Functionalized Materials for Carbon Capture and Their Systems

Abstract

The present disclosure relates to a functionalized material that can optionally be used as an adsorbent, a method of making such a material, and a system using such a material. The processes, methods, and systems herein can be used for the separation of carbon dioxide from a fluid stream.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the benefit of U.S. Provisional Patent Application No. 63 / 357,932, filed on July 1, 2022; U.S. Provisional Patent Application No. 63 / 357,950, filed on July 1, 2022; U.S. Provisional Patent Application No. 63 / 357,935, filed on July 1, 2022; U.S. Provisional Patent Application No. 63 / 357,941, filed on July 1, 2022; U.S. Provisional Patent Application No. 63 / 357,919, filed on July 1, 2022; U.S. Provisional Patent Application No. 63 / 357,912, filed on July 1, 2022; U.S. Provisional Patent Application No. 63 / 357,758, filed on July 1, 2022; U.S. Provisional Patent Application No. 63 / 357,770, filed on July 1, 2022; U.S. Provisional Patent Application No. 63 / 357,951, filed on July 1, 2022; U.S. Provisional Patent Application No. 63 / 358,006, filed on July 1, 2022; U.S. Provisional Patent Application No. 63 / 358,003, filed on July 1, 2022; and U.S. Provisional Patent Application No. 63 / 460,243, filed on April 18, 2023.

[0002] This disclosure relates to a functionalized material that can optionally be used as an adsorbent, a method of making such a material, and a system using such a material. The processes, methods, and systems herein can be used for the separation of carbon dioxide from a fluid stream.

Background Art

[0003] Atmospheric carbon concentrations have been rising over decades in correlation with industrialized activities. Carbon dioxide is a major contributor to the total carbon concentration. Concerns about global warming have led to an interest in the capture of carbon dioxide emissions.

Summary of the Invention

[0004] Generally, the present disclosure relates to functionalized materials, methods of making and using them, and systems that can be configured to use such materials. In certain embodiments, the functionalized materials can be used to capture and remove carbon dioxide from a gas environment.

[0005] Accordingly, in one aspect, the present disclosure encompasses a functionalized material comprising a plurality of porous particles and a surface modification layer disposed on at least a portion of the surface of at least one of the plurality of porous particles, the surface modification layer including an adsorption portion containing one or more amine moieties. In some embodiments, the material is configured to adsorb atmospheric CO2 under a first condition and reversibly desorb the adsorbed CO2 under a second condition.

[0006] 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 plurality of porous particles include porous silica or silicate, porous ceramic, porous metal-organic substrate, porous polymer substrate, porous ceramic / metal oxide together with porous silica, porous alumina, metal-organic framework (MOF), or resin. In some embodiments, the plurality of porous particles include a substrate provided in a precipitated form, sol-gel form, fumed form, calcined form, aggregated form, granulated form, powder, or granule.

[0007] In some embodiments, the plurality of porous particles include an average dimension or mean dimension (e.g., diameter) of about 25 μm to 4 mm (e.g., 25 μm to 3 mm, 25 μm to 2 mm, 25 μm to 1 mm, or other ranges described herein).

[0008] In some embodiments, the plurality of porous particles include a plurality of pores. In some embodiments, the plurality of pores include a dimension of about 1 to 200 nm, an average pore size of about 30 to 80 nm, and / or a volume of greater than about 0.1 mL / g or 0.5 mL / g (e.g., 0.1 to 5 mL / g).

[0009] In some embodiments, the plurality of porous particles include a maximum dimension of at least 25 μm. In some embodiments, the plurality of pores of the plurality of porous particles include a dimension of at least about 1 nm and / or a volume of greater than about 0.5 mL / g.

[0010] In some embodiments, the surface modification layer includes 5% to 60% (weight / weight) polyamine (e.g., any of those described herein, e.g., small molecule polyamine, macromolecule polyamine, low molecular weight (MW) polyamine, high MW polyamine, oligomeric form of polyamine, or polymeric form of polyamine) with respect to the plurality of porous particles lacking the surface modification layer. In some embodiments, the polyamine is a macromolecule polyamine, a high MW polyamine, or a polymeric form of polyamine. In some embodiments, the polyamine is any of those described herein (e.g., those in formulas (IIIa)-(IIIi)). In some embodiments, the polyamine is present in an amount of about 5% to 60% (weight / weight) polyamine with respect to the plurality of porous particles (e.g., 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% (weight / weight) amount).

[0011] In some embodiments, the surface modification layer comprises 5% to 80% (weight / weight) of an aminosilane with respect to a plurality of porous particles lacking the surface modification layer. In some embodiments, the aminosilane is any of those described herein (e.g., those in Formula (I), (Ia)-(If), (II), or (IIa)-(IId)). In some embodiments, the aminosilane is present in an amount of about 5% to 80% (weight / weight) of aminosilane with respect 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% (weight / weight)).

[0012] In some embodiments, the plurality of porous particles comprise a total surface area of greater than about 100 m 2 per dry gram. In some embodiments, the material adsorbs greater than about 0.8 mol of CO2 (mol of CO2 / kg) or about 0.8 to 2.5 mol of CO2 / kg per dry kilogram.

[0013] In some embodiments, the material adsorbs CO2 at a relative humidity in the range of about 0% to 100% or about 5% to 95%.

[0014] In some embodiments, the surface modification layer comprises (i) an amine moiety and a silane moiety, (ii) a plurality of amine moieties, or (iii) both (i) and (ii). In some embodiments, the surface modification layer is provided by causing one or more compounds to interact with at least a portion of the surface of at least one of the plurality of porous particles. In some embodiments, the one or more compounds are selected from the group consisting of aminosilanes and / or polyamines. In some embodiments, the aminosilane comprises a structure having one of formulas (I), (Ia)-(If), (II), and (IIa)-(IId). In some embodiments, the polyamine comprises a structure having one of formulas (IIIa)-(IIIi). In some embodiments, the polyamine is a small molecule polyamine, a low MW polyamine, a large molecule polyamine, a high MW polymer, an oligomer polyamine, a polymer polyamine, or a mixture thereof.

[0015] In some embodiments, the first condition includes a first temperature range, and the second condition includes a second temperature range higher than the first temperature range. In some embodiments, the first condition includes a first gas pressure (e.g., a partial pressure for CO2), and the second condition includes a second gas pressure lower than the first gas pressure (e.g., a partial pressure for CO2). In some embodiments, the first condition includes a first CO2 concentration, and the second condition includes a second CO2 concentration lower than the first CO2 concentration.

[0016] In some embodiments, the material further comprises an antioxidant moiety, an additive, a hydrophobic silane compound, and / or a hydrophobic polymer (e.g., any of those described herein).

[0017] In another aspect, the present disclosure is a method of forming a functionalized material, the method comprising introducing a first reagent into a plurality of porous particles and a solvent medium, thereby providing a functionalization mixture, wherein the first reagent comprises at least one adsorption moiety comprising one or more amine moieties; removing the functionalized material from the functionalization mixture, wherein the functionalized material comprises a plurality of porous particles and a surface modification layer disposed on at least a portion of the surface of at least one of the plurality of porous particles, and the surface modification layer comprises at least one adsorption moiety; and drying the functionalized material.

[0018] In some embodiments, the first reagent comprises an aminosilane, the aminosilane comprising at least one amino moiety and at least one silane moiety. In some embodiments, the 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. In some embodiments, the at least one silane moiety comprises any of those described herein. In some embodiments, the aminosilane comprises a structure having one of Formulas (I), (Ia)-(If), (II), and (IIa)-(IId). In some embodiments, the first reagent comprising an aminosilane is provided in the presence of a second reagent, the second reagent comprising a polyamine. In some embodiments, the first reagent is provided to the plurality of porous particles, and then the second reagent comprising a polyamine is provided to the functionalization mixture.

[0019] In some embodiments, the method further comprises providing the second reagent comprising a polyamine to the functionalized material after removal from the functionalization mixture.

[0020] In some embodiments, the first reagent comprises a polyamine. In some embodiments, the polyamine is a small molecule polyamine, a low MW polyamine, a large molecule polyamine, a high MW polymer, an oligomeric polyamine, a polymeric polyamine, or a mixture thereof. In some embodiments, the polyamine comprises a structure having one of formulas (IIIa)-(IIIi). In some embodiments, the first reagent comprising the polyamine is provided in the presence of a second reagent, and the second reagent comprises an aminosilane. In some embodiments, the first reagent is provided to a plurality of porous particles, and then the second reagent comprising the aminosilane is provided to a functionalization mixture.

[0021] In some embodiments, the first reagent comprises a small molecule polyamine or a mixture comprising a plurality of small molecule polyamines.

[0022] In some embodiments, the functionalization mixture comprises from 5% to 80% (weight / weight) of the first reagent with respect to the plurality of porous particles. In some embodiments, the first reagent comprises a polyamine, and the functionalization mixture comprises from 5% to 60% (weight / weight) of the polyamine with respect to the plurality of porous particles. In some embodiments, the first reagent comprises an aminosilane, and the functionalization mixture comprises from 5% to 80% (weight / weight) of the aminosilane with respect to the plurality of porous particles. Other ranges may be used (e.g., any range described herein).

[0023] In some embodiments, the solvent medium comprises water. In some embodiments, the solvent medium comprises a polar aprotic solvent or a neutral aprotic solvent. In some embodiments, the solvent medium comprises an organic solvent selected from toluene, hexane, cyclohexane, and tetrahydrofuran. In some embodiments, the solvent medium comprises methanol, cyclohexane, hexane, ethanol, water, or a combination thereof.

[0024] In some embodiments, drying comprises drying the functionalized material to a hydration threshold of about 5% (weight / weight) solvent medium. In some embodiments, the method provides an adsorbent material that includes a functionalized material (e.g., any of those described herein).

[0025] In another aspect, the present disclosure is a method of forming a functionalized material, the method comprising introducing a first reagent and a second reagent into water, thereby providing a functionalization mixture; introducing a plurality of porous particles into the functionalization mixture over a period of time, thereby forming a functionalized material; removing the functionalized material from the functionalization mixture; and drying the functionalized material.

[0026] In some embodiments, the first reagent includes a polyamine and the second reagent includes an aminosilane. In some embodiments, the aminosilane includes a structure having one of formulas (I), (Ia)-(If), (II), and (IIa)-(IId), and the polyamine includes a structure having one of formulas (IIIa)-(IIIi).

[0027] In some embodiments, the functionalized material includes a plurality of porous particles and a surface modification layer disposed on at least a portion of at least one surface of the plurality of porous particles, the surface modification layer including at least one adsorption portion.

[0028] In some embodiments, the plurality of porous particles includes an amount of at least 25 kilograms. In some embodiments, the method provides an adsorbent material that includes a functionalized material (e.g., any of those described herein).

[0029] In some embodiments, said drying comprises drying the functionalized material to a hydration threshold of about 5% (weight / weight) of solvent medium. In some embodiments, said drying is performed in a double cone vacuum dryer, a conveyor belt dryer, or a Nutsche filter dryer.

[0030] In another aspect, the present disclosure is a method for removing CO2 from air, comprising providing ambient air containing CO2 to a holder containing an adsorbent material, thereby providing a rich adsorbent material, and optionally desorbing CO2 from the rich adsorbent material, thereby providing a lean material. In some embodiments, the adsorbent material comprises a functionalized material (e.g., any of those described herein).

[0031] In another aspect, the present disclosure encompasses a direct air capture (DAC) system comprising a first inlet configured to receive an adsorbent material, an adsorber system configured to adsorb CO2 from ambient air using the adsorbent material, thereby providing a rich adsorbent material, and a desorber system configured to desorb CO2 from the rich adsorbent material, thereby providing a lean material and delivering the lean adsorbent material to the adsorber system.

[0032] In some embodiments, the adsorbent material comprises a plurality of porous particles and a surface modification layer disposed on at least a portion of the surface of at least one of the plurality of porous particles, the surface modification layer comprising an adsorption portion containing one or more amine moieties. In some embodiments, the adsorbent material is configured to adsorb atmospheric CO2 under a first condition and reversibly desorb the adsorbed CO2 under a second condition. In some embodiments, the adsorbent material comprises a functionalized material (e.g., any of those described herein).

[0033] In another aspect, the present disclosure includes a reactor comprising a reaction chamber extending from a first chamber wall along a first direction to a second chamber wall opposite the first chamber wall, the reaction chamber including a hollow compartment extending from a base to a top wall in a second direction perpendicular to the first direction, the compartment having a base portion proximal to the base and a top portion distal to the base in a cross-section perpendicular to the first direction, the base portion being narrower than the top portion.

[0034] In some embodiments, the reactor further includes an inlet in the first chamber wall providing access for delivery of a powdered adsorbent material into the reaction chamber, and an outlet in the second chamber wall providing for discharge of the powdered adsorbent material from the reaction chamber.

[0035] In some embodiments, the reactor further includes one or more air chambers each in fluid communication with the hollow compartment via a channel at the base of the hollow compartment, one or more blowers each configured to receive ambient air and blow air into a corresponding one of the air chambers during operation of the reactor, and one or more exhaust ports configured to remove air from the compartment of the reaction chamber during operation of the reactor.

[0036] In some embodiments, the reactor further includes a distribution plate in fluid communication with the one or more air chambers and the hollow compartment. In some embodiments, the distribution plate is W-shaped. In some embodiments, the distribution plate is flat. In some embodiments, the reactor further includes an additional distribution plate, the additional distribution plate being flat.

[0037] In some embodiments, the one or more exhaust ports are disposed in the top wall of the reaction chamber.

[0038] In some embodiments, the reactor further includes a feeder disposed to be in fluid communication with the inlet, and the feeder is configured to deliver the powdered adsorbent material to the reaction chamber during operation of the reactor. In some embodiments, the inlet is located proximal to the base.

[0039] In some embodiments, the reactor is configured such that during operation, the pressure drop from the reaction chamber to the air chamber is 9.0 psi or less.

[0040] In some embodiments, the reactor is configured such that during operation, the adsorbent chamber accommodates at least about 10 liters of air per gram of adsorbent material.

[0041] In some embodiments, the reactor further includes one or more louvers, the one or more louvers are arranged along a first direction and are located on one or more walls of the reactor, and the louvers are configured to draw ambient air into the one or more air chambers.

[0042] In some embodiments, the hollow section includes a first tapered portion proximal to the base in cross-section. In some embodiments, the hollow section further includes a second tapered portion spaced from the first tapered portion in cross-section.

[0043] In some embodiments, the powdered adsorbent material includes particles having a diameter of about 25 to 4,000 μm. In some embodiments, the powdered adsorbent material is a CO2 adsorbent. In some embodiments, the powdered adsorbent material includes a functionalized material (e.g., any of those described herein).

[0044] In another aspect, the present disclosure is a method for removing CO2 from the atmosphere, the method comprising: providing ambient air containing CO2 to a reactor comprising one or more air chambers; blowing the ambient air such that the ambient air migrates from the one or more air chambers into a reaction chamber; delivering a powdered adsorbent material to the reaction chamber via an inlet; creating a fluidized bed of the powdered adsorbent material and air under conditions such that the powdered adsorbent material adsorbs CO2 from the air to form CO2-reduced air and spent powdered adsorbent material; continuously removing the spent powdered adsorbent material from the reaction chamber; and continuously removing the CO2-reduced air from the reaction chamber via one or more exhaust ports. In some embodiments, the powdered adsorbent material comprises a functionalized material (e.g., any of those described herein).

[0045] In another aspect, the present disclosure encompasses a direct air capture (DAC) system, the system comprising: a fluidized bed adsorption reactor configured to adsorb CO2 from ambient air using a powdered adsorbent material; a desorption reactor configured to receive the powdered adsorbent material from the fluidized bed adsorption reactor and desorb CO2 from the powdered adsorbent material; and industrial process equipment that generates waste heat, the waste heat being provided to the desorption reactor to heat the powdered adsorbent material. In some embodiments, the powdered adsorbent material comprises a functionalized material (e.g., any of those described herein).

[0046] In another aspect, the present disclosure encompasses a structure comprising a chamber defined by a plurality of panels, each panel being suspended between a pair of beams extending from a base of the structure in a first direction, and the height of each panel extending from a bottom of the panel to a top of the panel in the first direction.

[0047] In some embodiments, each panel comprises a porous inner sheet, a porous outer sheet, and a cavity between the inner and outer sheets extending from the top of the panel to the bottom of the panel.

[0048] In some embodiments, the structure further includes an inlet that provides access for delivery of the adsorbent material to cavities at the tops of the plurality of panels, an outlet that provides for discharge of the adsorbent material from the bottoms of the cavities of the plurality of panels, and a blower arranged to direct fluid into the chamber.

[0049] In some embodiments, the adsorbent material within the cavities of the panels forms a vertically falling moving bed absorber.

[0050] In some embodiments, the cavity between the inner sheet and the outer sheet is divided into a plurality of channels, and the plurality of channels are separated by fabric ribs that connect the inner sheet and the outer sheet at intervals between the side edges of the panel.

[0051] In some embodiments, each channel of the plurality of channels has a substantially square cross-section in a plane perpendicular to the first direction.

[0052] In some embodiments, the cavity has a thickness between the inner sheet and the outer sheet, and the thickness is 20 centimeters or less.

[0053] In some embodiments, the chamber has a substantially cylindrical shape with a cylindrical axis extending in a first direction. In some embodiments, the chamber has a substantially rectangular prism shape with four walls.

[0054] In some embodiments, at least one of the four walls includes a panel of the plurality of panels.

[0055] In some embodiments, the structure further includes a metering device configured to control the flow of the adsorbent material from the cavity to the outlet.

[0056] In some embodiments, the inner sheet and the outer sheet include a fabric material.

[0057] In some embodiments, the adsorbent material has a pelletized form and is configured to adsorb carbon dioxide from a fluid. In some embodiments, the adsorbent material includes a functionalized material (e.g., any of those described herein).

[0058] In some embodiments, the blower is positioned in the lower third of the chamber in a first direction, where the lower third is the portion closest to the base of the structure, or the blower is positioned in the middle third of the chamber in the first direction. In some embodiments, the blower is configured to direct the fluid in the first direction. In some embodiments, the fluid includes a gas or air.

[0059] In another aspect, the present disclosure includes a method that includes feeding an adsorbent material at an inlet of a structure, where the structure includes a chamber defined by a plurality of panels. In some embodiments, each panel is suspended between a pair of beams. In some embodiments, each panel includes a porous inner sheet, a porous outer sheet, and a cavity between the inner and outer sheets that extends from the top to the bottom of the panel, and the inlet provides access for delivery of the adsorbent material to the cavity at the top of the plurality of panels.

[0060] In some embodiments, the method includes extracting the adsorbent material from an outlet of the structure, where the outlet provides for discharge for removal of the adsorbent material from the bottom of the cavity of the plurality of panels, and extracting the adsorbent material from the outlet causes the adsorbent material in the cavity to fall due to gravity, and further includes directing a fluid through the plurality of panels in a direction from the inner sheet toward the outer sheet.

[0061] In some embodiments, the method includes controlling the rate of extraction of the adsorbent material from the outlet to control the volumetric flow rate of the adsorbent material passing through the cavity due to gravity.

[0062] In some embodiments, the method includes controlling the rate at which an adsorbent material is fed at an inlet of a structure based on the rate at which the adsorbent material is withdrawn from an outlet.

