization mixture is heated (e.g., to a heating temperature above ambient temperature and below 90 °C) and / or cooled (e.g., passively, for example, by way of radiant cooling) to any useful temperature, such as room temperature).

[0494] In the functionalization mixture, any useful crosslinking agent is introduced in some embodiments. In some embodiments, the crosslinking agent is introduced at a weight ratio of 5% or less wt / wt to another reagent present in the functionalization mixture (e.g., 4% or less, 3% or less, 2% or less, or 1% or less). In some embodiments, the crosslinking agent is present in an amount of about 0.1 mol % to 50 mol % of the crosslinking agent to the number of moles of amines present.

[0495] In some examples, optional activation steps are performed to cause the crosslinking agent to be reactive and form the crosslinking network on the substrate and / or the surface modification layer. In some embodiments the optional steps include modulating a temperature, a pressure, an acidity, a humidity of one or more of the coating liquid, the porous particles, the first reagent, the second reagent, the third reagent, or the crosslinking agent. The optional activation steps are specific to the crosslinking agent of the material.

[0496] In processes in which the optional activation steps are performed, the crosslinking agent is brought to (or below) the gelation point, e.g., the gel point. The gel point is specific a characteristic of crosslinker polymerizations that form networks over the surface of the substrate. The gel point and coating parameters to achieve the gel point, is specific to respective crosslinking agents. The gel point describes the point at which the network formation is substantially complete e.g., the majority of the components have been converted to a network.

[0497] In some embodiments, the process 300A further include introducing porous particles (e.g., porous silica particles) to the functionalization mixture to provide a plurality of functionalized crosslinked particles (step 306A). In some embodiments the porous particles are provided by particles 102A-E of FIGs. 1A-1E.

[0498] In some embodiments a crosslinking agent is added in any useful manner. As seen in FIG. 3B, a non-limiting process 300B for making functionalized material includes preparing a functionalization mixture (step 302B) and then introducing a crosslinking agent to the functionalization mixture to form a crosslinked mixture (step 302B). Then, the process 300B includes introducing porous particles to the crosslinked mixture to provide functionalized crosslinked particles (step 306B).

[0499] As seen in FIG. 3C, a non-limiting process 300C for making functionalized material includes preparing a functionalization mixture (step 302C) and then introducing porous particles to the functionalization mixture to form functionalized particles (step 302C). Then, the process 300C includes introducing a crosslinking agent to the functionalized particles to provide functionalized crosslinked particles (step 306C).

[0500] In some embodiments a polymer is employed in the process. As seen in FIG. 3D, in some embodiments the process 300D includes introducing porous particles (e.g., porous silica particles) to a crosslinking agent and a first reagent including a polymer to provide a plurality of crosslinked particles (step 302D). If a chelating agent is desired within the polymer coating, then any useful chelating agent (e.g., any described herein) is included with the first reagent.

[0501] In some embodiments, the porous particles is provided by particle 102A-E of FIG. 1A-1E. In some embodiments a solvent into which the porous particles and the first reagent are introduced solvates the polymer and crosslinking agent into a coating liquid and provides the dissolved molecules to the porous particles. The dissolved molecules adsorb to the surfaces and pores of the particles to form crosslinked particles.

[0502] In some embodiments the crosslinking agent is introduced at a ratio to the first reagent to crosslink a portion of the first reagent, e.g., less than all of the first reagent. In some embodiments, the crosslinking agent is introduced at a weight ratio of 5% or less wt / wt to the first reagent (e.g., 4% or less, 3% or less, 2% or less, or 1% or less). In some embodiments, the crosslinking agent is present in an amount of about 0.1 mol % to 50 mol % of the crosslinking agent to the number of moles of amines present.

[0503] In some examples, optional activation steps are performed to cause the crosslinking agent to be reactive and form the crosslinking network on the substrate. In some embodiments the optional steps include modulating a temperature, a pressure, an acidity, and / or a humidity of one or more of the coating liquid, the porous particles, the first reagent, and the crosslinking agent. The optional activation steps are specific to the crosslinking agent of the material. Some of the crosslinking agents described herein may be heated (e.g., curing) to completely react. An example optional activation step is raising the temperature of the mixtures described herein to a temperature threshold for a duration. In one embodiment, the crosslinking agent is brought to a temperature threshold of 80 °C for a duration of 4 hours or less.