[0063] In some embodiments, the method includes controlling the rate at which an adsorbent material is withdrawn from an outlet to control the exposure time of the adsorbent material to a fluid.

[0064] In some embodiments, the method includes controlling the exposure time of the adsorbent material to a fluid to be 30 minutes or more and 90 minutes or less.

[0065] In another aspect, the present disclosure includes a structure including a first beam extending from a base of the structure toward a top of the structure in a first direction, a second beam spaced apart from the first beam and extending parallel to the first beam, and a panel coupled to the first beam at a first edge and coupled to the second beam at a second edge, the width of the panel extending from the first edge to the second edge in a direction orthogonal to the first direction and the height of the panel extending from a bottom of the panel to a top of the panel in the first direction.

[0066] In some embodiments, the panel includes a porous inner sheet, a porous outer sheet, and a cavity between the inner sheet and the outer sheet extending from a top of the panel to a bottom of the panel.

[0067] In some embodiments, the structure further includes an inlet providing access for delivery of an adsorbent material to the cavity at a top of the panel, an outlet providing discharge for removal of the adsorbent material from a bottom of the cavity, and a blower arranged to direct a fluid passing through the panel in a direction from the inner sheet toward the outer sheet.

[0068] In another aspect, the present disclosure is a system for removing carbon dioxide from an adsorbent material comprising a bulk solid, the system comprising: a first heat exchanger configured to evaporate water vapor from the adsorbent material by transferring heat from a working fluid and a heat source fluid to the adsorbent material; a condenser configured to condense water vapor by transferring heat from the water vapor to the working fluid; a second heat exchanger configured to desorb carbon dioxide from the adsorbent material by transferring heat from the working fluid to the adsorbent material; a pump configured to remove carbon dioxide from the second heat exchanger; a closed loop flow path for circulating the working fluid between the first heat exchanger, the condenser, and the second heat exchanger; an open loop flow path for providing a heat source fluid to the first heat exchanger; and a channel for transporting the adsorbent material from the first heat exchanger to the second heat exchanger.

[0069] In some embodiments, the first heat exchanger includes a first inlet providing access for delivery of the adsorbent material to the first heat exchanger and a first outlet providing access for removal of the adsorbent material from the first heat exchanger. In some embodiments, during operation, the first inlet has a higher elevation than the first outlet.

[0070] In some embodiments, the second heat exchanger includes a second inlet providing access for delivery of the adsorbent material to the second heat exchanger and a second outlet providing access for removal of the adsorbent material from the second heat exchanger. In some embodiments, during operation, the second inlet has a higher elevation than the second outlet.

[0071] In some embodiments, the second inlet of the second heat exchanger has a higher elevation (e.g., during operation) than the first outlet of the first heat exchanger. In some embodiments, the second inlet of the second heat exchanger has a lower elevation (e.g., during operation) than the first outlet of the first heat exchanger.

[0072] In some embodiments, the first heat exchanger and the second heat exchanger include a plate heat exchanger, a shell and tube heat exchanger, or a shell and plate heat exchanger. In some embodiments, the first heat exchanger includes an evaporator and the second heat exchanger includes a desorber.

[0073] In some embodiments, the closed loop flow path and the open loop flow path are fluidly isolated from each other.

[0074] In some embodiments, the structure further includes a metering device configured to control the flow of the adsorbent material into the first heat exchanger.

[0075] In some embodiments, the adsorbent material has a pelletized form and is configured to adsorb carbon dioxide from a fluid. In some embodiments, the adsorbent material includes a functionalized material (e.g., any of those described herein).

[0076] In another aspect, the present disclosure is a method for removing carbon dioxide from an adsorbent material including a bulk solid, the method including circulating a working fluid in a closed loop between a first heat exchanger, a condenser, and a second heat exchanger; providing a heat source fluid to the first heat exchanger; evaporating water vapor from the adsorbent material by transferring heat from the working fluid and the heat source fluid to the adsorbent material in the first heat exchanger; condensing the water vapor by transferring heat from the water vapor to the working fluid in the condenser; transporting the adsorbent material from the first heat exchanger to the second heat exchanger via a channel; desorbing carbon dioxide from the adsorbent material by transferring heat from the working fluid to the adsorbent material in the second heat exchanger; and removing the carbon dioxide from the second heat exchanger by a pump. In some embodiments, the adsorbent material includes a functionalized material (e.g., any of those described herein).

[0077] In some embodiments, the method further includes sending the adsorbent material at the inlet of the first heat exchanger and extracting the adsorbent material from the outlet of the first heat exchanger. In some embodiments, the adsorbent material moves from the inlet of the first heat exchanger to the outlet of the first heat exchanger due to gravity.

[0078] In some embodiments, the method further includes sending the adsorbent material at the inlet of the second heat exchanger and extracting the adsorbent material from the outlet of the second heat exchanger. In some embodiments, the adsorbent material moves from the inlet of the second heat exchanger to the outlet of the second heat exchanger due to gravity.

[0079] In some embodiments, the method further includes transferring heat from the water vapor evaporated from the adsorbent material in the first heat exchanger to the adsorbent material in the second heat exchanger via a working fluid, and cooling the adsorbent material in the second heat exchanger using a heat source fluid pre-cooled in the first heat exchanger.

[0080] In some embodiments, the method further includes using a second pump to establish a vacuum pressure in the first heat exchanger and transporting water vapor from the first heat exchanger to a condenser.

[0081] In some embodiments, the method further includes removing the condensed water vapor from the condenser via a water outlet.

[0082] In some embodiments, the method further includes using a pump to establish a vacuum pressure in the second heat exchanger and using an airlock to maintain the vacuum pressure in the first heat exchanger and the second heat exchanger.

[0083] In another aspect, the present disclosure is a system for removing carbon dioxide from an adsorbent material containing a bulk solid, the system including a first heat exchanger configured to evaporate water vapor from the adsorbent material by transferring heat from a heat source fluid to the adsorbent material, a second heat exchanger configured to desorb carbon dioxide from the adsorbent material by transferring heat from a working fluid to the adsorbent material, a pump configured to remove carbon dioxide from the second heat exchanger, a third heat exchanger configured to cool the adsorbent material by transferring heat from the adsorbent material to a cooling fluid, and a channel for transporting the adsorbent material from the first heat exchanger to the second heat exchanger and the third heat exchanger.

[0084] In some embodiments, the system further includes an inlet providing access for delivery of the adsorbent material to the first heat exchanger and an outlet providing discharge for removal of the adsorbent material from the third heat exchanger. In some embodiments, during operation, the inlet has a higher elevation than the outlet.

[0085] In some embodiments, the first heat exchanger includes an evaporator, the second heat exchanger includes a desorber, and the third heat exchanger includes a cooler. In some embodiments, the adsorbent material has a pelletized form and is configured to adsorb carbon dioxide from a fluid.

[0086] In some embodiments, the pump is configured to establish a vacuum pressure in the first heat exchanger, the second heat exchanger, and the third heat exchanger. In some embodiments, the adsorbent material includes a functionalized material (e.g., any of those described herein).

[0087] 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.

[0088] 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 in a particular location in the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0089]

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[0090] In the figures, like reference numerals indicate like elements. DETAILED DESCRIPTION OF THE INVENTION

[0091] Generally, the present disclosure relates to a functionalized material (e.g., a functionalized porous material) and a method of making the same, the functionalized material being functionalized with an adsorption moiety (e.g., a compound, e.g., an amine moiety provided by an amine, an aminosilane, a polyamine, a monoamine, or a combination thereof). In some embodiments, the functionalization further includes an interaction moiety (e.g., a compound, e.g., a silane moiety provided by a silane, an aminosilane, etc.). Such moieties (e.g., an amine moiety and / or a silane moiety) can be provided by any compound and any useful combination of two or more compounds (e.g., one or more of an amine, an aminosilane, a polyamine, a monoamine, or any combination thereof).

[0092] In certain embodiments, the functionalized material can be used to reversibly capture carbon dioxide from a gas at a low concentration (e.g., less than 400 ppm) or under atmospheric conditions (e.g., 350 - 550 ppm). In some embodiments, a porous substrate is used, the substrate being characterized by a large pore size and / or a high surface area, and the amine moiety being used as an adsorption moiety to provide increased carbon capture (e.g., more than 0.8 mol of CO2 (mol of CO2 / kg) per kg of dry adsorbent, more than 1.2 mol of CO2 / kg or more than 2 mol of CO2 / kg). One or more compounds can be used to provide the adsorption moiety and / or the interaction moiety. Such compounds can include amines, aminosilanes, polyamines, monoamines, and others described herein.

[0093] In some embodiments, the adsorption moiety includes an amine moiety and the interaction moiety includes a silane moiety (e.g., any of those described herein). For example, without limitation, an aminosilane compound having both an amine moiety and a silane moiety can be used with a particular substrate, whereby the silane moiety interacts with the surface of the substrate, such that the amine moiety is accessible at the surface to adsorb CO2.

[0094] In other embodiments, both the adsorption moiety and the interaction moiety include an amine moiety. For example, without limitation, a polyamine compound having at least two amine moieties can be used with a particular substrate, whereby the first moiety interacts with the surface of the substrate, such that the second amine moiety is accessible at the surface for adsorbing CO2.

[0095] In still other embodiments, the adsorption moiety includes at least two amine moieties, the first amine moiety is provided by a first compound (e.g., an aminosilane), and the second amine moiety is provided by a second compound (e.g., a polyamine). As will be appreciated, any useful combination of the adsorption moiety and / or the interaction moiety can be used.

[0096] Accordingly, functionalized materials, as well as methods of forming and using such materials (e.g., as adsorbents) are described herein. In some embodiments, the method includes forming or using a functionalized material that includes a porous structure that allows gases to diffuse through the material and provides a large surface area for gases to be captured or "adsorbed." Also described herein are systems for using such materials in various capture processes. In some embodiments, the system includes a sample holder, a reactor, an adsorber, a desorber, etc., which are used to adsorb carbon dioxide using a functionalized material (e.g., any of those described herein) and / or to regenerate a functionalized material having adsorbed carbon dioxide (e.g., any of those described herein).

[0097] I. Functionalized Materials The present disclosure relates to a functionalized material having one or more functional groups. For example, without limitation, an initial material or substrate can be functionalized to include one or more functional groups (e.g., one or more amine groups) configured to capture carbon dioxide (CO2). In some non-limiting embodiments, the material can have any useful structure (e.g., as particles), any useful sub-structure (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. A silica substrate having amine functionalization, e.g., one or more amine-containing moieties covalently bonded on the surface, can achieve reversible capture of carbon dioxide from a gas mixture (e.g., air). Also, other substrates and moieties that can provide a functionalized material for carbon capture are described herein.

[0098] For example, FIG. 1A provides a non-limiting functionalized material 100A, and the functionalized material 100A includes a substrate 102A having a plurality of pores 104A-a, 104A-b. Then, the surface 103A of the substrate 102A can include a functional moiety 106A, and then the functional moiety 106A can include an adsorption moiety 110A (e.g., a CO2 adsorption moiety) and an interaction moiety 108A (e.g., a silane-containing interaction moiety). The functional moiety 106A can further include other moieties, groups, or molecules to provide an adsorption material for use as an adsorbent. Such moieties, groups, or molecules can include an amine group (e.g., -NR N1 R N2 as described herein, which can be present in amines, aminosilanes, polyamines, etc.), a polymer (e.g., a hydrophobic polymer or a polyamine), an antioxidant, etc. Further, such moieties, groups, or molecules can form interactions (e.g., covalent and / or non-covalent interactions) among themselves or between themselves and the surface of the substrate.

[0099] The functional moiety can have any number of moieties to facilitate the capture of CO2. Further, such moieties can be provided by any number of compounds. For example, FIG. 1B provides a non-limiting functionalized material 100B, which includes a substrate 102B having a plurality of pores 104B-a, 104B-b. The surface 103B of the substrate 102B can then include a functional moiety 106B, which can then include a first adsorption moiety 110B (e.g., a first CO2 adsorption moiety), a second adsorption moiety 112B (e.g., a second CO2 adsorption moiety), and an interaction moiety 108B (e.g., a silane-containing interaction moiety).

[0100] Such moieties can be provided in any useful manner. In some embodiments, the surface of the substrate is functionalized by the use of a first CO2 adsorption compound (e.g., including an aminosilane) and a second CO2 adsorption compound (e.g., a polyamine). The first CO2 adsorption compound can then provide a first adsorption moiety (e.g., moiety 110B in FIG. 1B), and the second CO2 adsorption compound can provide a second adsorption moiety (e.g., moiety 112B in FIG. 1B).

[0101] When the first CO2 adsorption compound is an aminosilane, the aminosilane can include a silane moiety as a non-limiting interaction moiety (e.g., interaction moiety 108B in FIG. 1B) and an amine moiety as a non-limiting first adsorption moiety (e.g., first adsorption moiety 110B in FIG. 1B). In some embodiments, the aminosilane is covalently bonded to the outer surface of the substrate (e.g., surface 102B in FIG. 1B) and covalently bonded within the pores (e.g., pores 104B-a, 104B-b in FIG. 1B). Other examples of adsorption compounds can include any of the compounds described herein (e.g., any aminosilane, or other compounds including one or more amine moieties). In some embodiments, the aminosilane and the polyamine together form a network and provide a stable CO2 adsorption function.

[0102] The second adsorption moiety can be provided by any useful second adsorption compound. Examples of adsorption compounds can include any of the compounds described herein (e.g., any compound containing one or more amine moieties). Any useful combination of the second and first adsorption compounds can be used, and such compounds can interact in any useful manner to provide a functionalized network or coating disposed on the surface of the substrate. Such a network or coating can then be characterized by any useful combination of the adsorption moiety and the interaction moiety.

[0103] The second adsorption moiety may be provided with a second interaction moiety or may be provided without it. The second interaction moiety can provide direct or indirect attachment to the surface of the substrate. For example, without limitation, a polyamine can include a plurality of amine moieties and at least one linker disposed between at least two amine moieties (e.g., -(R A -L) n -, where in the formula, R A is an amine moiety, L is a linker, and n is an integer). The amine moiety R A can act as an adsorption moiety. Depending on the other components present in the functionalized material, either the amine moiety R A or the linker L can act as an interaction moiety. For example, the amine moiety R A of the polyamine can interact with other amine moieties or silane moieties by hydrogen bonding or ionic interaction.

[0104] In some embodiments, the second adsorption compound is a polyamine, and the polyamine can include an amine moiety as a non-limiting second adsorption moiety (e.g., the second adsorption moiety 112B in FIG. 1B). The second adsorption moiety can be a certain specific functional group (e.g., -NR N1 R N2 or -NR N1-amine group), or a specific compound having a specific functional group (e.g., -NR described herein N1 R N2 or -NR N1 -compounds containing one or more amine groups). Other examples of the adsorption compound may include any of the compounds described herein (e.g., any polyamine, or other compounds containing one, two, or more amine moieties).

[0105] The second adsorption moiety can interact with other functional groups, moieties, or compounds in the functionalized material in various ways. For example, without limitation, the second adsorption moiety can interact with the first adsorption moiety, the interaction moiety, the surface of the substrate, or another second adsorption moiety. Such interactions can include covalent and / or non-covalent interactions (e.g., any of those described herein). In some embodiments, the second adsorption moiety can interact with the first adsorption moiety. In some embodiments, the second adsorption moiety can interact with the interaction moiety.

[0106] In some embodiments, the second adsorption moiety includes a polyamine or an amine moiety from a polyamine. When the first adsorption moiety is provided by an aminosilane, the polyamine can interact with the amine moiety of the aminosilane or the interaction moiety of the aminosilane. In some embodiments, the amine moieties of the aminosilane and the polyamine can interact with the silanol group of the aminosilane via hydrogen bonding and ionic interactions to form a functional group, thereby forming a composite network on the surface of the substrate. Referring to FIG. 1B for use, the functional group 106B can include the amine moiety 110B of the aminosilane and the amine moiety 112B of the polyamine, and the amine moiety 110B and the amine moiety 112B interact with the silanol group 108B of the aminosilane.

[0107] FIG. 1C provides a non-limiting functionalized material 100C, which includes a substrate 102C having a plurality of pores 104C-a, 104C-b. Then, the surface 103C of the substrate 102C can include a functional moiety 106C, and then the functional moiety 106C can include at least one adsorption moiety (e.g., a first CO2 adsorption moiety). In some embodiments, a plurality of adsorption moieties are provided. For example, a polyamine having a plurality of adsorption moieties (e.g., polyethyleneimine (PEI)) can react with the substrate. The polyamine can be characterized by a high interaction surface area that facilitates 1- or 2D van der Waals interactions with the surface of the substrate. The polyamine introduced into the substrate can form a surface modification layer for reversibly binding CO2 from atmospheric gases. In some embodiments, a polyamine (e.g., PEI having a larger molecular weight compared to short-chain amine functionalization, e.g., greater than about 800 Da or about 800 Da - 1 MDa (or 1,000,000 Da)) can be overall less volatile.

[0108] In another case, the plurality of adsorption moieties can be provided by one or more oligomeric amines, or small molecule polyamines, or a mixture of any of these. In some embodiments, the oligomeric amine can include oligomeric ethyleneamine or a mixture containing such an oligomer (e.g., an ethyleneamine / oligomer mixture). For example, the oligomer can be an ethyleneamine-containing molecule (e.g., a molecule containing a -CH2CH2NR N1 - group), or an oligomer, e.g., H2N[CH2CH2NH] n H (e.g., wherein n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more, and R N1can include any of those described herein). Tetraethylenepentamine (TEPA) and triethylenetetramine (TETA) are non-limiting examples of oligomeric amines having low volatility. In some embodiments, the oligomeric amine can include small molecule polyamines (e.g., having a molecular weight (MW) of 100 - 800 g / mol). Other examples of oligomers are described herein.

[0109] In some embodiments, a small molecule amine mixture (e.g., Amix 1000) includes amine-containing molecules as a commercially available amine mixture, such as 2-[(2-aminoethyl)amino]ethanol, (aminoethyl)piperazine, and / or (hydroxyethyl)piperazine.

[0110] In some non-limiting embodiments, Amix 1000, TEPA, TETA, or a mixture of these or similar compounds can be used to functionalize a substrate to form a functionalized material. In some embodiments, Amix 1000, TEPA, TETA, and similar compounds are a low-cost source of reactive amines that facilitate low-cost functionalization and carbon capture from atmospheric gases.

[0111] In some embodiments, the oligomeric amine or small molecule amine mixture can react with a porous silica substrate to form a functionalized substrate. In some embodiments, the oligomeric amine or small molecule amine mixture can be a compound bound to the surface of the substrate and can form a surface modification layer on the surface via van der Waals interactions.

[0112] Referring to FIG. 1C, the functional group 106C can include a polyamine group. In some implementations, the polyamine group can include one or more primary, secondary, or tertiary amine groups; repeating units of ethylamine or propylamine; or two or more amine groups connected via various linkers (e.g., alkylene groups); or a linear or branched polyamine. In some embodiments, the polyamine group has an increased interaction surface area due to the increased number of amine groups in the polymer chain compared to short-chain amine-containing compounds. In some embodiments, the polyamine group is bonded to the substrate 102C via van der Waals interactions, hydrogen bonds, and / or ionic interactions.