[0504] In processes in which the optional activation steps are performed, the crosslinking agent is brought to (or below) the gelation point, e.g., the gel point. The gel point is a specific characteristic of crosslinker polymerizations that form 2- or 3-dimensional networks over the surface of the substrate. The gel point and coating parameters to achieve the gel point are specific to respective crosslinking agents.

[0505] In one embodiment, the crosslinking agent is terephthalaldehyde and the crosslinking agent is applied to the substrate and dried. Then the amine-containing materials are applied to the substrate and the amines react with the terephthalaldehyde as it is heated and dried to form the crosslinked sorbent. If the crosslinked sorbent is exposed to water, less amines are removed compared to un-crosslinked sorbents as the amines are crosslinked into a network and are less soluble.

[0506] In one embodiment, the crosslinking agent is terephthalaldehyde and the crosslinking agent and the solvent is a mixture of hexane / IPA. The amine-containing materials and the crosslinking agent are mixed in the solvent. Some crosslinking can occur in the mixture, e.g., the mixture does not fully crosslink, though additional steps of heating and / or drying the mixture on the substrate surface completes the crosslinking reaction. The solvent for step 302D depends on the polymer and crosslinking agent to be suspended. Using the example polymer provided herein, PVA is water-soluble and therefore an example of the solvent is water. In other embodiments, other solvents are selected based on the criteria of the polymer and crosslinking agent that creates the crosslinking coating.

[0507] In an example, the process 300D can be a ‘wet’ method, such as dip-coating, in which the volume of solvent is much larger than the volume of liquid the porous particles are capable of adsorbing. In some embodiments, the porous substrate particles are introduced to the solvent such that the particles are fully submerged in the solvent and at a wt:wt ratio in a range from 1.5 to 4:1 solvent to substrate (e.g., porous substrate particles). In some embodiments, the solvent to particle ratio is at least 0.5:1, atleast 1:1, atleast 1.5:1, at least 2:1, at least 2.5:1, at least 3:1, at least 3.5:1, or at least 4:1 wt / wt. In some embodiments, the solvent to particle ratio is no more than 5:1, no more than 4:1, no more than 3:1, no more than 2:1, or no more than 1:1 wt / wt. In some embodiments, the solvent to particle ratio falls within another range starting no lower than 0.5:1 wt / wt and ending no higher than 5:1 wt / wt.

[0508] In some embodiments of the batch method, the polymer is introduced to the solvent at a ratio sufficient that the polymer is fully dissolved in the solvent, e.g., no precipitation occurs, no precipitant is present. In some embodiments, the quantity of polymer introduced to the solvent is sufficient to coat the quantity of porous substrate particles to be coated in the process 300D to achieve the desired characteristics described herein. In the example of PVA (or any other polymer), the polymer is introduced in a (wt / wt) percentage of up to 20% of the polymer to the substrate (e.g., porous substrate particles), such as, e.g., up to 18% (wt / wt), up to 12% (wt / wt), up to 8% (wt / wt), less than 12% (wt / wt), or less than 9% (wt / wt). In some embodiments, the polymer is introduced (e.g., to a first solvent) in a (wt / wt) percentage from about 1% to 20% (wt / wt) of the polymer to the substrate (e.g., from about 1% to 5%, 1% to 10%, 1% to 15%, 3% to 5%, 3% to 10%, 3% to 15%, 3% to 20%, 5% to 10%, 5% to 15%, 5% to 20%, 7% to 10%, 7% to 15%, 7% to 20%, 10% to 15%, 10% to 20%, 1 3% to 15%, 13% to 20%, or 15% to 20% (wt / wt)).

[0509] Furthermore, in some embodiments one or more chelating agent(s) is introduced to a coating liquid including the polymer used to coat the substrate. In some embodiments, the chelating agent(s) is introduced in a (wt / wt) percentage of up to 5% of the chelating agent(s) to the substrate (e.g., porous particles), such as, e.g., from about 0.1% to 5% (wt / wt) to the substrate.