[0113] In some embodiments of any of the functional materials herein, the functional moiety can include an adsorption moiety that captures CO2 (e.g., as in a CO2 adsorption moiety). In some embodiments, the CO2 adsorption moiety includes one or more amine-containing moieties. The amine-containing moiety can be provided by an aminosilane, an amine compound, a polyamine compound, or any combination thereof. Further details regarding the CO2 adsorption moiety are described herein.

[0114] Also, as described herein, the functional moiety can include an interaction moiety that interacts with at least a portion of the surface of the substrate. The interaction moiety can be 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 the silica. In some embodiments, the interaction moiety includes 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 includes 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 includes an amine moiety that reacts with the surface of the resin substrate. The interaction moiety can interact with the surface of the substrate by covalent and / or non-covalent interactions (e.g., those described herein). Further details regarding the interaction moiety and the substrate are described herein.

[0115] Such moieties can be introduced in any useful manner. For example, such moieties can be present in one or more compounds, and then the one or more compounds can be provided in a suspension or mixture (e.g., a functionalized mixture). When a substrate is also present, the compounds can interact with the substrate to provide a functionalized material. Any useful compound(s) can be used. In one non-limiting example, an amine moiety and a silane moiety are provided by an aminosilane compound, and then the aminosilane compound reacts with or interacts with the surface of the substrate to provide an amine-containing group. In another non-limiting example, the amine moiety is provided by a polyamine compound, and then the polyamine compound reacts with or interacts with the surface of the substrate to provide an amine-containing group. In yet another non-limiting example, both an aminosilane compound and a polyamine compound are used to provide a functionalized surface. Such reactions can result in covalent and / or non-covalent interactions, and in the covalent and / or non-covalent interactions, a linking group (e.g., one by an optionally substituted aliphatic, alkylene, alkenylene, alkynylene, heteroaliphatic, heteroalkylene, heteroalkenylene, heteroalkynylene, aromatic, arylene, heteroaromatic, heteroarylene, etc.) is present between the functional group (or moiety) and the surface of the substrate. The amine moiety can be the amine functional group itself (e.g., -NR N1 R N2 ) or a part of a compound containing an amine functional group (e.g., -L-NR N1 R N2 , wherein L, R N1 , and R N2 can be any of those described herein). Further details regarding compounds, suspensions, and mixtures for providing functional moieties are described herein.

[0116] In use, the functionalized material can be provided as a layer (e.g., a layer of beads or powder) or a bed, and a gas mixture containing CO2 can be flowed over or through the layer or bed. Such a material can be considered a "sorbent" or "adsorbent", and these terms are used interchangeably unless otherwise specified. The gas exiting the adsorbent has a lower CO2 concentration than the entering gas. In some embodiments, the functionalized material can reversibly adsorb CO2 over several cycles, e.g., over several adsorption and desorption steps, and the cycle can include at least one adsorption step and at least one desorption step. Higher cycle counts can be used to characterize materials having a longer product life 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 this specification, for references to measurable values, such as amounts, durations, etc., the listing of values includes exact values, approximate values, and within ±10% of the value. For example, here, 100 cycles includes exactly 100 cycles, approximately 100 cycles, and within ±10% of 100 cycles.

[0117] CO2 adsorbed to a functionalized material can be released (e.g., desorbed) under some conditions. As an example, reducing the gas pressure surrounding the functionalized material can desorb the captured CO2. As another example, reducing the partial pressure of CO2 surrounding the functionalized material can desorb the captured CO2 (e.g., by purging with N2 or another gas). One or more of these techniques can facilitate re-capture of the adsorbed CO2 in a secondary environment. In some implementations, 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).

[0118] As a second example, increasing the temperature of the functionalized material can destabilize the bond between the amine group and CO2, thereby desorbing the CO2 from the functionalized material. In some implementations, the functionalized material desorbs CO2 at a temperature above 60 °C (e.g., 60 °C, 70 °C, 80 °C, or above 90 °C). Increasing the temperature and simultaneously decreasing the gas pressure can increase the rate of desorption of CO2 from the functionalized material.

[0119] In fact, the release of gas from the adsorbent can include any useful process. In one example, a swing process can be used. Such a swing process can include a change in temperature, a change in pressure, and / or the application of a vacuum to release the gas from the adsorbent composition. Swing processes can include temperature swing adsorption (TSA), pressure swing adsorption (PSA), and vacuum swing adsorption (VSA), or combinations thereof. In some embodiments, the released gas can be provided as an output, and such an output can be generated by exposing the adsorbent to a temperature swing adsorption process, pressure swing adsorption, vacuum swing adsorption process, or any combination thereof.

[0120] i. Substrate The functionalized material can include any useful substrate. In some embodiments, the substrate provides a porous surface and the functional moiety can be disposed on the porous surface. In some embodiments, the substrate includes a porous substrate, such as a porous ceramic (e.g., a porous metal oxide, a porous metalloid oxide, or a combination or mixed form thereof), a porous metal-organic substrate, or a porous polymer substrate. In some embodiments, the substrate includes a porous ceramic / metal oxide with porous silica (e.g., including porous alumina, calcium silicate, sodium aluminosilicate). Still other non-limiting examples of the substrate include porous silica or silicate (e.g., amorphous silica, calcium silicate, sodium aluminosilicate), porous alumina (e.g., including sodium aluminosilicate), a metal-organic framework (MOF), or a resin (e.g., those described herein). The substrate can be provided in any form (e.g., it can be provided in a precipitated form, a sol-gel form, a fumed form, a calcined form, an aggregated form, or a granulated form, and then this form can be provided as a powder, granules, etc.). The substrate can be obtained from standard industrial sources or synthesized. In some embodiments, the substrate is water-stable and / or resistant to corrosion and oxidation.

[0121] The dimensions of the substrate can vary based on the application and / or the source. Depending on the shape of the substrate, the dimensions can include length, width, height, cross-sectional dimensions, perimeter, radius (e.g., external or internal radius), diameter, or another measure for indicating the size of the substrate. The substrate can include a population of particles, and the population is characterized by a certain effective average particle size and / or a certain size distribution. For example, without limitation, the substrate can be characterized by an effective average particle size where at least 50% of the particles in the substrate are of a specified size. For example, without limitation, the substrate can be characterized by a size distribution that is from about 25 micrometers (μm) to 3 millimeters (mm) or 25 μm to 4 mm.

[0122] In some non-limiting embodiments, the substrate can have a diameter distribution with an average diameter in the range of 25 μm to 4 mm (e.g., 45 to 800 μm, 50 to 500 μm, 60 to 300 μm, 45 to 150 μm, 70 to 80 μm, 25 μm to 3 mm, 25 μm to 2 mm, 25 μm to 1 mm, 50 μm to 4 mm, 50 μm to 3 mm, 50 μm to 2 mm, 50 μm to 1 mm, 100 μm to 4 mm, 100 μm to 3 mm, 100 μm to 2 mm, 100 μm to 1 mm, 200 μm to 4 mm, 200 μm to 3 mm, 200 μm to 2 mm, 200 μm to 1 mm, 250 μm to 4 mm, 250 μm to 3 mm, 250 μm to 2 mm, 250 μm to 1 mm, 500 μm to 4 mm, 500 μm to 3 mm, 500 μm to 2 mm, 500 μm to 1.5 mm, 1 to 2 mm, 1 to 2.5 mm, 1 to 3 mm, or 1 to 4 mm). In some embodiments, the average diameter of the substrate is less than 500 μm (e.g., less than 400 μm, less than 350 μm, less than 300 μm, less than 200 μm, or less than 100 μm). In some embodiments, the substrate (e.g., porous silica particles) has an average radius of at least 0.5 mm.

[0123] The width of the distribution about the mean can affect the adsorption performance of the substrate. In some non-limiting embodiments, the width of the distribution is in the range of 5 to 50 μm (e.g., 10 to 40 μm or 20 to 30 μm) about the mean. In some examples, the width of the distribution is in the range of 50 μm to 2 mm (e.g., 75 μm to 1.5 mm, 100 μm to 1.25 mm, 200 μm to 1 mm, 300 to 800 μm, 500 μm to 2 mm, 500 μm to 1.5 mm, 500 μm to 1 mm, 1 to 2 mm, 1.2 to 1.8 mm, 1.4 to 2 mm, or 1.5 to 2 mm) about the mean.

[0124] Alternatively, the width of the distribution can be described using the D 90 、D 50 、and / or D 10 values. These values refer to the percentage of the total size distribution of the material in the sample up to and including this value. For example, D 90The value indicates that 90% of the material in the sample has a size of 500 μm or less. In some implementation modes, the functionalized material has a D 10 value of 30 μm or a D 90 value of 150 μm. In some examples, the functionalized material has a D 10 value of 100 μm or a D 90 value of 500 μm, a D 10 value of 150 μm or a D 90 value of 1000 μm, a D 10 value of 400 μm or a D 90 value of 1500 μm, a D 10 value of 500 μm or a D 90 value of 2000 μm, or a D 10 value of 1000 μm or a D 90 value of 3000 μm. In some implementation modes, the functionalized material has a D 50 value of 1000 μm, 1100 μm, 1200 μm, 1300 μm, 1400 μm, or 1500 μm.

[0125] Without wishing to be bound by theory, smaller particle sizes with high porosity or high pore volume and BET surface area can facilitate better functionalized material synthesis results, which can then enable a higher CO2 capture capacity due to a relatively higher surface area that results in a higher amine coating concentration. Such smaller particles of that type can enable faster adsorption into the interior of the particles because the gas diffusion pathway can be shorter. If the gas diffusion rate to the particle surface is not limited, smaller particle sizes can be beneficial for gas adsorption. Smaller particle sizes (e.g., having a smaller average diameter, radius, or width) can reduce the adsorption process energy cost for the fluidization process.

[0126] Other particle effects for smaller particle sizes can include smaller inter-particle volume, slower inter-particle gas dynamics (e.g., due to longer inter-particle diffusion lengths), faster intra-particle gas dynamics (e.g., due to shorter intra-particle diffusion lengths), higher packed bed backpressure, higher packing density, and / or higher external surface area. Particle effects for larger particle sizes can include larger inter-particle volume, faster inter-particle gas dynamics (e.g., due to shorter inter-particle diffusion lengths), slower intra-particle gas dynamics (e.g., due to longer intra-particle diffusion lengths), lower packed bed backpressure, lower packing density, and / or lower external surface area. One of ordinary skill in the art can adapt such sizes and effects to provide a particular adsorbent for a particular use.

[0127] The substrate can be characterized by the presence of one or more pores. As shown in FIG. 1A, pore 104 can be considered an opening that extends from the external surface of the substrate into the internal volume. In some embodiments, the presence of such pores can increase the surface area of the substrate. The dimensions of the pores can vary by pore and within individual pores, see, e.g., pores 104A-a, 104A-b. Further, depending on the shape of the pores, the dimensions can include length, width, height, cross-sectional dimensions, perimeter, radius (e.g., external or internal radius), diameter, or another measure for indicating the size of the pores.

[0128] The pores can have any useful dimension. In some embodiments, the dimension (e.g., diameter) of the pore(s) is in the range of 60 to 700 angstroms (Å) (e.g., 60 to 400 Å, 60 to 300 Å, 80 to 300 Å, 100 to 700 Å, 100 to 500 Å, 100 to 200 Å, 150 to 250 Å, 200 to 700 Å, 300 to 700 Å, 300 to 500 Å, or 500 to 700 Å). In some embodiments, the dimension (e.g., diameter) of the pore(s) is in the range of 100 to 150 Å. In some implementations, the dimension (e.g., diameter) of the pore(s) is greater than 90 Å (e.g., greater than 100 Å, 120 Å, or 150 Å). Without wishing to be bound by theory, a larger diameter of the pores can increase the adsorption and desorption rates and can facilitate a higher filling of the pores at the amine moiety without having pore clogging that can reduce the adsorption and desorption efficiency.

[0129] In some embodiments, the substrate can be characterized by a porosity of 1 to 200 nm and / or an average pore size of 30 to 80 nm. In some embodiments, the dimension (e.g., diameter) of the pore(s) is in the range of 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, the average dimension (e.g., average diameter) of the pore(s) is in the range of 30 to 80 nm, 20 to 100 nm, or 20 to 70 nm).

[0130] In some embodiments, a substrate (e.g., a silica substrate) can be characterized by a plurality of pores of different sizes. For example, but not limited to, smaller pores in the range of 1 to 30 nm can contribute to a relatively higher surface area, which can enable more surface attachment at the amine moiety and improve the stability of the coating or surface functionalization layer. Larger pores in the range of 30 to 90 nm can contribute to a relatively larger pore volume, which can enable a larger volume of active amine moieties to be accommodated within the pores and improve CO2 uptake. The largest pores in the range of 70 to 200 nm can provide open channels that contribute to a relatively higher gas diffusion rate for improved CO2 adsorption kinetics. Without wishing to be limited by mechanism, a substrate (e.g., a silica substrate) having significant porosity in these three ranges can be used as a substrate for an amine-coated adsorbent. In some non-limiting embodiments, a substrate having reduced porosity in one or two of these ranges can suffer a relatively decreased performance in the corresponding function but can still function as a substrate for an amine-coated adsorbent.

[0131] In some embodiments, a substrate (e.g., a silica substrate) can be characterized by a plurality of pores, each pore can be characterized by a pore dimension, and 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.

[0132] The pores can have any useful shape (e.g., cylindrical, spherical, tubular, etc.), configuration, distribution, and arrangement (e.g., hexagonal, cubic, etc.). The pores can have an irregularly round cross-sectional shape or a hexagonal cross-sectional shape, which is non-limiting. Also, the pores can be characterized by a pore size distribution, 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 an appropriate method such as the Barrett-Joyner-Halenda (BJH) or non-local density functional theory (NLDFT) model).

[0133] Non-limiting examples of pore size distributions are provided in FIGS. 30A - 30D and FIG. 31. Pore size distribution profiles are provided for a non-limiting adsorbent having only narrow pores with a high surface area but a relatively lower pore volume and gas kinetics (FIG. 30A), a non-limiting adsorbent having only medium-sized pores with a high pore volume and a medium surface area and gas kinetics (FIG. 30B), a non-limiting adsorbent having only large pores with a fast gas kinetics and a high pore volume but a relatively lower surface area (FIG. 30C), and a non-limiting adsorbent having a plurality of ranges of pores with a high surface area, pore volume, and channels for gas diffusion enabling a stable surface coating, a relatively higher concentration of active amines, and a fast gas kinetics (FIG. 30D). Also, pore size distributions (FIG. 31) are provided for raw silica, impregnated-coated adsorbents, and spray-coated adsorbents.

[0134] The pores can have any useful configuration. In some embodiments, the pores can be provided on the surface of the substrate. Such pores may or may not be interconnected. For example, without limitation, the pores can extend into the central volume of the substrate and can form interconnected channels. Without wishing to be limited by theory, the pores can create a volume within the substrate, through which gas can flow into the volume within the substrate, enhancing the capture of such gas. Further, such pores can create additional (e.g., accessible) surface area for functionalization.

[0135] The pores can be characterized by pore volume, total surface area, accessible surface area, porosity, etc. 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, from 0.1 to 4 mL / g, from 0.1 to 3 mL / g, from 0.1 to 3.5 mL / g, from 0.1 to 3 mL / g, from 0.1 to 2.5 mL / g, from 0.1 to 2 mL / g, from 0.1 to 1.5 mL / g, from 0.1 to 1.2 mL / g, from 0.1 to 1 mL / g, from 0.5 to 5 mL / g, from 0.5 to 4.5 mL / g, from 0.5 to 4 mL / g, from 0.5 to 3.5 mL / g, from 0.5 to 3 mL / g, from 0.5 to 2.5 mL / g, from 0.5 to 2 mL / g, from 0.5 to 1.5 mL / g, from 0.5 to 1 mL / g, from 1 to 5 mL / g, from 1 to 4.5 mL / g, from 1 to 4 mL / g, from 1 to 3.5 mL / g, from 1 to 3 mL / g, from 1 to 2.5 mL / g, from 1 to 2 mL / g, from 1.5 to 5 mL / g, from 1.5 to 4.5 mL / g, from 2.5 to 5 mL / g, from 2.5 to 4.5 mL / g, from 3.5 to 5 mL / g, from 3.5 to 4.5 mL / g, from 1.5 to 3.5 mL / g, from 1 to 3 mL / g, from 1 to 1.5 mL / g, from 1 to 1.2 mL / g, or from 1.5 to 2.5 mL / g). Without wishing to be bound by limited theory, the increased total volume of the pores can enable more amine moieties to be grafted into or be within the pores, and thus increase the adsorption potential of the functionalized material.

[0136] The total surface area can be used to characterize the substrate. The total surface area of the substrate includes not only the surface area of the outer surface but also the surface area within the pores. In some embodiments, the total surface area is 100 m 2 per (m 2 / g) per dry gram of the substrate. In some implementations, the total surface area is greater than 300 m 2 / g (e.g., greater than 200 m 2 / g, 400 m 2 / g, 500 m 2 / g, or greater than 800 m 2 / g). In some implementations, the total surface area is greater than 1200 m 2 / g (e.g., greater than 200 m 2 / g, 400 m 2 / g, 500 m 2 / g, or greater than 800 m 2 / g). In some implementations, the total surface area is greater than 2000 m 2 / g (e.g., 2500 m 2 / g, 3000 m 2 / g, 4000 m 2 / g, 5000 m 2 / g, or greater than 6000 m 2 / g). In some examples, the total surface area is from 100 to 1200 m 2 / g (e.g., from 200 to 1200 m 2 / g, from 400 to 1200 m 2 / g, from 500 to 1200 m 2 / g, from 700 to 1200 m 2 / g, from 800 to 1200 m 2 / g, from 1000 to 1200 m 2 / g, from 100 to 1000 m 2 / g, from 100 to 800 m 2 / g, from 100 to 500 m 2 / g, from 100 to 400 m 2 / g, from 100 to 900 m 2 / g, from 200 to 900 m 2 / g, from 400 to 900 m 2 / g, from 500 to 1000 m 2 / g, or from 500 to 800 m 2 / g) and is in the range. In some examples, the total surface area is 1000 - 12000 m 2 / g (for example, 1000 - 11000 m 2 / g, 1000 - 10000 m 2 / g, 1000 - 9000 m 2 / g, 1000 - 8000 m 2 / g, 1000 - 7000 m 2 / g, 1000 - 6000 m 2 / g, 1000 - 5000 m 2 / g, 1000 - 4000 m 2 / g, 2000 - 12000 m 2 / g, 2000 - 11000 m 2 / g, 2000 - 10000 m 2 / g, 2000 - 9000 m 2 / g, 2000 - 8000 m 2 / g, 2000 - 7000 m 2 / g, 2000 - 6000 m 2 / g, 2000 - 5000 m 2 / g, 2000 - 4000 m 2 / g, 3000 - 12000 m 2 / g, 3000 - 11000 m 2 / g, 3000 - 10000 m 2 / g, 3000 - 9000 m 2 / g, 3000 - 8000 m 2 / g, 3000 - 7000 m 2 / g, 3000 - 6000 m 2 / g, 3000 - 5000 m 2 / g, 3000 - 4000 m 2 / g, 4000 - 12000 m 2 / g, 4000 - 11000 m 2 / g, 4000 - 10000 m 2 / g, 4000 - 9000 m 2 / g, 4000 - 8000 m 2 / g, 4000 - 7000 m 2 / g, 4000 - 6000 m 2 / g, or 4000 - 5000 m 2 / g) and is in the range. In some examples, the total surface area is 100 - 12000 m 2in the range of / g (e.g., the range between them, e.g., including those described herein).