[0510] In some embodiments, the process 300D is a spray method in which the volume of solvent is similar to the volume of liquid the porous particles are capable of adsorbing. In such an example, the solvent is introduced to the particles such that the particles are ‘wetted’ by the solvent and at a wt:wt ratio in a range from 0.2 to 2.3:1 solvent to substrate (e.g., porous particles).

[0511] In one embodiment, the crosslinking agent is applied in a separate step from the amine containing materials. In an embodiment of the spray method, the crosslinking agent is applied to (e.g., sprayed on) the silica substrate first and then the amine-containing materials are added. Alternatively, the amine-containing materials are added first and then the crosslinking agent. In one embodiment, the amine-containing materials and crosslinking agent are applied separately (e.g., from separate streams) and coincidentally (e.g., at substantially similar times) onto the substrate. In such an embodiment, the crosslinking reaction begins when the materials and agents mix on substrate surface.

[0512] In some embodiments, the process 300D includes introducing a second reagent comprising at least one adsorbing moiety to the crosslinked particles, thereby providing a plurality of functionalized crosslinked particles (step 304D).

[0513] Introducing the second reagent functionalizes the surfaces and pores of the coated particles with an adsorbing moiety (e.g., one or more amine moi eties provided by a compound, such as an amine, an aminosilane, a polyamine, a monoamine, and the like). This also generates the plurality of functionalized coated particles for adsorbing CO2.

[0514] In some embodiments the process 300D includes introducing an optional antioxidant, and a third reagent comprising at least one interaction moiety to the functionalized crosslinked particles (step 306D).

[0515] In some embodiments, introducing the third reagent functionalizes the surfaces and pores of the coated particles with an interaction moiety (e.g., a silane moiety provided by a compound, such as a silane, an aminosilane, and the like). In some embodiments, the second reagent is a polyamine, and the third reagent is an aminosilane. Other combinations are possible (e.g., any described herein). For example, and without limitation, in some embodiments the second reagent is an amine (e.g., a polyamine, a monoamine, or an aminosilane), and the third reagent is an aminosilane or a silane (e.g., any described herein). In some embodiments, the second reagent includes both an adsorbing moiety and an interaction moiety (e.g., as in aminosilane), and the third reagent is omitted.

[0516] Introducing the anti oxi dant(s) provides compounds to scavenge oxygen or other oxidative species, which in turn results in reduced oxidation of amine-containing functional groups of the adsorbing species.

[0517] In some embodiments, the polymer coating, interaction moiety, and adsorbing moiety to create a functionalized coated material is done before the crosslinking agent is introduced. As seen in FIG. 3E, such a process 3OOE includes introducing porous particles (e.g, porous silica particles) to a first reagent including a polymer to provide a plurality of coated particles (step 302E). Any useful chelating agent in any useful amount (e.g., any described herein) can be included with the first reagent.

[0518] The process 3OOE further includes functionalizing the coated particles by exposing the particles to a functionalization mixture (step 304E). In turn, the functionalization mixture includes a second reagent and a third reagent. Details regarding the second and third reagents are as provided herein for process 300A.

[0519] Optionally, an antioxidant (e.g., any useful antioxidant in any useful amount, such as described herein) is introduced in step 302E or 304E.

[0520] The process 3OOE further includes crosslinking the coated particles by exposing the particles to a crosslinking agent (step 306E). Any useful crosslinking agent in any useful amount (e.g., any described herein) is included. In some examples, optional activation steps are performed to cause the crosslinking agent to be reactive and form the crosslinking network on the substrate. The optional steps include modulating a temperature, a pressure, an acidity, a humidity of one or more of the coating liquid, the porous particles, the first reagent, or the crosslinking agent. The optional activation steps are specific to the crosslinking agent of the material.

[0521] The steps of the process 300A-300E, e.g., steps 302A-E, 304B-E, or 306A-E, can be performed in any order, e.g., in other examples, the particles are crosslinked and then functionalized; the particles are functionalized and then crosslinked; the particles are functionalized, chelated, and then coated; the particles are coated, functionalized, and then crosslinked; or the particles are functionalized, crosslinked, and then coated; or the particles are functionalized and then coated, with optional drying separating the steps.

[0522] Optionally, the process 300A-E includes one or more steps (e.g, a separate step or a step combined with another step present in the process) for introducing a fifth reagent comprising an antioxidant. Examples of antioxidants for use in the method include sacrificial antioxidants and cyclic antioxidants. In some examples, more than one antioxidant is introduced. In some embodiments, the antioxidant(s) are added during steps 302A-E, 304B-E, or 306A-E of the process 300A-E, or afterward.