[0137] Without wishing to be limited by theory, a higher total surface area can increase the available area for functionalization (e.g., by the interaction between the silane moiety and the surface of the substrate) and / or can increase the adsorption potential of the functionalized material. The surface area can be determined in any useful manner, e.g., by using the BET model or other methods described herein.

[0138] Any useful combination of features can be present in the substrate. In some embodiments, the substrate includes a maximum dimension (e.g., average maximum dimension) of at least 70 μm and a plurality of pores, the plurality of pores being characterized by a volume greater than 0.8 mL / g and a size of at least 90 Å (e.g., average size). In some embodiments, the substrate includes a maximum dimension (e.g., average maximum dimension) in the range of 0.5 - 2 mm and a plurality of pores, the plurality of pores being characterized by a volume greater than 0.5 ml / g and a size in the range of 20 - 1000 Å. Other combinations of features are possible.

[0139] a. Silica In some embodiments, the substrate includes silica (e.g., silicon dioxide). Any of the methods or compounds herein can be used to functionalize the silica substrate to provide a functionalized silica. For example, without limitation, the functionalized silica can be characterized by an amine moiety bonded (e.g., by siloxane bonds, other covalent bonds, or even non-covalent bonds) to the silica surface.

[0140] Silica can be provided in any useful form, such as beads (e.g., microbeads, nanobeads, or combinations thereof), powders (e.g., micropowders, nanopowders, or combinations thereof, or those from micrometer size to millimeter size), particles (e.g., microparticles, nanoparticles, or combinations thereof), etc. Further, silica can include any useful type, such as amorphous or non-crystalline silica (e.g., precipitated form, sol-gel form, fumed form, calcined form, aggregated form, or other forms of silica), or silicates (e.g., calcium silicate, sodium aluminosilicate, etc.). In some embodiments, silica can include one or more pores (e.g., as in porous silica). Further, within such a substrate, the pores can have any useful shape, configuration, distribution, and arrangement (e.g., the hexagonal-arranged pores in MCM-41, and then the hexagonal-arranged pores can be spherical or any other shape). In some embodiments, the substrate can be in bead shape, but this is non-limiting. Silica can be obtained or provided in any useful manner, for example, by using a synthesis method or by procuring from standard industrial sources.

[0141] In some non-limiting embodiments, the substrates 102A, 102B, 102C are silica substrates. In some non-limiting embodiments, the substrates 102A, 102B, 102C are composed of amorphous silica, such as non-crystalline silica.

[0142] b. Metal-organic framework (MOF) A metal-organic framework (MOF) is a class of compounds that includes metal ions or clusters, where the metal ions or clusters are coordinated to organic ligands and form a one-dimensional, two-dimensional, or three-dimensional structure (e.g., a porous three-dimensional structure). Various types of MOFs can be synthesized with different combinations of metal ions and organic ligands (e.g., those described herein). In some embodiments, the MOF substrate is used to achieve carbon capture as a porous structure for functionalization.

[0143] In some embodiments, the substrate includes an MOF. Any method or compound herein can be used to functionalize the MOF substrate to provide a functionalized MOF. Without wishing to be bound by theory, the functionalized MOF can be characterized by a larger surface area for increased functionalization (e.g., greater than 2000 m 2 / g) than alternative substrates (e.g., zeolites, silica, etc.). For example, without limitation, the functionalized MOF can be characterized by an amine moiety bonded to a hydroxy-functional side group present on the surface, thereby enabling CO2 uptake. The amine moiety can be provided by any of the compounds described herein (e.g., an aminosilane compound) for increased carbon capture (e.g., greater than 2 mol of CO2 / kg).

[0144] The MOF can be provided in any useful form. In some embodiments, the MOF can be produced using a reactor-based solvothermal (e.g., hydrothermal) synthesis method, in which a metal source (e.g., a metal substrate or a metal-containing salt), an organic ligand, and an optional competitor / additive react together to produce MOF crystals having a size of 10 μm to 1 mm (e.g., diameter), the size including ranges therebetween (e.g., sizes of 10 - 500 μm, 10 - 300 μm, 50 - 300 μm, or 50 - 100 μm). The crystals can be extruded, pelletized, and functionalized at the adsorption portion to provide functional groups disposed on the surface of the MOF, thereby providing a functionalized MOF.

[0145] MOFs can be synthesized by providing a metal source and an organic ligand. Under certain conditions, metal-containing centers form nodes and the organic ligands form cross-links between the nodes to provide a self-organized network structure. By selecting certain metals and ligands with certain reaction conditions, various structural features of the MOF material (e.g., topology, pore structure, pore size, etc.) can be controlled.

[0146] Any useful metal source can be used. Non-limiting examples include metal sources containing aluminum (Al), chromium (Cr), copper (Cu), iron (Fe), titanium (Ti), vanadium (V), zinc (Zn), zirconium (Zr), and their salts (e.g., halogen salts, nitrates, or others described herein). In some embodiments, the metal source can be 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 can include economically commercially available cost-effective metal ion sources, such as aluminum (Al), iron (Fe), titanium (Ti), zinc (Zn) (e.g., zinc nitrate (ZnNO3)), zirconium (Zr) (e.g., zirconium tetrachloride (ZrCl4)).

[0147] Any useful organic ligand can be used. Non-limiting ligands are, for example, 3,3’,5,5’-azobenzenetetracarboxylate (ABTC 4- ); 1,4-benzenedicarboxylate (BDC 2- ); (X)-BDC 2- or (X)2-BDC 2- (wherein each X is independently alkyl, halo, hydroxy, nitro, amino, carboxyl, alkoxy, cycloalkoxy, aryloxy, or benzyloxy) (e.g., 2-amino-1,4-benzenedicarboxylate (NH2-BDC 2- )), 2-hydroxy-1,4-benzenedicarboxylate (OH-BDC2- ) 2,5-diamino-1,4-benzenedicarboxylate ((NH2)2-BDC 2- ) 2,5-dihydroxy-1,4-benzenedicarboxylate ((OH)2-BDC 2- or DHBDC 2- ) 2,3-dihydroxy-1,4-benzenedicarboxylate, or 2,6-dihydroxy-1,4-benzenedicarboxylate); 1,1'-biphenyl-4,4'-dicarboxylate (BPDC 2- ); (X)-BPDC 2- or (X)2-BPDC 2- (wherein each X is independently alkyl, halo, hydroxy, nitro, amino, carboxyl, alkoxy, cycloalkoxy, aryloxy, or benzyloxy) (for example, 2-amino-1,1'-biphenyl-4,4'-dicarboxylate (NH2-BPDC 2- ) 2-hydroxy-1,1'-biphenyl-4,4'-dicarboxylate (OH-BPDC 2- ) 2,2'-diamino-1,1'-biphenyl-4,4'-dicarboxylate ((NH2)2-BPDC 2- ) or 2,2'-dihydroxy-1,1'-biphenyl-4,4'-dicarboxylate ((OH)2-BPDC 2- )); 1,3,5-benzenetricarboxylate or 1,2,4-benzenetricarboxylate (BTC 3- ); 2,5-dihydroxy-1,4-benzenedicarboxylate (DHBDC 2- ); 2,5-dioxide-1,4-benzenedicarboxylate (DOBDC 4- ); 4,4',4”-s-triazine-2,4,6-triyl-tribenzoate (TATB 3- ); 1,3,6,8-tetrakis(p-benzoate)pyrene (TBAPy 4- ); 1,1'-triphenyl-4,4'-dicarboxylate (TPDC 2- ); and (X)2-TPDC 2- or (X)4-TPDC 2-(Wherein each X is independently alkyl, halo, hydroxy, nitro, amino, carboxyl, alkoxy, cycloalkoxy, aryloxy, or benzyloxy) (for example, 2,2'-dihydroxy-1,1'-triphenyl-4,4'-dicarboxylate (di-OH-TPDC) or 2,2',6,6'-tetrahydroxy-1,1'-triphenyl-4,4'-dicarboxylate (tetra-OH-TPDC)). Such ligands can be provided to the metal source as the compound in its protonated form. In some embodiments, the ligand can optionally include one or more counterions (e.g., one or more counteranions or countercations), and their cations, their anions, their protonated forms, their salts, or their esters.

[0148] In some embodiments, the ligand includes a hydroxy functional side group. Without wishing to be bound by theory or mechanism, the presence of the hydroxy functional side group can facilitate post-synthetic functionalization of the MOF surface at the adsorption moiety (e.g., the amine moiety).

[0149] In some embodiments, the hydroxy increases the density of the amine moiety on the surface of the MOF substrate, thereby increasing the CO2 capture capacity of the MOF substrate while reacting with the silane moiety of the aminosilane compound to covalently bond the silane moiety to the hydroxy group of the organic ligand. Non-limiting examples of aminosilanes suitable for bonding to the MOF substrate for carbon capture include methoxysilane, chlorosilane, ethoxysilane, and others described herein.

[0150] In some embodiments, the organic ligand is provided by a compound that is 1,4-di-(4-carboxy-2,6-dihydroxyphenyl)benzene. Within the MOF, this compound can provide a 2,2’,6,6’-tetrahydroxy-1,1’-terphenyl-4,4’-dicarboxylate (tetra-OH-TPDC) ligand. In some embodiments, this compound is used with a metal source comprising Zn(NO3)2·6H2O.

[0151] In some embodiments, the organic ligand is provided by a compound that 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-boronobenzen-1,4-dicarboxylic acid (e.g., to provide a 2-borono-BDC ligand).

[0152] Any useful MOF can be used. Non-limiting examples of MOFs include, for example, 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 or MOF-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, for example, OH - or Cl -is 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 - is NH2-MIL-101-Al [Al3O(NH2-BDC)6X3 or Al3O(NH2-BDC)3(H2O)2X, where X is a monoanion such as OH - or Cl - is 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(μ3-OH)4(OH)6(H2O)6(BTC)2], NU-1000 [Zr6(μ3-O)4(μ3-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(μ3-OH)4(TATB)2(OH)6(H2O)6 or Zr3O4(OH)(TATB)(H2O)6], UiO-66 [Zr6(O)4(OH)4(BDC) 12 , 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], or UiO-67 [Zr6O4(OH)4(BPDC)6]. Any of these can be 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.

[0153] The MOF can be provided in any useful form, such as particles, crystals, powders, etc. In some embodiments, the MOF particles include MIL-101-Fe, MIL-101-Al, MIL-125-Ti, PCN-250, UiO-66, or UiO-67. In some embodiments, the MOF particles can be water-stable MOF particles.

[0154] The MOF substrate can be processed under various synthesis conditions to obtain different pore sizes and porosities. In some embodiments, the MOF substrate is a mesoporous or macroporous MOF material. Generally, without wishing to be bound by theory, higher pore opening sizes can facilitate an increased surface area and increase the number of exposed active sites where post-synthesis modification can occur. The increased exposed active sites can facilitate a higher concentration of adsorption moieties on the MOF substrate, which can then enable a higher CO2 capture capacity.

[0155] The MOF substrate can include pores, which are openings that extend within the internal volume of the MOF substrate. The pores can increase the surface area of the MOF substrate. The dimensions of the pores can vary and can vary within individual pores. Mesoporous and macroporous MOF materials can enable a large volume of adsorption moieties (e.g., amine moieties) to be incorporated within the porous matrix. In some embodiments, the mesoporous material includes pores having a maximum opening dimension (e.g., diameter) in the range of 2 nanometers (nm) to 50 nm, and the macroporous material includes pores having a maximum opening dimension greater than 50 nm. For the MOF substrate, the pore size, pore volume, and / or total surface area can be any of those described herein (e.g., a pore size in the range of 30 to 400 Å or greater than 90 Å, a pore volume of 0.5 to 5 mL / g, and / or a total surface area greater than 100 m 2 / g).

[0156] The MOF matrix can be functionalized to provide a functional moiety having an adsorption moiety. In some embodiments, the adsorption moiety is an amine moiety (e.g., a primary, secondary, or tertiary amine group as described herein). In some embodiments, the amine moiety binds to the surface of the MOF from which the hydroxy-functional side groups extend. In this example, the interacting moiety can include any that react with the hydroxy groups present on the surface of the MOF. Non-limiting interacting moieties can be, for example, silane moieties (e.g., any of those described herein). By forming an interaction between the interacting moiety and the surface, the amine bond stability and / or the lifetime of the adsorbent can be improved. The functionalization methods herein can be applicable to MOF matrices of all morphological factors.

[0157] In some embodiments, an aminosilane is provided to the surface of the MOF. In some embodiments, the aminosilane can include a silane moiety (e.g., a trimethoxysilane moiety, a triethoxysilane moiety, a dimethoxyethoxysilane moiety, a diethoxymethoxysilane moiety, etc.) and an amine moiety. In some embodiments, the aminosilane includes 1, 2, or 3 amine moieties (e.g., any of those described herein for R A ). In some embodiments, the aminosilane includes a structure having the formula [R A 3SiX, wherein each R A is independently an amine moiety containing at least one amine group (e.g., any of those described herein), and X is a side group, a reactive group, or a leaving group (e.g., any of those described herein). In some embodiments, the aminosilane includes a structure having the formula [R N1 R N2 N]3SiX, wherein R N1 and R N2Each of them is independently any of those 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 of those described herein, e.g., halo, hydroxy, etc.). In some embodiments, the aminosilane is tris(ethylmethylamino)chlorosilane or includes it. Other examples of aminosilanes include any of those described herein (e.g., aminosilanes including a structure having formula (I)).

[0158] In some embodiments, the aminosilane is provided on the surface of the MOF, and the aminosilane interacts with the hydroxy groups present on the organic ligands within the MOF. In some embodiments, the organic ligand interacts with (e.g., binds to) the metal centers within the MOF, and the hydroxy groups are unbound from the metal centers. In certain embodiments, the silane moiety of the aminosilane interacts with (e.g., binds to or reacts with) the hydroxy groups present on the organic ligand.

[0159] In some non-limiting embodiments, substrates 102A, 102B, 102C are MOF substrates, and pores 104A-a, b, 104B-a, b, 104C-a, b represent pores provided by the MOF structure. In some non-limiting embodiments, substrates 102A, 102B, 102C are composed of crystalline nanoporous MOF.

[0160] c. Resin Ion exchange resins generally have a porous structure, which can provide a large surface area for the exchange of ionic compounds. To provide a functionalized resin, a functional group-containing compound can be adsorbed into the pores and interact with reactive sites present within such pores. Such interactions can include ionic bond interactions, hydrogen bond interactions, van der Waals force interactions, and the like. This process can be carried out with various types of reactive sites, for example, multiple types of ion exchange resins having polystyrene sulfonate (e.g., acidic reactive sites where sulfonic acid in the ion exchange resin forms ionic bonds with various amines via ionic bonds). In some embodiments, the resin matrix is used to achieve carbon capture as a porous structure for functionalization. In certain embodiments, the reactive sites present in the resin are used during functionalization.

[0161] In some embodiments, the substrate includes a resin (e.g., an ion exchange resin). Any method or compound herein can be used to functionalize the resin substrate to provide a functionalized resin. For example, without limitation, the functionalized resin can be characterized by an amine moiety bonded to acidic reactive sites present on the surface, thereby enabling CO2 uptake. The amine moiety can be provided by any compound described herein (e.g., a polyamine) for increased carbon capture (e.g., greater than 1 mol of CO2 / kg or 1 - 3 mol of CO2 / kg).

[0162] In some embodiments, the substrate includes an ion exchange resin (e.g., ion exchange resin particles). In some embodiments, the ion exchange resin is sufficiently cross-linked to retain a porosity sufficient to facilitate gas diffusion and adsorption when dry.

[0163] Generally, the resin matrix is a portion of an ion exchange resin that can be procured from standard industrial sources. Non-limiting types of ion exchange resins include "weak base" functionalized resins, "acid" functionalized resins, e.g., those having carboxylic or sulfonic acid groups, and neutral resins having no chemical functionalization.

[0164] In these types, different molecular interactions can be used to retain the introduced amine moiety. In weak base resins, the amine moiety is present in the resin and functions as a reactive site. These reactive sites can then interact (e.g., by hydrogen bonding) with the adsorbed moieties (e.g., by introducing polyamines, monoamines, aminosilanes, etc.) introduced during functionalization. In acidic resins, the acidic moiety is present in the resin as a reactive site. Introducing an amine (e.g., polyamine, monoamine, aminosilane, etc.) to this resin can result in an acid-base reaction, which can form an ionic bond between the reactive site and the amine. In neutral resins, van der Waals forces and the encapsulation of larger amines within the resin pores are the primary interactions. Without wishing to be limited by theory, the ionic bond interaction in acidic resins can provide the highest binding strength relative to other binding modes, the hydrogen bonding in weak base resins has less strength than ionic bonds, and the van der Waals forces in neutral resins have the lowest binding strength relative to the other two binding modes.

[0165] The ion exchange resin is a class of porous polymers including polystyrene (e.g., optionally cross-linked with divinylbenzene), polyacrylate, polymethacrylate (e.g., optionally cross-linked with divinylbenzene), polyphenol / phenol-aldehyde resins (e.g., phenol-formaldehyde), melamine resins, agarose, cellulose, polyacrylamide, polysaccharides (e.g., dextran), polyolefins, or similar resins and thermosetting resins, as well as cross-linked forms of any of these or copolymers of any of these.

[0166] The resin can include ionizable, chelating, ionic, acidic, or basic functional groups that can interact with ions. These functional groups can include, but are not limited to, carboxylic acid, phosphonic acid, sulfonic acid, sulfoalkyl acid, thiol, iminodiacetic acid, thiourea, aminophosphonic acid, pyridine, phenol, picolylamine, primary amine, secondary amine, tertiary amine, quaternary amine, and alcoholamine.

[0167] Any useful resin can be used. Non-limiting examples of resins include base-functionalized resins, acid-functionalized resins, or neutral resins without chemical functionalization. In some embodiments, the acid-functionalized resin can include carboxyl and / or sulfonic acid groups. In some embodiments, the resin can be a combination of a porous polystyrene, polyacrylamide, or phenol-formaldehyde resin that retains porosity when dry and a molecular alkylamine. Non-limiting examples of porous ion exchange resins include Purolite® A110 (polystyrene-based macro-porous, weak base anion resin, free base form, having a primary amine as a functional group), Purolite® A105 (polystyrene-based macro-porous, weak base anion resin, free base form, having a tertiary amine as a functional group), Purolite® C145H (polystyrene-based macro-porous, strong acid cation resin, hydrogen form, having sulfonic acid as a functional group), Purolite® C160H (polystyrene-based macro-porous, strong acid cation resin, hydrogen form, having sulfonic acid as a functional group), Purolite® Macronet™ MN502 (crosslinked polystyrene-based macro-porous, adsorbent resin, strong acid functionality, hydrogen form, having sulfonic acid as a functional group), Purolite® C104Plus (polyacrylic-based porous, weak acid cation resin, hydrogen form, having carboxylic acid as a functional group), PuroSorb™ PAD900 (polydivinylbenzene macro-porous, adsorbent resin, non-ionic form), Amberlite® IRA-402 (strongly basic anion exchanger, Cl -form, having a quaternary ammonium as a functional group), or Dowex® 50W-X8 (a strong acid cation exchanger, H + form, having a sulfonic acid as a functional group), and the like, but not limited thereto. The resin can be provided in any useful form, for example, beads, granules, powders, membranes, fibers, particles, crystals, and the like.