[0523] Optionally, the process 300A-E includes one or more steps for washing the surface of the porous particles to minimize the presence of one or more metals. In some embodiments, washing includes the use of an acid (e.g., a dilute acid).

[0524] Optionally, any of processes 300A-E include one or more steps for oxidizing metals present in porous particles by raising the temperature of the particles above a threshold for a duration before the first, second, third, fourth, or fifth reagents are introduced. Metals found on the surfaces and pores of porous particles are available for oxygenation during the lifetime of the functionalized particles. By raising the temperature of the porous particles, the metals are completely- or near-completely oxidized, in some embodiments, thereby reducing the effects of oxidation on the functionalized particles during carbon capture processes when the functionalized particles are exposed to atmospheric oxygen. One non-limiting example of the temperature threshold is 300 °C (e.g., 400 °C, 500 °C). One non-limiting example of the duration is at least one hour (e.g., at least two hours, at least three hours).

[0525] The temperature to which the porous silica particles are raised depends on the composition of metals that are determined to be present in the porous silica particles, in some embodiments. Iron and copper are examples of metal contaminants that can be oxidized by raising the temperature of the porous silica particles in the presence of an oxygen-containing gas, e.g., air.

[0526] Optionally, any of the processes 300A-E includes one or more steps for filtering the coated particles, functionalized coated particles, or both. In some embodiments filtering is performed using methods known in the art for separating solid phase from liquid phase. This includes, but is not limited to, vacuum filtration, centrifugation, vacuum evaporation, or a combination of these or other methods. The volume of solvent separated from the coated particles or functionalized particles is discarded, stored, or recycled, in some embodiments.

[0527] Optionally, any of processes 300A-E includes washing the substrate, coated particles, and / or functionalized coated particles in at least one wash volume of fresh (e.g., a new volume) solvent medium. For example, in some embodiments, the functionalized material is immersed in a wash volume of fresh solvent medium (e.g., 40 mL of solvent for 4 g of functionalized material), in which a single wash or a plurality of washes is performed. In some embodiments, the wash solvent dissolves the silane moiety to remove moieties coated on the surface of functionalized substrate but not reacted.

[0528] Optionally, any of processes 300A-E includes one or more steps for drying the coated particles, functionalized coated particles, or both. In some embodiments, drying the particles includes increasing the temperature, reducing the atmospheric pressure, passing an inert dry gas over the sample, passing a heated dry gas over the sample, or a combi...

Claims

1. A method of forming a plurality of functionalized crosslinked particles, the method comprising:introducing at least a portion of a surface of each porous particle in at least a subset of a plurality of porous particles to (i) a crosslinking agent and (ii) a first reagent comprising at least one adsorbing moiety.

2. The method of claim 1 wherein the adsorbing moiety is a first silane-functionalized amine, a first amino-functionalized silane (aminosilane), or a first polyamine.

3. The method of claim 1 or 2, wherein the introducing further comprises introducing the at least the portion of the surface of each porous particle in at least the subset of a plurality of porous particles to a second reagent comprising at least one interaction moiety.

4. The method of claim 3, wherein the at least one interaction moiety is other than the adsorbing moiety and is a second silane-functionalized amine, a second amino-functionalized silane (aminosilane), or a second polyamine.

5. The method of any one of claim 1-4, wherein the crosslinking agent is a multivalent crosslinking agent.

6. The method of any one of claims 1-5, wherein the crosslinking agent comprises a structure having one of formulas VII, Vila, Vllb, Vile, Vlld, Vile, Vllf, Vllg, Vllh, Vlli, Vllj, Vllk, VIII, or Vllm.

7. The method of any one of claims 1-5, wherein the crosslinking agent is a dialdehyde.

8. The method of claim 7, wherein the dialdehyde is 2,5-diformylfuran, glutaraldehyde,glyoxal, 1,3-phenylenediacetaldehyde, or mixtures thereof.