[0168] The resin can be porous enough to facilitate the diffusion of gas ions into and out of the polymer matrix. Some resins are highly cross-linked and hard, and retain their porosity in a dry state (e.g., hydration with less than 15% (weight / weight) water). The term "(weight / weight)" refers to the ratio of the weight (weight) of the first component to the weight of the second component. For example, 1 g of the first substance and 10 g of the second substance define a ratio of the first substance to the second substance of 10% (weight / weight).

[0169] In some embodiments, the resin matrix is porous in a dry state. Without wishing to be limited by mechanism, such a matrix can facilitate the diffusion of a gas containing CO2 into the polymer matrix for CO2 capture. Ion exchange resins can be polymerized under various synthetic conditions to obtain different pore sizes and porosities. Larger meso- and macropores can enable a large volume of adsorption groups to be incorporated into the porous matrix. In some embodiments, the mesoporous resin includes pores having a maximum aperture dimension (e.g., diameter) in the range of 2 to 50 nm, and the macroporous resin includes pores having a maximum aperture dimension greater than 50 nm.

[0170] Generally, without wishing to be bound by theory, suitable pore sizes (e.g., those in adsorbents having pores in any of the ranges herein) can be characterized by a stable coating or surface functionalization layer, a relatively higher concentration of adsorption moieties (e.g., active amines), and / or a high surface area, pore volume, and channels for gas diffusion that enable fast gas kinetics. This can then enable a higher CO2 capture capacity. In some embodiments, the higher porosity can reduce the adsorption process energy cost for the fluidization process.

[0171] The resin matrix can include pores, which are openings extending within the internal volume of the resin matrix. The pores can increase the surface area of the resin matrix. For the resin matrix, the pore size, pore volume, and / or total surface area can be any of those described herein (e.g., pore sizes greater than 90 Å, or in the range of 60 - 400 Å or 1 - 200 nm, an average pore size in the range of 30 - 80 nm, a pore volume greater than 0.5 mL / g, or in the range of 0.1 - 5 mL / g, 0.1 - 4 mL / g, or 0.1 - 1.5 mL / g, and / or a total surface area greater than 100 m 2 / g, greater than 1200 m 2 / g, or in the range of 100 - 1200 m 2 / g).

[0172] The resin matrix can be functionalized to provide a functional moiety having an adsorption moiety. In some embodiments, the adsorption moiety is an amine moiety (e.g., a primary, secondary, or tertiary amine group as described herein). In some embodiments, the amine moiety binds to the reactive site of the resin. In this example, the interaction moiety can include anything that reacts with the reactive site present on the surface of the resin. Non-limiting interaction moieties can be, for example, an amine moiety (e.g., any of those described herein). In some implementations, the resin includes a first amine moiety, and the reaction introduces a second amine moiety bound to the first amine moiety. By forming an interaction between the interaction moiety and the surface, the amine bond stability and / or the lifetime of the adsorbent can be improved. The functionalization methods herein can be applicable to ion exchange resins of all form factors.

[0173] ii. Functional moiety The functional moiety can include any combination of moieties, groups, or compounds to facilitate the adsorption of the desired gas by the adsorbent. In some embodiments, the functional moiety includes an adsorption moiety and an interaction moiety. The adsorption moiety is configured to adsorb the desired gas, and the interaction moiety is configured to attach the adsorption moiety to the surface of the substrate (either directly or indirectly). Optionally, the interaction moiety can be further configured to stabilize the functional moiety, for example, by forming a bond with the adsorption moiety and / or the surface of the substrate. In another optional embodiment, the interaction moiety can be further configured to provide an additional adsorption moiety to enhance the adsorption of the adsorbent. The functional moiety can include any useful combination of one or more adsorption moieties (e.g., one or more amine moieties) and one or more interaction moieties (e.g., one or more silane moieties). In some embodiments, when multiple amine moieties are present (e.g., when a first amine moiety and a second amine moiety are present), such moieties can react with or bind to carbon dioxide.

[0174] As shown in FIGS. 1A-1C, the surfaces 103A-C of substrates 102A-C can be functionalized to provide functional moieties 106A-C. In some embodiments (e.g., those in FIG. 1A), the functional moiety 106A includes an interaction moiety 108A bound to an adsorption moiety 110A. In some embodiments (e.g., those in FIG. 1B), the functional moiety 106B includes an interaction moiety 108B bound to a first adsorption moiety 110B and a second adsorption moiety 112B associated with the interaction moiety 108B and / or the first adsorption moiety 110B. In some embodiments (e.g., those in FIG. 1C), the functional moiety 106C includes an adsorption moiety.

[0175] The functional moiety can include an adsorption moiety. In some embodiments, the adsorption moiety can include one, two, three, or more amine moieties (e.g., any of those described herein). In some implementations, the amine moiety is hereinafter a primary amine (e.g., -NH2), a secondary amine (e.g., -NHR N1 wherein R N1 is not hydrogen and can be any of those described herein), a tertiary amine (e.g., -NR N1 R N2 wherein each of R N1 and R N2 is not hydrogen and can be any of those described herein), an aminoalkyl group (e.g., -Ak-NR N1 R N2 ), a terminal amine group (e.g., -NR N1 R N2 ), an internal amine group (e.g., -NR N3 -, e.g., -NH-), a linking group (e.g., -N(-L 1 -NR N1 R N2 )-;-N(-L 2 -NR N3 -L 1 -NR N1 R N2 )-;-N[-L 2 -N(-L 1 -NR N1 R N2)2] - ; - L 1 - NR N1 R N2 ; - NR N3 - L 1 - NR N1 R N2 ; - L 2 - NR N3 - L 1 - NR N1 R N2 ; - NR N4 - L 2 - NR N3 - L 1 - NR N1 R N2 ; or - L 3 - NR N4 - L 2 - NR N3 - L 1 - NR N1 R N2 ), an aminoalkylamino group (e.g., - NR N3 - Ak - NR N1 R N2 ), an aminoalkylaminoalkyl group (e.g., - Ak - NR N3 - Ak - NR N1 R N2 or - Ak - N(- Ak - NR N1 R N2 ), a linking group containing an amino and a silane group (e.g., - L 1 - SiR S1 R S2 - NR N1 R N2 , - L 2 - SiR S1 R S2 - L 1 - NR N1 R N2 , and - L 3 - SiR S1 R S2 - L 2 - NR N3 - L 1 - NR N1 R N2) can include one or more of nitrogen-containing heterocyclyl (e.g., optionally substituted piperazinyl, e.g., unsubstituted piperazinyl, or piperazinyl substituted with optionally substituted alkyl, aminoalkyl, hydroxyalkyl, amino, etc.).

[0176] In other embodiments, the adsorbing moiety can include one or more R moieties described herein. In some embodiments, R A is -NH-, -NR A -, -N(-L N1 -NR 1 R N1 )-, -N(-L N2 -NR 2 -NR N3 -L 1 -NR N1 R N2 )-, -N[-L 2 -N(-L 1 -NR N1 R N2 )2]-, -NH2, -NR N1 R N2 , -L 1 -NR N1 R N2 , -NR N3 -L 1 -NR N1 R N2 , -L 2 -NR N3 -L 1 -NR N1 R N2 , or -NR N4 -L 2 -NR N3 -L 1 -NR N1 R N2 or includes it.

[0177] The amine moiety includes any combination of a linker and an R A moiety. In some implementations, the amine moiety is hereinafter -L 1 -[R A1 -L 2 n1 -R A2 ;-NR​N1 -[L 1 -NR N2 n1 -L 2 -NR N3 R N4 ;-NH-[L-NH] n -H;-N[L-NH2]2;-NH[CH2CH2NH] n H;-[CH2CH2NH] n R N1 ;-[CH2CH2NH] n -;-[CH2CH2NR A n R N1 ;-[CH2CH2NR A n -and includes one or more of the like.

[0178] In some non-limiting embodiments for any amine moiety herein, R A , R A1 , or each of R A2 is any one or includes any one described herein for R A , and each of R N1 and R N2 can be any one described herein, and each of R N3 , R N4 , and R N5 can be any one described herein for R N1 and R N2 , and each of R S1 and R S2 can be any one described herein, and each of L, L 1 , L 2 , or L 3 ​​​Each of them is, independently, a linker, each Ak is, independently, an optionally substituted alkylene, and each of n and n1 is, independently, an integer (e.g., 1 or more, e.g., 1 to 25000, 1 to 24000, 1 to 23000, 1 to 22000, 1 to 21000, 1 to 20000, 1 to 19000, 1 to 18000, 1 to 17000, 1 to 16000, 1 to 15000, 1 to 14000, 1 to 13000, 1 to 12000, 1 to 11000, 1 to 10000, 1 to 7500, 1 to 5000, 1 to 4000, 1 to 3000, 1 to 2000, 1 to 1000, 1 to 500, 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 2 to 25000, 2 to 24000, 2 to 23000, 2 to 22000, 2 to 21000, 2 to 20000, 2 to 19000, 2 to 18000, 2 to 17000, 2 to 16000, 2 to 15000, 2 to 14000, 2 to 13000, 2 to 12000, 2 to 11000, 2 to 10000, 2 to 7500, 2 to 5000, 2 to 4000, 2 to 3000, 2 to 2000, 2 to 1000, 2 to 500, 2 to 100, 2 to 50, 2 to 20, 2 to 10, 2 to 5, 5 to 25000, 5 to 24000, 5 to 23000, 5 to 22000, 5 to 21000, 5 to 20000, 5 to 19000, 5 to 18000, 5 to 17000, 5 to 16000, 5 to 15000, 5 to 14000, 5 to 13000, 5 to 12000, 5 to 11000, 5 to 10000, 5 to 7500, 5 to 5000, 5 to 4000, 5 to 3000, 5 to 2000, 5 to 1000, 5 to 500, 5 to 100, 5 to 50, 5 to 20, 5 to 10, and integers in the ranges therebetween).

[0179] In some embodiments, R A , R A1 , or R A2 is -NH-, -NR N1 -, -N(-L 1 -NR N1 R N2 )-, -N(-L 2 -NR N3 -L 1 -NR N1 R N2 )-, -N[-L 2 -N(-L 1 -NR N1R N2 )2]-, -NH2, -NR N1 R N2 , -L 1 -NR N1 R N2 , -NR N3 -L 1 -NR N1 R N2 , -L 2 -NR N3 -L 1 -NR N1 R N2 , or -NR N4 -L 2 -NR N3 -L 1 -NR N1 R N2 or includes the same.

[0180] In some embodiments, each of R N1 , R N2 , R N3 , R N4 , and R N5 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, wherein R is optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, wherein R is optionally substituted aryl), trialkylsilyloxy (e.g., -OSiR3, wherein each R is independently optionally substituted alkyl), or trialkoxysilyloxy (e.g., -OSi[OR]3, wherein each R is independently optionally substituted alkyl). In some embodiments, each of R N1 , R N2 , R N3 , R N4 , R N5 , and R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0181] In some embodiments, R S1 and R S2 each independently is a side group (e.g., any of those described herein), a leaving group (e.g., halo, acyl, acyloxy, etc.), a reactive group (e.g., hydroxy, halo, alkoxy, etc.), hydrogen (H), optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted amine, or an R A moiety (e.g., any of those described herein), or R S1 and R S2 together with the silicon atom to which each is attached form a heterocyclyl group. In some embodiments, R S1 and R S2 each independently is hydrogen (H), optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0182] In some embodiments, the linker comprises, for example, a covalent bond, an atom (e.g., carbonyl, oxy, thio, imino, etc.), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene.

[0183] The functional moiety can include an interaction moiety. In some embodiments, the interaction moiety can include one, two, three, or more silane moieties (e.g., any of those described herein). In some embodiments, the interaction moiety includes one or more Si—O bonds.

[0184] In some implementations, the silane moiety is an alkoxysilane group (e.g., -Si(OAk) d (X) 3~d , or -Si(OAk) d1 (X) 2~d1 , or -Si(OAk) d(X) 2~d R A ); trialkoxysilane group (e.g., -SiR S1 R S2 R S3 wherein each of R S1 , R S2 , and R S3 is independently alkoxy; e.g., trimethoxysilane or triethoxysilane); dialkoxysilane group (e.g., e.g., -SiR S1 R S2 R S3 or -SiR S1 R S2 - wherein each of R S1 and R S2 is independently alkoxy and R 3 is a side group, leaving group, reactive group, or any of those described herein); monoalkoxysilane group (e.g., -SiR S1 R S2 R S3 or -SiR S1 R S2 - wherein R S1 is alkoxy and each of R S2 and R S3 is independently a side group, leaving group, reactive group, or any of those described herein); dialkoxysilanol group (e.g., -Si(OR)2OH wherein each R is independently alkyl); monoalkoxysilanol group (e.g., -Si(OR)(R S1 )OH wherein each R is independently alkyl and R S1 is a side group, leaving group, reactive group, or any of those described herein); hydrosilane group (e.g., -SiH3 or -SiH2-); monoalkylsilane group (e.g., -SiR S1 R S2 R S3 or -SiR S1 R S2 - wherein R S1 is alkyl and each of R S2 and R S3Each of them is independently a side group, a leaving group, a reactive group, or any of those described herein. Non-limiting examples of monoalkylsilanes are alkyldialoxysilanes or alkyldihalosilanes); dialkylsilane groups (e.g., -SiR S1 R S2 R S3 or -SiR S1 R S2 -, wherein each R S1 and R S2 is independently alkyl, and R S3 is a side group, a leaving group, a reactive group, or any of those described herein. Non-limiting examples of dialkylsilanes include dialkylalkoxysilanes or dialkylhalosilanes); trihalosilane groups (e.g., -SiZ3, wherein each Z is independently halo, e.g., trichlorosilane); dihalosilane groups (e.g., -SiZ2R S1 wherein each Z is independently halo and each R S1 is a side group, a leaving group, a reactive group, or any of those described herein); monohalosilane groups (e.g., -SiZR S1 R S2 wherein Z is halo and each R S1 and R S2 is independently a side group, a leaving group, a reactive group, or any of those described herein); silanetriol groups (e.g., -Si(OH)3); or hydroxysilane groups (e.g., -Si(OH)R S1 -, -Si(OH)2-, or -Si(OH)3).

[0185] 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, reactive group, or leaving group as any of those described herein, d is an integer of 1, 2, or 3, and d1 is an integer of 1 or 2. In some embodiments, R S1 , R S2 , and R S3Each of them is independently a side group (e.g., any of those described herein), a leaving group (e.g., halo, acyl, acyloxy, etc.), a reactive group (e.g., hydroxy, halo, alkoxy, etc.), hydrogen (H), optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted amine, or R A portion (e.g., any of those described herein), or R S1 and R S2 together with the silicon atom to which each is attached form a heterocyclyl group. In some embodiments, R S1 and R S2 each is independently hydrogen (H), optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0186] Any useful combination of the portions can exist. For example, the functional portion can include a combination of one or more adsorption portions, a combination of one or more interaction portions, a combination of an adsorption portion and an interaction portion, and a combination of one or more adsorption portions and one or more interaction portions.

[0187] The functional portion can be provided in any useful manner. For example, a compound having both an adsorption portion and an interaction portion can be provided to the substrate. Non-limiting examples of such compounds can include aminosilanes containing an amino portion (e.g., as an adsorption portion) and a silane portion (e.g., as an interaction portion). In some embodiments, the compound provides a long-chain polyamine-containing portion. In some embodiments, the compound provides a silane portion chemically bonded to the surface of each of the particles (e.g., porous silica particles) that function as a substrate.

[0188] In another example, a plurality of compounds can be used to provide one or more adsorption moieties and one or more interaction moieties. For example, a first compound can include both an adsorption moiety and an interaction moiety, and a second compound can include one or more adsorption moieties. As a non-limiting example, a first compound that is an aminosilane including an amino moiety (e.g., as an adsorption moiety) and a silane moiety (e.g., as an interaction moiety) can be used in combination with a second compound that is a polyamine including a plurality of amino moieties (e.g., as adsorption moieties). In some embodiments, the first compound is attached to the surface of the substrate (e.g., by one or more covalent or non-covalent bonds), and the second compound may or may not be attached to the substrate. In some embodiments, the second compound can interact with the first compound (or a portion thereof). In some embodiments, the second compound can interact with the first compound (or a portion thereof) and the surface of the substrate. Such attachment and interaction can include covalent and / or non-covalent interaction. Non-covalent interactions include, but are not limited to, hydrogen bonds, ionic interactions, halogen bonds, electrostatic interactions, η-bond interactions, hydrophobic interactions, inclusion complexes, inclusion, van der Waals interactions, and combinations thereof.

[0189] When one or more compounds are provided to a substrate, a reaction can occur to provide covalent and / or non-covalent interactions, thereby providing functional moieties disposed on the surface of the substrate. Non-limiting examples of compounds for providing functional moieties include amines, aminosilanes, polymers, polyamines, and others described herein.

[0190] a. Aminosilane In some embodiments, the compound is an aminosilane. For example, without limitation, the surface of a substrate (e.g., a silica substrate) is functionalized with an aminosilane compound that includes a silane moiety bonded to an amine moiety. The surface can then include a functional group having a silane moiety and an amine moiety. As used herein, such moieties can also include, as would be understood by one of ordinary skill in the art, the reactive forms of these moieties (e.g., the reactive form of the silane moiety upon reaction with the surface of the substrate) that can exist when forming one or more bonds.

[0191] An aminosilane can include at least one silane moiety (e.g., 1, 2, 3, or more silane moieties) and at least one amine moiety (e.g., 1, 2, 3, or more amine moieties). Non-limiting examples of aminosilane compounds, silane moieties, and amine moieties can be any of those described herein.

[0192] An aminosilane compound can include 1, 2, 3, or more silane moieties. In some implementations, the silane moiety is a trialkoxysilane (e.g., -SiR S1 R S2 R S3 wherein each of R S1 , R S2 and R S3 is independently an alkoxy; e.g., trimethoxysilane or triethoxysilane), a dialkoxysilane (e.g., -SiR S1 R S2 R S3 wherein each of R S1 and R S2 is independently an alkoxy and R S3 is a leaving group or a reactive group, e.g., any of those described herein), a dialkoxysilanol group (e.g., -Si(OR)2OH wherein each R is independently an alkyl), a hydrosilane group (e.g., -SiH3), a monoalkylsilane group (e.g., -SiR S1 R S2 R S3 wherein R S1is alkyl, R S2 and R S3 each independently is a leaving group or a reactive group, such as any of those described herein, and non-limiting examples of monoalkylsilanes are alkyldialkoxysilanes or alkyldihalosilanes), a dialkylsilane group (e.g., -SiR S1 R S2 R S3 wherein R S1 and R S2 each independently is alkyl, and R S3 is a reactive group or a leaving group, such as any of those described herein, and non-limiting examples of dialkylsilanes include dialkylalkoxysilanes or dialkylhalosilanes), a trihalosilane group (e.g., -SiZ3 where each Z independently is halo, such as trichlorosilane), or a silanetriol (e.g., -Si(OH)3). A higher number (e.g., three or more) of silane moieties in an aminosilane compound can increase the higher number of siloxane bonds between the silane moiety and the substrate surface, thus increasing the covalent bond stability with the substrate. Additionally, a silane group can form up to three siloxane bonds (Si-O-Si) to the surface, which can increase stability. The number of siloxane bonds that can be formed by a silane moiety depends on the composition of side groups (e.g., -OMe, -OEt, -Cl, -OH, or any combination thereof) that are capable of forming siloxane bonds (e.g., X 1 X 2 and / or X 3 one or more of).