9. The method of any one of claims 1-5, wherein the crosslinking agent is a diisocyanate.

10. The method of claim 9, wherein the diisocyanate is 2,4-diisocyanatotoluene, methylene diphenyl diisocyanate (4,4'-diisocyanatodiphenylmethane), hexamethylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, or mixtures thereof.

11. The method of any one of claims 1-5, wherein the crosslinking agent is a dihaloalkane.

12. The method of claim 11, wherein the dihaloalkane is 1,4-dibromobutane, 1,2-dibromoethane, 1,5-dibromopentane, or mixtures thereof.

13. The method of claim 11, wherein the dihaloalkane has the formula: Xiwherein Xi and X2 are each, independently, F, Cl, Br, I, and n is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

14. The method of any one of claims 1-5, wherein the crosslinking agent is a diepoxide.

15. The method of any one of claims 1-5, wherein the crosslinking agent is diglycidylether, ethylene glycol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, Neopentyl Glycol Diglycidyl Ether, or mixtures thereof.

16. The method of any one of claims 1-5, wherein the crosslinking agent is a dianhydride.

17. The method of any one of claims 1-5, wherein the crosslinking agent is methylenedianhydride (MDA; 2,2'-oxydioxydiethanone), benzophenone-3,3',4,4'-tetracarboxylic dianhydride (2,2'-(4-oxocyclohexa-2,5-dien-l-ylidene)bis(benzenecarboxylic acid), 3,3',4,d'biphenyl dianhydride (2,2'-dicarboxy-4,4'-dioxo-[l,l'-biphenyl]-3,3'-dicarboxylic acid anhydride), 4,4'-oxydiphthalic anhydride, 1,2,3,4-cyclohexane tetracarboxylic dianhydride, or mixtures thereof.

18. The method of any one of claims 1-5, wherein the crosslinking agent is a diacid chloride.

19. The method of claim 18, wherein the diacid chloride is succinyl chloride, glutaryl chloride, adipoyl chloride, sebacoyl chloride, 4,4'-oxydiphthaloyl chloride, terephthaloyl chloride, or mixtures thereof.

20. The method of any one of claims 1-19, wherein the introducing comprises introducing the crosslinking agent to the plurality of porous particles to form a plurality of crosslinked particles.

21. The method of any one of claims 1-19, wherein the introducing comprises introducing the crosslinking agent with the first reagent to form the plurality of functionalized crosslinked particles.

22. The method of any one of claims 3-21, wherein the introducing comprises introducing the crosslinking agent with the first reagent and the second reagent to form the plurality of functionalized crosslinked particles.

23. The method of any one of claims 1-20, further comprising, prior to the introducing, exposing the plurality of porous particles to a third reagent comprising a polymer, thereby coating the plurality of porous particles.

24. The method of claim 23, after the exposing and before the introducing, drying the plurality of porous particles in a vacuum oven at between 50 °C and 100 °C until a hydration threshold of less than 5% (wt / wt) of water to the plurality of particles is reached.

25. The method of claims 23 or 24, wherein the polymer is poly(vinyl alcohol) (PVA).

26. The method of any one of claims 1-25, wherein the plurality of porous particles are in a solvent during the introducing, and wherein a ratio of solvent to the plurality of porous particles at the onset of the introducing is between 1.5 wt / wt and 4:1 wt / wt of the solvent to the plurality of porous particles.

27. The method of any one of claims 1-25, wherein the crosslinking agent is in a first solvent during the introducing, wherein a ratio of crosslinking agent to the plurality of porous particles at the onset of the introducing is up to 15% (wt / wt) of the crosslinking agent to the plurality of porous particles.

28. The method of any one of claims 3-25, wherein the crosslinking agent is in a first solvent during the introducing, wherein a ratio of crosslinking agent to the plurality of porous particles at the onset of the introducing is up to 50 mol% of the crosslinking agent to the second reagent.

29. The method of any one of claims 1-28, wherein the first reagent is in a second solvent during the introducing, wherein a ratio of the first reagent to the second solvent is between 20% to 80% (wt / wt) of the first reagent to the plurality of porous particles.

30. The method of any one of claims 1-29, wherein the at least one adsorbing moiety of the first reagent comprises an aminosilane.

31. The method of any one of claims 1-29, wherein the at least one adsorbing moiety of the first reagent consists of an aminosilane.

32. The method of claim 30 or 31, wherein the aminosilane has a structure in accordance with any of formulas I, la, lb, Ic, Id, Ie, If, Ig, If, II, Ila, lib, lie, lid, Illa, Illb, or IV.

33. The method of claim 30 or 31, whereinthe aminosilane comprises at least one amino moiety and at least one silane moiety, andthe at least one silane moiety comprises an alkoxysilane moiety, a trihalosilane moiety, a dihalosilane moiety, a monohalosilane moiety, a silanetriol moiety, a dialkoxysilanol moiety, a monoalkoxysilanol moiety, or an aminosilane oligomer.

34. The method of claim 30 or 31, wherein the aminosilane is3-aminopropyl)trimethoxy silane, (3-aminopropyl)tri ethoxy silane, [3-(2-aminoethylamino)propyl]trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl silanetriol, N1-(3-trimethoxysilylpropyl) diethylenetriamine, 3-aminopropylsilanetriol, N-(2aminoethyl)-3-aminopropylsilanetriol, tris(ethylmethylamino)chlorosilane, tris(dimethylamino)chlorosilane, 3-aminopropyl(diethoxy)methylsilane, N-[3-(trimethoxysilyl)propyl]ethylenediamine, bis(3-(methylamino)propyl)-trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, N-[3-(trimethoxysilyl)propyl]aniline, (N,N-dimethylamino propyl)trimethoxysilane, or a mixture thereof.

35. The method of any one of claims 1-29, wherein the at least one adsorbing moiety of the first reagent is a linear or a branched polyamine.

36. The method of any one of claims 1-29, wherein the at least one adsorbing moiety of the first reagent is a polyamine having the structure of any one of formulas Via, VIb, Vic, Vid, Vie, VIf, Vig, VIh, or Vli.

37. The method of any one of claims 1-29, wherein the at least one adsorbing moiety of the first reagent is poly(lysine, poly(L-lysine), poly(D-lysine), poly(LD-lysine), poly(ethyleneimine), poly(propyleneimine), poly(vinylamine), poly(N-methylvinylamine), poly(allylamine), poly(N-isopropyl acrylamide), poly(4-aminostyrene), chitosan, spermidine, spermine, norspermine, putrescine, cadaverine, tetraethylenepentamine, triethylenetetramine, an ethylene amine / oligomeric mix, diethylenetriamine, 2-(2-aminoethylamino)ethanol, ethylenediamine, piperazine, 2-piperazin-l-ylethylamine, 2-piperazin-l-ylethanol, pentaethylenehexamine, tetramethylethylenediamine, ethanolamine, trientine, 2,2’-iminodi(ethylamine), 2-aminoethanol, salts thereof, and / or copolymers thereof and / or mixtures thereof.

38. The method of any one of claims 1-37, wherein the first reagent and the second reagent are introduced to the plurality of porous particles before the crosslinking agent is introduced.

39. The method of any one of claims 1-38, wherein the interaction moiety of the second reagent comprises an aminosilane or a silane.

40. The method of any one of claims 1-38, wherein the interaction moiety of the second reagent comprises an aminosilane having a structure of any one of formulas I, la, lb, Ic, Id, Ie, If, Ig, If, II, Ila, lib, lie, lid, Illa, Illb, or IV.

41. The method of any one of claims 1-38, wherein the second reagent comprises a silane having a structure of any one of formulas V and Va.

42. The method of claim 3, wherein introducing the first reagent and the second reagent comprises mixing the first reagent and the second reagent in a second solvent to form a functionalization mixture and introducing the functionalization mixture on at least a portion of the surface of at least one of the plurality of porous particles.

43. The method of claim 42, wherein the functionalization mixture further comprises the crosslinking agent.

44. The method of any one of claims 1-43, the method further comprising drying the functionalized crosslinked particles to a hydration threshold of less than about 5% (wt / wt) of a solvent medium to the functionalized, crosslinked particles.

45. A composition comprising a plurality of crosslinked particles modified according to the method of any one of claims 1-44.

46. A composition comprising a plurality of functionalized crosslinked particles modified according to the method of any one of claims 1-44.

47. The composition of claim 45 or 46, wherein the composition adsorbs carbon dioxide.

48. The composition of any one of claims 45-47, wherein the composition adsorbs CO2 per dry kilogram in a range between 0.5 mol and 2.5 mol.