[0193] An aminosilane compound can contain one, two, three, or more amine moieties. In some implementations, the amine moiety is a primary amine (e.g., -NH2), a secondary amine (e.g., -NHR N1 wherein R N1 can be any of those described herein that is not hydrogen), a tertiary amine (e.g., -NR N1 RN2 and wherein R N1 and R N2 each can be any of those described herein that are not hydrogen), or an aminoalkyl group (e.g., -Ak-NR N1 R N2 wherein Ak is optionally substituted alkylene and R N1 and R N2 each can be any of those described herein), and can include. In some embodiments, R N1 and R N2 each independently is 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 where R is optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR where R is optionally substituted aryl), trialkylsilyloxy (e.g., -OSiR3 where each R is independently optionally substituted alkyl), or trialkoxysilyloxy (e.g., -OSi[OR]3 where each R is independently optionally substituted alkyl). In some embodiments, R N1 , R N2 , and each of R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0194] In some implementations, the amine moiety includes two or more amine groups connected via various linkers (e.g., any of those described herein for L). For example, the amine moiety can include a terminal amine group (e.g., -NR N1 R N2 ), one or more internal amine groups (e.g., -NR N3-), and can include a linker (e.g., -L-) disposed between the terminal amine group and the internal amine group. Non-limiting examples of the amine moiety include aminoalkylamino groups (e.g., -NR N3 -Ak-NR N1 R N2 wherein Ak is optionally substituted alkylene, and R N1 R N2 and R N3 each can be any of those described herein), or aminoalkylaminoalkyl groups (e.g., -Ak-NR N3 -Ak-NR N1 R N2 wherein each Ak is independently optionally substituted alkylene, and R N1 R N2 and R N3 each can be any of those described herein). In some embodiments, R N1 R N2 and R N3 each are 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 where R is optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR where R is optionally substituted aryl), trialkylsilyloxy (e.g., -OSiR3 where each R is independently optionally substituted alkyl), or trialkoxysilyloxy (e.g., -OSi[OR]3 where each R is independently optionally substituted alkyl). In some embodiments, R N1 R N2 R N3 and each of R are independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0195] Higher numbers (e.g., three or more) of amine moieties in an aminosilane compound can increase the adsorption capacity of the adsorbent. In some embodiments, the amine moiety can interact with other moieties and groups to stabilize the stability of the functional group.

[0196] In some embodiments, the amine moiety of one aminosilane (which can be, for example, an amine group) can interact with an adjacent aminosilane (e.g., with a silane moiety or side group within the silane moiety of the adjacent aminosilane). Alternatively, the amine moiety of one aminosilane may not interact with an adjacent aminosilane (e.g., may not interact with a silane moiety or side group within the silane moiety of the adjacent aminosilane). In still another embodiment, the amine moiety of one aminosilane can interact with other groups, moieties, or compounds (e.g., those present in another compound, such as a polyamine or another type of aminosilane). In some embodiments, the amine moiety of an aminosilane (which can be, for example, an amine group) can interact with a polyamine (e.g., the amine moiety of a polyamine).

[0197] The aminosilane compound can have any useful structure. In a non-limiting example, the aminosilane has the formula (I), [R A a Si[X] 4~a (I) and includes a structure having the formula, wherein each R A is independently an amine moiety containing 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.

[0198] The amine moiety (e.g., R A ) can contain one or more amine groups. In one instance, the amine group can be -NR N1 R N2 or -NR N1 -, wherein R N1 and R​N2 Each of which 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, wherein R is optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, wherein R is optionally substituted aryl), trialkylsilyloxy (e.g., -OSiR3, wherein each R is independently optionally substituted alkyl), or trialkoxysilyloxy (e.g., -OSi[OR]3, wherein each R is independently optionally substituted alkyl). In some embodiments, R N1 , R N2 , and each of R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0199] In some embodiments, the amine moiety (e.g., R A ) contains 1, 2, 3, or more amine groups. In other embodiments, the amine moiety contains a terminal amine group (e.g., as -NR N1 R N2 ) and / or an internal amine group (e.g., as -NR N1 -).

[0200] Non-limiting examples of the amine moiety (e.g., R A ) include -NR N1 R N2 , -L-NR N1 R N2 , -NR N3 -L-NR N1 R N2 , -L 2 -NR N3 -L 1 -NR N1 R N2 , -L 3 -NR N4 -L2 -NR N3 -L 1 -NR N1 R N2 ,-L 2 -SiR S1 R S2 -L 1 -NR N1 R N2 , and -L 3 -SiR S1 R S2 -L 2 -NR N3 -L 1 -NR N1 R N2 include, where R N1 , R N2 , R S1 , and R S2 each can be any of those described herein, and each of R N3 and R N4 can be any of those described herein for R N1 and R N2 , and each L, L 1 , L 2 , or L 3 is independently a linker. Examples of linkers include, for example, covalent bonds, atoms (such as carbonyl, oxy, thio, imino, etc.), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene. In some non-limiting embodiments, each of R N1 , R N2 , R N3 , R N4 , R S1 , and R S2 is independently H, optionally substituted aliphatic, or optionally substituted alkyl. Other examples of R N1 , R N2 , and R N3 are described herein.

[0201] The aminosilane can contain 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, where R is optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, where R is 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.

[0202] In a non-limiting example, the aminosilane has the structure of formula (Ia), R A1 SiX 1 X 2 X 3 (Ia) wherein R A1 is an amine moiety containing at least one amine group, and each of X 1 , X 2 , and X 3 is independently a side group, a reactive group, or a leaving group. Each of R A1 , X 1 , X 2 , and X 3 can each be any of those described herein for R A and X.

[0203] In another non-limiting example, the aminosilane has the structures of formulas (Ib)-(Ie), R A1 -L 1 -SiX 1 X 2 X 3 (Ib) R N1 R N2 N-L1 -SiX 1 X 2 X 3 3 (Ic) R A1 -L 1 -R A2 -L 2 -SiX 1 X 2 X 3 (Id) or R N1 R N2 N-L 1 -N(R N3 )-L 2 -SiX 1 X 2 X 3 (Ie) comprises a structure having, wherein each R A1 or R A2 is, independently, an amine moiety containing at least one amine group, and each of R N1 , R N2 , and R N3 can be any of those described herein, and each of X 1 , X 2 , and X 3 is, independently, a side group, a reactive group, or a leaving group, and each of L 1 and L 2 is a linker. Each of R A1 , R A2 , X 1 , X 2 , X 3 , L 1 , and L 2 can each be any of those described herein for R A , X, and L, respectively. In some embodiments, each of X 1 , X 2 , and X 3 is, independently, H, halo, optionally substituted alkyl (e.g., optionally substituted C 1~3 alkyl), or optionally substituted alkoxy (e.g., optionally substituted C 1~3 alkoxy). In other embodiments, each of X 1 , X 2 , and X3 Each of them is independently an optionally substituted alkoxy (e.g., optionally substituted C 1~3 alkoxy). In other embodiments, L is an optionally substituted alkylene (e.g., optionally substituted C 1~12 , C 1~10 , C 1~8 , or C 1~6 alkylene).

[0204] In yet another non-limiting example, the aminosilane has a structure represented by formula (If), R A1 R A2 R A3 SiX 1 (If) wherein each R A1 , R A2 , or R A3 is independently an amine moiety containing at least one amine group, and X 1 is a side group, a reactive group, or a leaving group. Each of R A1 , R A2 , R A3 , and X 1 can each be any of those described herein for R A and X.

[0205] In some examples, the aminosilane has a structure represented by formula (II), [R B b N[Y] 3~b (II) wherein each R B is independently a silane moiety containing at least one silane group, 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.

[0206] The silane moiety (e.g., R B ​) can contain one or more silane groups. In one example, the silane group can be -SiR S1 R S2 R S3 or -SiR S1 R S2 -, where in the formula, each of R S1 , R S2 , and R S3 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 where R is optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR where R is optionally substituted aryl), trialkylsilyloxy (e.g., -OSi R3 where in the formula, each R is independently optionally substituted alkyl), or trialkoxysilyloxy (e.g., -OSi[OR]3 where in the formula, each R is independently optionally substituted alkyl). In some embodiments, each of R S1 , R S2 , R S3 , and R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0207] In some embodiments, the silane moiety (e.g., R B ) contains 1, 2, 3, or more silane groups. In other embodiments, the silane moiety contains a terminal silane group (e.g., -SiR S1 R S2 R S3 ) and an internal silane group (e.g., -SiR S1 R S2 -).

[0208] Non-limiting examples of the silane moiety (e.g., R B ) include -SiR S1R S2 R S3 ,-Si(OR S1 )(R S2 )(R S3 ),-Si(OR S1 )(OR S2 )(R S3 ),-Si(OR S1 )(OR S2 )(OR S3 ),-L-SiR S1 R S2 R S3 ,-L-Si(OR S1 )(R S2 )(R S3 ),-L-Si(OR S1 )(OR S2 )(R S3 ),-L-Si(OR S1 )(OR S2 )(OR S3 ),-SiR S4 R S5 -L-SiR S1 R S2 R S3 ,and -SiR S1 R S2 -NR N1 R N2 are included, where each of R S1 , R S2 , R S3 , R N1 , and R N2 can be any of those described herein, and each of R S4 and R S5 can be any of those described herein for R S1 , R S2 , and R S3 , and L is a linker. Examples of linkers include, for example, covalent bonds, atoms (such as carbonyl, oxy, thio, imino, etc.), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene. In some non-limiting embodiments, R S1 , R S2 , R S3 , R S4 , RS5 , R N1 , and R N2 each is independently H, optionally substituted aliphatic, or optionally substituted alkyl.

[0209] In a non-limiting example, the aminosilane has the structure of formula (IIa), R B1 NY 1 Y 2 (IIa) wherein R B1 is a silane moiety containing at least one silane group, and each of Y 1 and Y 2 is independently any of those described herein for Y (e.g., side group, reactive group, or leaving group). R B1 can be any of those described herein for R B .

[0210] In another non-limiting example, the aminosilane has the structures of formulas (IIb) - (IId), R B1 R B2 NY 1 (IIb) [R S1 R S2 R S3 Si-L 1 -]NY 1 Y 2 (IIc) or [R S1 R S2 R S3 Si-L 1 -]NY 1 [-L 2 -SiR S1 R S2 R S3 (IId) wherein each R B1 or R B2 is independently a silane moiety containing at least one silane group, and each of Y 1 and Y 2 is independently a side group, reactive group, or leaving group, and R S1 , R S2、and R S3 Each of which can be any of those described herein, L 1 and L 2 Each of which is a linker. R B1 、R B2 、Y 1 、Y 2 、L 1 、and L 2 Each of which can be any of those described herein for R B 、Y, and L, respectively.

[0211] Figure 2A shows an example of an aminosilane 206, which has an amine moiety 210 (shown as R A ) and a non-limiting silane moiety 208, and the silane moiety 208 has three potential interaction sites or side groups (shown as X 1 、X 2 、and X 3 ). The side groups X 1 ~X 3 are occupied by functional groups, and the functional groups include, but are not limited to, a methoxy group (-OMe), an ethoxy group (-OEt), chloro (-Cl), a hydroxy group (-OH), hydrogen (-H), or an alkyl group (e.g., a straight-chain alkyl group, e.g., -(CH2) n (CH3) (where n is an integer from 0 to 10); or a branched-chain alkyl group). Other examples of functional groups can include any of the reactive or leaving groups 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, etc.

[0212] In some embodiments, the amine moiety 210 of one aminosilane (which can be, for example, an amine group) can interact with one or more of the side groups 208 of an adjacent aminosilane. Alternatively, the amine moiety 210 may not interact with other side groups. In yet another embodiment, the amine moiety 201 can interact with other groups, moieties, or compounds (such as those present in another compound, for example, a polyamine or another type of aminosilane). In some embodiments, the amine moiety 210 of the aminosilane 208 (which can be, for example, an amine group) can interact with a polyamine.

[0213] Optionally, a further linker can be present between the amine moiety and the silane moiety of the aminosilane compound. For example, the linker can be present between the amine moiety 210 and the silane moiety 208. In some embodiments, the aminosilane is R A -L-SiX 1 X 2 X 3 and can include, where R A is an amine moiety (such as any of those described herein), L is a linker (such as any of those described herein), and each of X 1 , X 2 , and X 3 is a side group, a reactive group, or a leaving group (such as any of those described herein).

[0214] The aminosilane 206 has these functional groups, such as the amine moiety 210 and the side groups 208 (such as side group X 1 , side group X 2 , or side group X 3It can include any combination of (things that can be included), 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) that can form a siloxane bond (e.g., Si - O or Si - O - Si linkage). Figure 2B shows a non - limiting example of a 3 - aminopropyl group, and in some examples, this group functions as one or more of the side groups 208 (e.g., X 1 , X 2 , and X 3 (one or more of them) or as the amine moiety 210. Figure 2C shows an example of an N - (2 - aminoethyl) - 3 - aminopropyl group, and in some examples, this group functions as one or more of the amine moieties 210.

[0215] As non - limiting examples, Figures 2D - 2G show examples of aminosilanes having side groups and amine moieties. In some embodiments, the aminosilane is an alkylalkoxy aminosilane having the formula R A (Ak) c Si(OAk) d , where each of c and d can be 1 or 2, R A is an amine moiety (e.g., any of those described herein), and each of Ak is independently an optionally substituted alkyl. Non - limiting examples of alkylalkoxy aminosilanes include 3 - aminopropyl(diethoxy)methylsilane (Figure 2D) and 3 - (ethoxydimethylsilyl)propylamine (Figure 2E).

[0216] In some embodiments, the aminosilane is an aminosilanetriol having the formula (HO)3SiR A , where R A is an amine moiety (e.g., any of those described herein). A non - limiting example of an aminosilanetriol is (3 - ((2 - aminoethyl)amino)propyl)silanetriol (Figure 2F).

[0217] In some embodiments, the aminosilane is a haloaminosilane having the formula (R A )3SiX, where each R A is independently an amine moiety (e.g., any of those described herein), and X is halo (e.g., any of those described herein). Non-limiting examples of haloaminosilanes include tris(dimethylamino)chlorosilane (Figure 2G), tris(ethylmethylamino)chlorosilane, and the like.

[0218] Other non-limiting examples of aminosilanes include (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, 3-aminopropyl(diethoxy)methylsilane, [3-(2-aminoethylamino)propyl]trimethoxysilane, N-(2-aminoethyl)-3-aminopropylsilanetriol, N-[3-(trimethoxysilyl)propyl]ethylenediamine, N1-(3-trimethoxysilylpropyl)diethylenetriamine, 3-aminopropylsilanetriol, tris(ethylmethylamino)chlorosilane, tris(dimethylamino)chlorosilane, bis(3-(methylamino)propyl)trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, N-[3-(trimethoxysilyl)propyl]aniline, (N,N-dimethylaminopropyl)trimethoxysilane, or an aminosilane oligomer (e.g., VPS SIVO 280, a modified organofunctional polysiloxane from Evonik Industries AG, Essen, Germany).

[0219] b. Silane As used herein, a silane compound can include any having a -SiR S1 R S2 R S3 moiety or a -SiR S1 R S2 - moiety, where R S1 , R S2 , and R S3Each of which can be any of those described herein. In some embodiments, R S1 , R S2 , and R S3 can each independently be H, optionally substituted aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, aryl, amine, or other as described herein, or R S1 and R S2 together with the silicon atom to which each is attached form a heterocyclyl group. In some embodiments, R S1 , R S2 , and R S3 can each independently be 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 where R is optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR where R is optionally substituted aryl), trialkylsilyloxy (e.g., -OSi R3 where each R is independently optionally substituted alkyl), or trialkoxysilyloxy (e.g., -OSi[OR]3 where each R is independently optionally substituted alkyl).

[0220] In some embodiments, the silane can include one or more amino moieties, such as those in an aminosilane compound (e.g., any of those described herein).

[0221] In some embodiments, the silane does not contain an amino moiety. In a non-limiting example, the silane has a structure including formula (IV), [R C1 a Si[X] 4~a (IV) where each R C1 ​It contains no amino groups, each X is independently a side group, a reactive group, or a leaving group (e.g., any of those described herein), and a is an integer from 1 to 4.

[0222] In some embodiments, R C1 is an optionally substituted aliphatic, heteroaliphatic, alkyl, aromatic, heteroaromatic, or aryl, and the optional substituent is not an amino group (e.g., as defined herein). In some embodiments, R C1 is a branched-chain optionally substituted aliphatic, heteroaliphatic, alkyl, aromatic, heteroaromatic, or aryl. In some embodiments, R C1 is a hydrophobic group (e.g., an optionally substituted C 4~30 aliphatic, heteroaliphatic, alkyl, perfluoroalkyl, cycloalkyl, aromatic, heteroaromatic, or aryl). Non-limiting examples of hydrophobic groups include optionally substituted C 4~24 , C 6~24 , C 8~24 , C 4~18 , C 6~18 , C 8~18 alkyl, haloalkyl, perfluoroalkyl, cycloalkyl, etc. (e.g., hexyl, octyl, nonyl, decyl, dodecyl, perfluorohexyl, perfluorooctyl, cyclohexyl, and cyclopentyl).

[0223] In some embodiments, the silane has a structure represented by formula (IVa), [X]3Si-L-Si[X]3 (IVa) wherein L is a linker (e.g., any of those described herein), and each X is independently a side group, a reactive group, or a leaving group (e.g., any of those described herein).

[0224] Examples of linkers include, for example, covalent bonds, atoms (e.g., carbonyl, oxy, thio, imino, etc.), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene. Other examples of linkers include any of those described herein (e.g., L, L 1 , L 2 , and L 3 as described herein).

[0225] Silanes can include 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 where R is optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR where R is optionally substituted aryl), optionally substituted alkanoyloxy, trialkylsilyloxy (e.g., -OSi R3 where each R is independently optionally substituted alkyl), or trialkoxysilyloxy (e.g., -OSi[OR]3 where each R is independently optionally substituted alkyl). In some embodiments, X is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0226] In some embodiments, the silane can be used as a crosslinking agent or additive for any of the compositions or uses herein (e.g., for any coating, surface functionalization layer, functionalized mixture, pre-functionalized mixture, etc.). Non-limiting examples of silanes include 1,2-bis(triethoxysilyl)ethane (BTESE) or 1,2-bis(trimethoxysilyl)ethane (BTME).

[0227] c. Polyamine As described herein, the functional moiety can be provided by any useful compound or combination of compounds. In some embodiments, the compound is a polyamine. A polyamine can include any compound or moiety having two or more amine moieties. In some embodiments, the polyamine is a non-polymeric compound and the polyamine does not contain 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). Considerations regarding the "polymer" and "oligomer" forms of a compound can be applied interchangeably unless otherwise specified. In some embodiments, the polyamine can include dimers, trimers, tetramers, pentamers, hexamers, and higher order amines. In some embodiments, the polyamine can include small molecule polyamines (e.g., having an MW of 100 - 800 g / mol). In some embodiments, the polyamine can include large molecule polyamines (e.g., having an MW greater than 800 g / mol).

[0228] The polyamine may be used alone or may be used together with other compounds (e.g., any of those described herein, e.g., aminosilanes, etc.). In some embodiments, the polyamine can be used in the presence of an aminosilane. In some embodiments, a first polyamine (e.g., one having a high MW, e.g., any of those described herein) can be used in the presence of a second polyamine (e.g., one having a low MW, e.g., any of those described herein).

[0229] In some embodiments, the high MW is greater than 300 Daltons (Da), 400 Da, 500 Da, or 600 Da, or from 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,a weight average molecular weight (Mw, w ) or a number average molecular weight (Mn n ) in the range of 700 - 7000 Da, 700 - 6000 Da, 700 - 5000 Da, 700 - 4000 Da, 700 - 3000 Da, 700 - 2000 Da, 700 - 1000 Da, 800 - 1000000 Da, 800 - 900000 Da, 800 - 800000 Da, 800 - 700000 Da, 800 - 600000 Da, 800 - 500000 Da, 800 - 400000 Da, 800 - 300000 Da, 800 - 200000 Da, 800 - 100000 Da, 800 - 90000 Da, 800 - 80000 Da, 800 - 70000 Da, 800 - 60000 Da, 800 - 50000 Da, 800 - 40000 Da, 800 - 30000 Da, 800 - 20000 Da, 800 - 10000 Da, 800 - 9000 Da, 800 - 8000 Da, 800 - 7000 Da, 800 - 6000 Da, 800 - 5000 Da, 800 - 4000 Da, 800 - 3000 Da, 800 - 2000 Da, or 800 - 1000 Da).

[0230] In some embodiments, low MW is less than 300 Da, in the range of 30 - 300 Da, in the range of 100 - 800 Da, or in a range therebetween (e.g., 30 - 800 Da, 30 - 700 Da, 30 - 500 Da, 30 - 200 Da, 30 - 100 Da, 50 - 800 Da, 50 - 700 Da, 50 - 600 Da, 50 - 500 Da, 100 - 700 Da, 100 - 600 Da, 100 - 500 Da, 100 - 400 Da, 100 - 300 Da, 150 - 800 Da, 150 - 700 Da, 150 - 600 Da, 150 - 500 Da, 150 - 400 Da, 150 - 300 Da, 200 - 800 Da, and 300 - 800 Da) of a weight average molecular weight (Mw w ) or a number average molecular weight (Mn nIt can include. Low MW polyamines (e.g., those that can be considered oligomeric amines) can include linear or branched chain forms. Low MW polyamines can include multiple primary amine moieties and / or multiple secondary amine moieties. In some embodiments, the low MW polyamine is provided in an oligomeric form.

[0231] Without desiring to be limited by the mechanism, high MW amines can be useful due to their lower volatility (e.g., compared to low MW amines). Higher MW polyamines can be characterized by higher viscosities, which can make handling more difficult. Higher MW polyamines are generally more expensive. In some non-limiting embodiments, polyamines having high relative concentrations of primary and secondary amine moieties can be used. In some non-limiting embodiments, tertiary amine moieties can be characterized by lower performance for DAC applications and are less desirable. Secondary amines have higher oxidation resistance equal to a longer operating life. Primary amines have higher reactivity equal to higher performance at low CO2 concentrations (DAC conditions).

[0232] The polyamine can have any useful structure. In one non-limiting example, the polyamine has the formulas (IIIa)-(IIIi),

Chemical formula

[0233] In some embodiments, R A , R A1 , R A2 , or R A3 is -NH-, -NR N1 -, -N(-L 1 -NR N1 R N2 )-, -N(-L 2 -NR N3 -L 1 -NR N1 R N2 )-, -N[-L 2 -N(-L 1 -NR N1 R N2 )2]-, -NH2, -NR N1 R N2 , -L 1 -NR N1 R N2 , -NR N3 -L 1 -NR N1 R N2 , -L 2 -NR N3 -L 1 -NR N1 R N2 , or -NR N4 -L 2 -NR N3 -L 1 -NR N1 R N2 or includes the same, wherein each of R N1 and R N2 can be any of those described herein, and each of R N3 and R N4 can be any of those described herein for R N1 and R N2 , and each of L 1 or L 2 is independently a linker.

[0234] Linker (e.g., L 1, L 2 , or with respect to L) Examples include, for example, covalent bonds, atoms (e.g., carbonyl, oxy, thio, imino, etc.), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene. In some embodiments, the linker is a monomer or polymer that can be used as a backbone to which the amine moiety R A can be attached. Alternatively, the backbone of the polymer itself can also contain an amine moiety. Non-limiting examples of monomers include sugars (e.g., glucosamine, N-acetyl-glucosamine, glucose, etc.), amino acids (e.g., lysine), alkylene, alkenylene, arylene, etc. Non-limiting examples of polymers include polysaccharides (e.g., chitosan, chitin, etc.), polypeptides (e.g., poly(lysine)), vinyl polymers, etc.

[0235] Additional 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-isopropylacrylamide), poly(4-aminostyrene), chitosan, spermidine, spermine, norspermine, putrescine, cadaverine, tetraethylenepentamine (TEPA), triethylenetetramine (TETA), ethyleneamine / oligomer mixtures (e.g., Amix 1000 having CAS number 68910-05-4), diethylenetriamine (DETA), 2-(2-aminoethylamino)ethanol, ethylenediamine, piperazine, 2-piperazin-1-ylethylamine, 2-piperazin-1-ylethanol, pentaethylenehexamine, tetramethylethylenediamine, and 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, diethylenetriamine (DETA), piperazine, 2-piperazin-1-ylethylamine, 2-piperazin-1-ylethanol, pentaethylenehexamine, tetramethylethylenediamine, and polymeric forms thereof. In some embodiments, the ethyleneamine / oligomer mixture includes one or more of the following: 2-(2-aminoethylamino)ethanol, trienchelin or TETA, 2,2'-iminodi(ethylamine) or DETA, 2-aminoethanol, ethylenediamine, piperazine, 2-piperazin-1-ylethylamine, and 2-piperazin-1-ylethanol.

[0236] In some embodiments, the polyamine includes H2N[CH2CH2NH] n H, wherein 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 includes H2N[-L-NH-]n Containing H or N[-L-NH2]3, wherein each L is independently a linker (e.g., any of those described herein, e.g., optionally substituted alkylene), and n is an integer of 1 or more. In some embodiments, the polyamine is H2N[CH2CH2CH2NH] n Containing H, wherein n is an integer of 1 or more (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more).

[0237] In some embodiments, the polyamine contains an oligomeric or polymeric form of ethyleneimine. In some embodiments, the polyamine is -[CH2CH2NH] n Containing -, wherein 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 -[CH2CH2NR A n Containing -, wherein R A is an amine moiety (e.g., any of those 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, R A is -Ak-NR N1 R N2 , or -Ak-N(-Ak-NR N1 R N2 )2, or -Ak-NR N1 -Ak-NR N2 R N3 , wherein Ak is optionally substituted alkylene, and each of R N1 , R N2 , and R N3 can be any of those described herein.

[0238] Figures 2H to 2K provide non-limiting general examples of polyamine chains that can provide a polyamine. The polyamines of Figures 2H and 2I are amine groups (e.g., -NH-, -NR N1 -, -NH2, or -NR N1 R N2 ​) and comprises repeating units composed of a linker. In some examples, the linker can be a carbon aliphatic-(CH2) n - spacer group, where n is an integer greater than 1 (e.g., an integer such as 1 - 20, 1 - 10, 1 - 12, 1 - 6, etc.). Figure 2H shows an n - propylene (-CH2CH2CH2-)(C3H6) spacer group. Figure 2I shows an ethylene (-CH2CH2-)(C2H4) spacer group. The polyamine has a repeating chain portion (in parentheses), and the repeating chain portion has an active group of length n in the chain portion of the polymer (e.g., when n = 2, two repeating groups are in the chain portion). Other linkers, such as any of those described herein (e.g., any optionally substituted alkylene described herein), and linkers having a peptide bond (e.g., -C(O)NH-) or a glycosidic linkage can be used. The linker can include peptides, polysaccharides, etc. Further, the polyamine can include those present in a linear or branched chain structure, such as a linear polymer, a branched polymer, a block polymer, or a dendrimer.

[0239] Figures 2H - 2I show a polyamine having an active group of length n in the repeating chain portion. Figures 2H - 2I also show the repeating chain portion, which includes two non - limiting amine groups (-N(X)-) separated by either a C3 (Figure 2H) or C2 (Figure 2I) spacer group. In NX, X can be any side group, reactive group, leaving group, or other group described herein. For example, X can be H, an optionally substituted aliphatic, heteroaliphatic, aromatic, etc. Further, X can include a further amine group. Thus, in some non - limiting embodiments, X can include any of the R A groups described herein (e.g., an aminoalkyl group, an alkylaminoalkyl group, etc.). Figure 2I shows amine groups extending from the carbon chain in different orientations, and Figure 2H shows amine groups extending in the same orientation.

[0240] Polyamines can be derived from natural polymers having amine moieties. For example, FIG. 2J is an example of poly(lysine), and FIG. 2K is an example of natural chitosan.

[0241] The amine moieties present in the polyamines can interact with other moieties, groups, or compounds that are proximal to the surface of the substrate. In some embodiments, the amine moieties of the polyamines can interact with silane moieties (e.g., silanol groups or other groups) present in the aminosilanes. In other embodiments, the amine moieties of the polyamines can interact with other polyamines, aminosilanes, or moieties of other groups that are proximal to the surface. Such interactions can include covalent or non-covalent interactions (e.g., hydrogen bonds, ionic interactions, and / or others described herein) to form a network over the surface of the substrate.

[0242] In some examples, the polyamine can be a polymer / oligomer amine, or a mixture containing a polymer / oligomer amine, such as poly(ethyleneimine) (PEI), poly(propyleneimine) (PPI), or a mixture of amines (e.g., a mixture containing multiple amines (e.g., polyamine and / or monoamine), such as Amix 1000 manufactured by BASF SE, Ludwigshafen, Germany, CAS number 68910-05-4). In some examples, the polyamine is a small molecule containing an amine moiety (e.g., small molecule amine), an oligomer containing an amine moiety (e.g., oligomer amine), or an oligomer containing an ethylene amine moiety (e.g., oligomer ethylene amine), such as tetraethylenepentamine (TEPA), triethylenetetramine (TETA), diethylenetriamine (DETA), ethylenediamine, a polymer or oligomer of monoethanolamine, a polymer or oligomer of diethanolamine, a polymer or oligomer of triethanolamine, 2-(2-aminoethylamino)ethanol, piperazine, 2-piperazin-1-ylethylamine, 2-piperazin-1-ylethanol, pentaethylenehexamine, tetramethylethylenediamine, or others described herein.

[0243] In some embodiments, the polyamine is a small molecule polyamine. In some embodiments, the small molecule polyamine is characterized by a boiling point high enough that the compound is not lost due to high volatility. In some embodiments, the small molecule polyamine has a boiling point of at least 170 °C. In some examples, these compounds have a reduced compound cost compared to alternatives.

[0244] In some embodiments, a mixture of one or more amines described herein (e.g., aminosilanes, polyamines, e.g., high molecular weight polyamines or low molecular weight polyamines, and / or monoamines) is used, and the presence of such amines provides a polymer or oligomer. In some embodiments, the mixture can further include an alcohol (e.g., ROH, where R is an optionally substituted aliphatic, alkyl, hydroxyalkyl, heteroaliphatic, heteroalkyl, aromatic, or aryl).

[0245] d. Monoamine As described herein, the functional moiety can be provided by any useful compound or combination of compounds. In some embodiments, the compound is a monoamine. A monoamine is any compound or moiety having one amine group (e.g., -NR N1 R N2 wherein R N1 and R N2 can be any of those described herein). The amine group can be attached to a linker (e.g., any of those described herein).

[0246] In certain embodiments, the monoamine is provided to a substrate and can act as an interaction or adsorption moiety.

[0247] In some embodiments, the monoamine can include an aminosilane having one amine group. Other examples of monoamine compounds include alkanolamines (e.g., HO-Ak-NR N1 R N2 where Ak is an optionally substituted alkylene and each of R N1 and R N2 can be any of those described herein, e.g., monoethanolamine), or alkylamines (e.g., Ak-NR N1 R N2 where Ak is an optionally substituted alkyl and R N1and R N2 Each of which can be any of those described herein, such as, for example, ethylamine or hexylamine). In some embodiments, the monoamine is of the formula R C1 N R1 R N2 a compound having the structure of, wherein R N1 and R N2 each can be any of those described herein, and R C1 is optionally substituted aliphatic, heteroaliphatic, alkyl, aromatic, heteroaromatic, or aryl, and the optional substituent is not an amino as defined herein, or R C1 does not contain an amino as defined herein.

[0248] iii. Interaction of moieties, groups, or compounds Any combination of moieties, groups, or compounds can be used to provide a functional moiety. In some embodiments, the functional moiety is provided as a coating or surface modification layer, and then the coating or surface modification layer can be formed from a complex network of interactions between one or more silanes, aminosilanes, polymer / oligomer amines, monoamines, and / or the surface of a substrate (e.g., a silica substrate).

[0249] In some embodiments, the interaction can be formed between the surface of the substrate and the silane moiety (e.g., those present in any of the silanes, aminosilanes, polymer silanes, or polymer aminosilanes described herein). In cases where the silane moiety is provided by a (poly)aminosilane, the silanol moiety on the silica surface can react with the silane moiety to form a siloxane linkage, which is a non-limiting example of a covalent bond. Such silanol moieties can be acidic and can be deprotonated by the basic amine moiety of the (poly)aminosilane to form an acid-base pair, which is a non-limiting example of an ionic interaction. The silanol moiety (on silica), as well as the silanol and amine moieties (on the (poly)aminosilane), can form various hydrogen-bonding interactions (e.g., by hydrogen bonding). In the case of large polymer silanes, the sum of these interactions can be significant. Silica and (poly)silane can be polar and can have weak dipole-dipole interactions. In the case of large polymer silanes, the sum of these interactions can be significant.

[0250] In some embodiments, the interaction can be formed between the surface of the substrate and the amine moiety (e.g., those present in any of the aminosilanes, polyamines, or monoamines described herein). In cases where the amine moiety is provided by a polyamine, the silanol moiety on the silica surface can be acidic and can be deprotonated by the basic amine moiety of the polyamine to form an acid-base pair, which is a non-limiting example of an ionic interaction. The silanol moiety (on silica) and the amine moiety (on the polyamine) can form various hydrogen-bonding interactions. Silica and polyamine can be polar and can have weak dipole-dipole interactions. Due to the large branched shape of some non-limiting polyamines, the sum of these weak interactions can be significant when the polyamine adheres to or otherwise interacts with the silica surface.

[0251] In some embodiments, the interaction can be formed between the surfaces of the substrate (e.g., the first and second surfaces of a silica substrate). In cases where the substrate contains silica, the silica-silica interaction can contribute to the formation and strength of the silica substrate. In some embodiments, the silica substrate can be composed of a single polymeric silicon dioxide molecule. In the case of precipitated silica, the silica substrate can be composed of a number of small nucleite particles, and the number of small nucleite particles can entangle into larger aggregates and ultimately aggregate into complete particles and be held together by physical interactions. Silicon dioxide can form siloxane (-Si-O-Si-) linkages between individual silicon atoms, and such siloxane linkages are non-limiting examples of covalent bonds. The silica nucleite particles and aggregates can physically entangle and aggregate to form substrate particles, and such entanglement and aggregation interactions are non-limiting examples of physical interactions. The surfaces of the silica nucleite particles and aggregates can contain silanol moieties, and the silanol moieties can form many hydrogen bond interactions that promote adhesion. The silica nucleite particles and aggregates can be polar and can form adhesive dipole-dipole interactions.

[0252] In some embodiments, the interaction can be formed between silane moieties (e.g., those present in any of the silanes, aminosilanes, or polymeric aminosilanes described herein). In instances where the silane moieties are provided by alkoxysilane groups or silanol groups, the silane moieties can react with each other to form siloxane condensation bonds. Both the silica surface and the silane can include silanol moieties, which can condense to form siloxane bonds. This process can be repeated multiple times to form a branched polysilane network having covalent bonds. The silanol or polysilane can include acidic silanol moieties, which can be deprotonated by basic amine moieties (e.g., those present in aminosilanes) to form acid-base interactions, which are a non-limiting example of ionic interactions. The silanol or polysilane can have silanol and amino moieties, which can form various hydrogen bond interactions. Large branched polysilanes can physically entangle with each other. The silanol and polysilane can be polar molecules and can have weak dipole-dipole interactions with each other. In the case of large branched polysilanes, the sum of these weak interactions can be significant.

[0253] In some embodiments, the interaction can be formed between amine moieties (e.g., those present in any amine, polyamine, aminosilane, or polymeric aminosilane). In instances where the amine moieties are provided by a polyamine, the polyamine can have various amine moieties that can donate and accept hydrogen bonds. Since the polyamine can be a polymer, a higher number of these intermolecular interactions are possible (e.g., by hydrogen bonding). Large polyamines can physically entangle with each other. The polyamine can be a polar molecule and can have some weak dipole-dipole interactions with each other. In the case of the large branched shapes present in some polyamines, the sum of these interactions can be significant.

[0254] In some embodiments, the interaction can be formed between an amino moiety (e.g., those present in any amine, polyamine, aminosilane, or polymeric aminosilane) and a silane moiety (e.g., those present in any silane, polymeric silane, aminosilane, or polymeric aminosilane). In the case where the amine moiety is provided by a polyamine, the polyamine can have multiple basic amine moieties, and the multiple basic amine moieties can deprotonate acidic silanol moieties (those in (poly)silane) to form acid-base interactions. In the case of large polyamines interacting with large polysilanes, the sum of these interactions can be even more significant (e.g., due to ionic interactions). The polyamine can have many amine moieties, and the many amine moieties can form various hydrogen-bonding interactions with silanol moieties (those in (poly)silane) and amine moieties. In the case of large polyamines interacting with large polysilanes, the sum of these interactions can be even more significant (hydrogen bonding). The polyamine and (poly)silane can be polar molecules and can have some weak dipole-dipole interactions with each other. In the case of large polyamines interacting with large polysilanes, the sum of these interactions can be significant.

[0255] iv. Additive Additives may be included. In some implementations, the additives may be included in the functionalized mixture to extend the operating life of the functionalized material. For example, the addition of bis[3-(trimethoxysilyl)propyl]amine (BTMSPA) to the mixture can increase the operating life of the functionalized material. BTMSPA is an aminosilane with two ends, and each end has a trimethoxysilyl reactive group. BTMSPA binds to six binding points on the substrate, in contrast to the three binding points for aminosilanes with a single reactive group, such as those present in compounds with a methoxydialkylsilyl reactive group. The increased number of binding points increases the binding stability with the silica substrate. BTMSPA can form a network with other aminosilanes and polyamines on the surface, which increases the binding stability of the entire network.