49. The composition of any one of claims 45-48, wherein the composition desorbs in a temperature range between 65 °C and 90 °C.

50. The composition of any one of claims 45-48, wherein the composition adsorbs CO2 at a relative humidity in a range between 5% and 95% relative humidity.

51. The composition of any one of claims 45-50, wherein the composition has a 50% strain crush strength of at least 1.5 MPa.

52. The composition of any one of claims 45-50, wherein the composition further comprises a hydrophobic moiety bound to the plurality of functionalized crosslinked particles.

53. The composition of claim 52, wherein the hydrophobic moiety is a hydrophobic silane compound or a hydrophobic polymer.

54. The composition of claim 52, wherein the hydrophobic moiety is a hydrophobic silane compound comprising a silane moiety and one, two, or three alkyl chains.

55. The composition of claim 52, wherein the hydrophobic moiety is a hydrophobic polymer comprising a polydimethylsiloxane, silicone oil, polyethylene, polytetrafluoroethylene, or polyurethane.

56. The composition of any one of claims 45-55, wherein the plurality of porous particles have (i) a distribution of pore sizes from 10 nanometers to 200 nanometers and (ii) a distribution of sieve diameters from 0.4 millimeters to 4 millimeters.

57. The composition of any one of claims 45-55, wherein the plurality of porous particles have (i) a distribution of pore sizes from 50 Angstroms to 300 Angstroms and (ii) a distribution of sieve diameters from 0.4 millimeters to 4 millimeters.

58. A method, comprising using the composition of any one of claims 45-57 to remove atmospheric CO2 from air by direct air capture.

59. A composition comprising:a plurality of porous particles;a surface modification layer disposed on at least a portion of a surface of each porous particle in at least a subset of the plurality of porous particles, wherein the surface modification layer comprises (i) an adsorbing moiety comprising one or more amine moieties and (ii) a linking moiety,wherein the composition is configured to adsorb atmospheric CO2 under a first condition and reversibly desorb adsorbed CO2 under a second condition.

60. A composition comprising:a plurality of porous particles;a polymer coated on at least a portion of a surface of each porous particle in at least a subset of the plurality of porous particles; anda surface modification layer disposed on at least a portion of a surface of each porous particle in the subset of the plurality of porous particles, wherein the surface modification comprises (i) an adsorbing moiety comprising one or more amine moieties and (ii) a linking moiety,wherein the composition is configured to adsorb atmospheric CO2 under a first condition and reversibly desorb adsorbed CO2 under a second condition.

61. The composition of claim 59 or 60, wherein the plurality of porous particles comprises a plurality of porous silica particles, a plurality of porous metal-organic framework (MOF) particles, or a plurality of ion-exchange resin particles.

62. The composition of claim 59 or 60, wherein the plurality of porous particles comprises a porous silica or silicate, a porous ceramic, a porous metal-organic substrate, a porous polymeric substrate, a porous ceramic / metal oxide together with porous silica, a porous alumina, a metal-organic framework (MOF), or a resin.

63. The composition of claim 59 or 60, wherein the plurality of porous particles comprises a substrate in a precipitated form, a sol-gel form, a fumed form, a calcined form, an agglomerated form, a granulated form, a powder, or granules.

64. The composition of any one of claims 59-63, wherein the plurality of porous particles have an average sieve diameter of between 25 pm and 4 mm.

65. The composition of any one of claims 59-64, wherein the plurality of porous particles include:pores that have a dimension from about 1 nm to 200 nm,an average pore size from about 30 nm to 80 nm, and / ora volume greater than 0.5 mL / g or from 0.1 mL / g to 5 mL / g.

66. The composition of any one of claims 59-64, wherein the plurality of porous particles have:(i) a distribution of pore sizes from 10 nanometers to 200 nanometers, and(ii) a distribution of sieve diameters from 0.4 millimeters to 4 millimeters.

67. The composition of any one of claims 59-64, wherein the plurality of porous particles have (i) a distribution of pore sizes from 50 Angstroms to 300 Angstroms and (ii) a distribution of sieve diameters from 0.4 millimeters to 4 millimeters.

68. The composition of any one of claims 59-67, whereinthe plurality of porous particles comprises a greatest dimension of at least 25 pm, the plurality of porous particles include a plurality of pores,the plurality of pores comprise a dimension of at least about 1 nm and a volume greater than about 0.5 mL / g.

69. The composition of any one of claims 59-68, wherein the surface modification layer is a polyamine and the composition consists of between 5% and 60% (wt / wt) polyamine.

70. The composition of any one of claims 59-68, wherein the surface modification layer is an aminosilane and the composition consists of between 5% and 80% (wt / wt) aminosilane.

71. The composition of any one of claims 59-70, wherein the surface modification layer comprises a crosslinker agent and the composition consists of 5% or less wt / wt of the crosslinker agent.

72. The composition of any one of claims 59-70, wherein the plurality of porous particles comprises a total surface area greater than about 100 m2 per dry gram.

73. The composition of any one of claims 59-71, wherein the composition adsorbs greater than 0.5 mol of CO2 per dry kilogram of composition or from about 0.5 mol to 2.5 mol of CO2 per dry kilogram of composition.

74. The composition of any one of claims 59-73, wherein the composition adsorbs CO2 at a relative humidity in a range between 5% and 95%.

75. The composition of any one of claims 49-73, wherein the surface modification layer comprises (i) an amine moiety and a silane moiety, (ii) a plurality of amine moieties, (iii) a linking moiety, or any combination thereof.

76. The composition of any one of claims 49-73, wherein the surface modification layer comprises an aminosilane, a polyamine, and / or a crosslinking agent.

77. The composition of claim 76, whereinthe aminosilane comprises a structure of one of formulas I, la, lb, Ic, Id, Ie, If, Ig, If, II, Ila, lib, lie, lid, Illa, Illb, or IV, andthe polyamine comprises a structure of one of formulas Via, VIb, Vic, Vid, Vie, VIf, Vig, VIh, or Vli, andthe crosslinking agent comprises a structure of one of formulas VII, Vila, Vile, Vlld, Vile, Vllf, Vllg, Vllh, Vllj, Vllk, VIII, Vllm.

78. The composition of any one of claims 59-77, further comprising a chelating agent bound to each porous particle in at least the subset of the plurality of porous particles.

79. The composition of claim 78, wherein the chelating agent comprises a phosphate-based chelator or a phosphonate-based chelator.

80. The composition of claim 78, wherein the chelating agent is etidronic acid or K3PO.

81. The composition of any one of claims 59-80, further comprising an antioxidant bound to at least the subset of the plurality of porous particles.

82. The composition of claim 81, wherein the antioxidant comprises a cyclic antioxidant, a hindered amine light stabilizer, or an organic sulfur-containing compound.

83. The composition of any one of claims 59-82, whereinthe first condition comprises a first temperature range, andthe second condition comprises a second temperature range higher than the first temperature range.

84. The composition of any one of claims 59-83, wherein the first condition comprises a first gas pressure, and the second condition comprises a second gas pressure lower than the first gaspressure.

85. The composition of any one of claims 59-84, whereinthe first condition comprises a first CO2 concentration, andthe second condition comprises a second CO2 concentration lower than the first CO2 concentration.

86. The composition of any one of claims 59-85, further comprising an additive, a hydrophobic silane compound, and / or a hydrophobic polymer attached to at least the subset of subset of the plurality of porous particles.

87. The composition of claim 59 or 60, wherein the composition comprises:15% wt / wt poly(vinyl alcohol),1% wt / wt etidronic acid or K3PO,10% wt / wt polyethyleneimine,45% wt / wt N-2-aminoethyl-3-aminoproplytrimethoxysilane,1% wt / wt hindered amine light stabilizer, and1% wt / wt terephthalaldehyde.

88. The composition of claim 59 or 60, wherein the composition comprises: between 5% wt / wt and 25% wt / wt poly(vinyl alcohol), between 0.3% wt / wt and 2% wt / wt etidronic acid or K3PO, between 5% wt / wt and 15% wt / wt polyethyleneimine,between 35% wt / wt and 55% wt / wt N-2-aminoethyl-3-aminoproplytrimethoxysilane, between 0.5% wt / wt and 2 % wt / wt hindered amine light stabilizer, and between 0.5% wt / wt and 2% wt / wt terephthalaldehyde.

Images