[0256] Other examples of additives may include polyamines (such as any of those described herein). Still other examples of additives include 1,2-bis(triethoxysilyl)ethane (BTESE), other bisaminosilane compounds (e.g., X 1 X 2 X 3 Si-L 1 -NR N -L 2 -SiX 4 X 5 X 6 wherein each of X 1 X 2 X 3 X 4 X 5 and X 6 is any of those described herein for X, each of L 1 and L 2 is any of those described herein for L, and R N is any of those described herein for R N1 ), or other bissilane compounds (e.g., X 1 X 2 X 3 Si-L 1 -SiX 4X 5 X 6 is, where X 1 , X 2 , X 3 , X 4 , X 5 and X 6 each is any one described in this specification for X, and L 1 is any one described in this specification for L).

[0257] In some embodiments, the functionalized material comprises an antioxidant additive. Without wishing to be bound by theory, the additive may prevent the decomposition of the amine moiety by atmospheric oxygen and / or may extend the cycle life of the functionalized material. For example, the antioxidant additive can be an organosulfur-containing compound such as 2,2'-thiodiethanol, 2-hydroxyethyldisulfide, and 3,3'-dithiodipropionic acid. In some embodiments, the organosulfur-containing compound has the formula R'SR", or R'SSR", or R'S-L-SR", where each of R' and R" is independently aliphatic, alkyl, hydroxyalkyl, carboxyalkyl, aromatic, aryl, hydroxyaryl, or carboxyaryl (e.g., as defined herein), each of which may be optionally substituted, and L is a linker (e.g., any one described herein).

[0258] Another example of an antioxidant additive can be a metal catalyst chelating agent. Without wishing to be bound by theory or mechanism, transition metal impurities (e.g., iron or copper) can increase the oxidation rate of the amine moiety, which can then reduce the lifespan of the adsorbent. In some embodiments, the catalyst chelating agent can be, for example, an alkali salt of phosphoric acid or phosphonic acid (e.g., sodium salt of phosphoric acid or phosphonic acid), aminopolycarboxylic acid or its salt (e.g., tetrasodium salt dihydrate of ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid), phosphonic acid or its salt (e.g., 1-hydroxyethane-1,1-diphosphonic acid monohydrate or ethylenediaminetetramethylenephosphonic acid), mercapto acid (e.g., can include meso-2,3-dimercaptosuccinic acid, etc.). In some embodiments, one or more catalyst chelating agents can be used to reduce the oxidation rate and improve the adsorbent lifespan.

[0259] Generally, the amount of antioxidant additive in the functionalized material is 5% (weight / weight) with respect to the substrate (e.g., 3%, 4%, 6%, or 8% (weight / weight)). The antioxidant additive can be added during (e.g., during the formation of the suspension mixture or the functionalization mixture) or after (e.g., dissolved in a solvent, e.g., an alcohol, e.g., methanol, and then the functionalized material is immersed in the additive / solvent mixture for 1 hour) any useful step of the following synthetic procedures.

[0260] In some implementations, the functionalized material may contain or be functionalized with other hydrophobic compounds, and the other hydrophobic compounds include hydrophobic silanes or hydrophobic polymer coatings. In some embodiments, the hydrophobic silane can include 1, 2, or 3 alkyl chains. In certain embodiments, the hydrophobic silane is R 1 R 2 R 3 SiX 1 or [R 1 a Si[X 1 4~a can be included, where R 1 、R​​2 and R 3 each is, independently, an optionally substituted aliphatic, alkyl, aromatic, or aryl, and X 1 is a side group, reactive group, or leaving group (e.g., any of those described herein for X), and a is 1, 2, or 3. Without wishing to be bound by theory, the alkyl chain on the silane molecule can increase the hydrophobicity of the silane molecule. The silane molecule can also increase the hydrophobicity of the functionalized material when bound to the substrate. Thus, the water adsorption capacity of the functionalized material can be reduced, which can be beneficial in some cases, for example, when using the adsorbent under high humidity conditions. For the same purpose of increasing the hydrophobicity of the functionalized material, an additional hydrophobic polymer coating can be used. Polydimethylsiloxane (PDMS), silicone oil, polyethylene, polypropylene, poly(tetrafluoroethylene), and polyurethane are possible hydrophobic polymers that can be used to coat the outer surface of the functionalized silica to reduce water adsorption for high humidity applications.

[0261] v. Features The functionalized material can be used as an adsorbent, and then the adsorbent can have any useful feature (e.g., any of those described herein).

[0262] In some embodiments, the functionalized material adsorbs CO2 at low concentrations and enables increased capture at levels present in atmospheric conditions. Capturing CO2 from atmospheric conditions can facilitate the use of the functionalized material in a number of applications.

[0263] In some embodiments, CO2 is desorbed from the functionalized material at laboratory temperature. This can reduce the energy required to remove the captured CO2, increase the applicability of the functionalized material to more industries and environments, and / or increase the rate at which CO2 is desorbed.

[0264] In some embodiments, the functionalized material can achieve a high adsorption / desorption count, which can reduce the operating costs in a carbon capture system. The functionalized material can enable repeated use of the substrate.

[0265] In some embodiments, the functionalized material can be produced using industrially available components, reducing the cost of production and increasing the scalability of production.

[0266] In some embodiments, the functionalized material includes a polymer, oligomer, or molecular source having a high density of amine functional groups, which can increase the uptake of CO2 per weight of the dry adsorbent.

[0267] In some embodiments, functionalizing the substrate with an aminosilane compound increases the binding stability of the polymer, oligomer, or high-density amine source, thereby increasing the useful life of the functionalized material.

[0268] In some embodiments, functionalizing the substrate with a polyamine (e.g., a high molecular weight polyamine) increases the binding stability compared to short-chain amine functionalization (e.g., using an oligomeric amine or low molecular weight amine having at least two amine moieties and a molecular weight of 100 - 800 g / mol).

[0269] In some embodiments, functionalizing the substrate with a small molecule polyamine (e.g., oligomeric amine, oligomeric ethylene amine, or ethylene amine / oligomeric mixture compound) reduces the cost of the functionalized substrate and facilitates large-scale functionalization of the substrate.

[0270] In some embodiments, the polyamine source has an increased amine density and is commercially available, which increases the cost-effectiveness of using the polyamine-functionalized material as an adsorbent.

[0271] In some embodiments, the functionalized material is produced on a short time scale in a one-pot reaction, reducing the cost of production, reducing the dependence on industrial solvents, and / or reducing the environmental impact of the product.

[0272] In some embodiments, the functionalized material is produced on a short time scale in a one-pot reaction using only water as a solvent, reducing the cost of production, reducing the dependence on industrial solvents, and / or reducing the environmental impact of the product.

[0273] In some embodiments, the functionalized material is produced on a short time scale at ambient pressure and temperature (e.g., using an immersion coating process) in a water-based one-pot reaction, reducing the cost of production, reducing the dependence on industrial solvents, and / or reducing the environmental impact of the product.

[0274] In some embodiments, the composition can adsorb atmospheric CO2 (e.g., in an adsorption moiety, e.g., an amine moiety) in a first temperature range and desorb previously adsorbed CO2 (e.g., from an adsorption moiety, e.g., an amine moiety) in a second temperature range higher than the first temperature range. The second temperature range can be in the range of 65 °C to 90 °C.

[0275] In some embodiments, the composition can adsorb atmospheric CO2 (e.g., to an adsorption moiety, e.g., an amine moiety) at a first gas pressure for CO2 and can desorb previously adsorbed CO2 (e.g., from the adsorption moiety, e.g., the amine moiety) at a second gas pressure for CO2 that is lower than the first gas pressure. In some embodiments, the second gas pressure can be less than 1.5 psi (e.g., for functionalized silica or other functionalized materials described herein). In some embodiments, the second gas pressure can be less than 0.3 psi (e.g., for functionalized MOF or other functionalized materials described herein). The first and second gas pressures are related to the pressure for CO2. Thus, when other gases are present proximal to the adsorbent, the first gas pressure and the second gas pressure are related to the partial pressure for CO2.

[0276] In some embodiments, the composition can adsorb atmospheric CO2 (e.g., to an adsorption moiety, e.g., an amine moiety) at a first CO2 concentration and can desorb previously adsorbed CO2 (e.g., from the adsorption moiety, e.g., the amine moiety) at a second CO2 concentration that is lower than the first CO2 concentration. The first CO2 concentration can be less than 420 ppm or less than 400 ppm.

[0277] In some embodiments, the composition can include or consist essentially of porous silica particles as a substrate. The porous silica particles can include a plurality of pores. The plurality of pores can have dimensions (e.g., diameters) in the range of 60 - 400 Å or 20 - 1000 Å. The pores can have sizes in the range of 100 - 150 Å. The plurality of pores can have a volume of greater than 0.5 mL / g. The porous silica particles can have a total surface area of greater than 100 m 2 per dry gram. The porous silica particles can have an average diameter in the range of 25 μm - 3 mm or 25 μm - 4 mm.

[0278] In some embodiments, the porous silica particles have a maximum dimension in the range of 70 - 80 μm. The porous silica particles can include a plurality of pores, and the plurality of pores can have a volume of more than 0.8 mL / g and a size of at least 90 Å.

[0279] In some embodiments, the composition may include or consist essentially of MOF particles as a substrate. The MOF particles can include a plurality of pores. The plurality of pores can have a dimension (e.g., diameter) in the range of 30 - 400 Å. The plurality of pores can have a volume of more than 0.5 mL / g. The MOF particles can have a total surface area of more than 100 m 2 per dry gram. The MOF particles can have an average diameter in the range of 10 μm - 1 mm or 50 - 100 μm.

[0280] In some embodiments, the composition may include or consist essentially of a resin as a substrate. The resin can include a plurality of pores. The plurality of pores can have a dimension (e.g., diameter) in the range of 1 - 200 nm. The plurality of pores can have a volume of more than 0.5 mL / g. The resin can have a total surface area of more than 100 m 2 per dry gram. The resin can have an average diameter in the range of 25 μm - 4 mm.

[0281] In some embodiments, the composition can adsorb 0.5 - 2.5 moles of CO2 per dry kilogram (mol of CO2 / kg), 0.5 - 2 mol of CO2 / kg, or 1 - 2 mol of CO2 / kg. The composition can adsorb CO2 at a relative humidity (RH) in the range of 0% - 100%, 5% - 95%, or 5% - 90% RH (e.g., for functionalized silica or other functionalized materials described herein), or 0% - 100% RH or 5% - 60% RH (e.g., for functionalized MOF, functionalized resin, or other functionalized materials described herein).

[0282] In some embodiments, the adsorbent can be reused via a desorption process. For example, the adsorbent can be reused over 100 times (e.g., over 1000 times, over 10000 times). For the desorption process, the sample can be heated to 70 °C under vacuum for 30 minutes or for another duration (e.g., the duration can vary based on the temperature and / or vacuum level). This can facilitate the release of the CO2 captured during the adsorption process, and the released CO2 can be collected for further sequestration, which is described herein with reference to systems for direct air capture. Non-limiting aspects of the desorption process can include maintaining that the adsorbent is heated under a water vapor-filled vacuum environment (e.g., > 10% RH). In some non-limiting embodiments, this can reduce adsorbent degradation.

[0283] When exposed to a gas mixture containing CO2, the amine moiety (or other adsorption moiety) reacts with CO2 to bind the CO2 to the functional moiety. Thereby, this functionally adsorbs CO2 to the substrate, and the interaction moiety binds the adsorption moiety to the surface of the substrate by covalent or non-covalent interactions. Without wishing to be bound by theory, the total surface area, pore volume, and number of adsorption moieties can determine the adsorption capacity of the functionalized material. The adsorption capacity (e.g., uptake) of the functionalized material can range from 0.1 to 2.5 mol of CO2 / kg of the functionalized material (e.g., 0.1 to 2 mol of CO2 / kg, 0.1 to 1.8 mol of CO2 / kg, 0.1 to 1.5 mol of CO2 / kg, 0.1 to 1.2 mol of CO2 / kg, 0.1 to 1.0 mol of CO2 / kg, 0.1 to 0.5 mol of CO2 / kg, 0.2 to 2 mol of CO2 / kg, 0.2 to 1.0 mol of CO2 / kg, 0.2 to 0.8 mol of CO2 / kg, 0.5 to 2.5 mol of CO2 / kg, 0.5 to 2.2 mol of CO2 / kg, 0.5 to 2 mol of CO2 / kg, 0.5 to 1.8 mol of CO2 / kg, 0.5 to 1.5 mol of CO2 / kg, 0.5 to 0.8 mol of CO2 / kg, 0.8 to 2.5 mol of CO2 / kg, 0.8 to 2.2 mol of CO2 / kg, 0.8 to 2 mol of CO2 / kg, 0.8 to 1.8 mol of CO2 / kg, 0.8 to 1.5 mol of CO2 / kg, 1 to 2 mol of CO2 / kg, 1 to 1.4 mol of CO2 / kg, 1 to 1.5 mol of CO2 / kg, 1.2 to 2.0 mol of CO2 / kg, 1.2 to 1.8 mol of CO2 / kg, 1.5 to 2.5 mol of CO2 / kg, 1.5 to 2 mol of CO2 / kg, or 2 to 2.5 mol of CO2 / kg). In some embodiments, the range is greater than 0.5, 1, 1.5, 2, or 2.5 mol of CO2 / kg. In some implementations, the functionalized material achieves a CO2 adsorption capacity of up to 1 mol of CO2 / kg or up to 2 mol of CO2 / kg at 420 ppm of CO2 under ambient air conditions.

[0284] In some embodiments, the functionalized material (e.g., a functionalized substrate containing polyamine) achieves a CO₂ adsorption capacity in the range of 0.8 - 2.5 mol of CO₂ / kg or 0.5 - 2.2 mol of CO₂ / kg (e.g., 1 - 2 mol of CO₂ / kg, 1 - 1.5 mol of CO₂ / kg, 1.5 - 2 mol of CO₂ / kg, 1.5 - 2.5 mol of CO₂ / kg, or 2 - 2.5 mol of CO₂ / kg). In some embodiments, the functionalized substrate achieves a CO₂ adsorption capacity of up to 2 mol of CO₂ / kg at 420 ppm of CO₂ under ambient air conditions.

[0285] In some embodiments, the functionalized material (e.g., a functionalized substrate containing ethylenediamine, oligomeric ethylenediamine, or a mixture thereof) achieves a CO₂ adsorption capacity in the range of 0.5 - 1.8 mol of CO₂ / kg or 0.5 - 2 mol of CO₂ / kg (e.g., 1.5 - 2 mol of CO₂ / kg, 1.5 - 1.8 mol of CO₂ / kg, 1 - 1.5 mol of CO₂ / kg, or 1.2 - 1.8 mol of CO₂ / kg). In some embodiments, the functionalized substrate achieves a CO₂ adsorption capacity of up to 2 mol of CO₂ / kg at 420 ppm of CO₂ under ambient air conditions.

[0286] In some embodiments, the functionalized material (e.g., a functionalized substrate prepared by an immersion coating process) achieves a CO₂ adsorption capacity in the range of 1 - 2 mol of CO₂ / kg. In some embodiments, the functionalized substrate achieves a CO₂ adsorption capacity of up to 2 mol of CO₂ / kg at 420 ppm of CO₂ under ambient air conditions.

[0287] In some embodiments, the functionalized material (e.g., a functionalized MOF) achieves a CO₂ adsorption capacity in the range of 0.8 - 2.5 mol of CO₂ / kg or 0.1 - 1 mol of CO₂ / kg (e.g., 0.2 - 0.8 mol of CO₂ / kg). In some embodiments, the functionalized MOF substrate achieves a CO₂ adsorption capacity of up to 2 mol of CO₂ / kg at 420 ppm of CO₂ under ambient air conditions.

[0288] In some embodiments, the functionalized material (e.g., functionalized resin) achieves a CO2 adsorption capacity in the range of 0.8 - 2.5 mol of CO2 / kg, 0.8 - 3 mol of CO2 / kg, or 0.1 - 2.0 mol of CO2 / kg (e.g., 0.1 - 1.8 mol of CO2 / kg, 0.1 - 1.5 mol of CO2 / kg, 0.1 - 1.2 mol of CO2 / kg, 0.1 - 1.0 mol of CO2 / kg, 0.1 - 0.5 mol of CO2 / kg, 0.2 - 1.0 mol of CO2 / kg, 0.2 - 0.8 mol of CO2 / kg, 0.5 - 2.0 mol of CO2 / kg, 0.5 - 1.5 mol of CO2 / kg, 0.5 - 0.8 mol of CO2 / kg, 1.2 - 2.0 mol of CO2 / kg, 1.2 - 1.8 mol of CO2 / kg, or any range described herein). In some embodiments, the functionalized resin achieves a CO2 adsorption capacity of up to 2 mol of CO2 / kg at 420 ppm of CO2 under ambient air conditions.

[0289] Under environmental conditions, the atmosphere can contain a certain concentration of water vapor (e.g., humidity). The functionalized material can be used to capture CO2 from atmospheric conditions in the range of RH levels. For example, the functionalized material can capture CO2 from atmospheric conditions in the range of 0% - 100% RH, e.g., 5% - 95% RH (e.g., 15% - 50% RH, 25% - 40% RH, 10% - 60% RH, 5% - 90% RH, 10% - 90% RH, or 20% - 80% RH). In some embodiments, the functionalized material captures CO2 from atmospheric conditions having an RH greater than 60%, greater than 75%, greater than 90%, or greater than 95%.

[0290] vi. Chemical Definitions Unless otherwise specified, the term "material" can be used to encompass compounds, molecules, structures (e.g., substrates or particles), or combinations thereof (e.g., functionalized substrates).

[0291] As used herein, the term "moiety" is used to describe a characteristic portion of an organic molecule, compound, or material. For example, an amine moiety is a molecule, compound, or portion of a compound containing an amine group (e.g., -NR N1 R N2 ) as described herein, and a silane moiety is a molecule, compound, or portion of a compound containing a silane group (e.g., -SiR S1 R S2 R S3 ) as described herein. In a non-limiting example, an amine moiety can include an aminoalkyl group (e.g., -Ak-NR N1 R N2 ) that can be present in an amino silane compound or a polyamine compound. In another non-limiting example, an amine moiety can include an amino group (e.g., -NR N1 R N2 ) alone. The term moiety can be used to describe either a larger molecule containing a group or the group itself.

[0292] As used herein, "interaction" is used to describe a covalent or non-covalent interaction between chemical substances, e.g., by physical adsorption or ionic interaction.

[0293] As used interchangeably herein, "acyl" or "alkanoyl" means an aliphatic or alkyl group as defined herein attached to a parent molecular group via a carbonyl group. In certain embodiments, alkanoyl is -C(O)-Ak, where Ak is an aliphatic or alkyl group as defined herein. In some embodiments, an unsubstituted alkanoyl is a C 2~7 alkanoyl group. Non-limiting examples of alkanoyl groups include acetyl.

[0294] As used interchangeably herein, "acyloxy" or "alkanoyloxy" means an acyl or alkanoyl group as defined herein attached to a parent molecular group via an oxygen group. In certain embodiments, alkanoyloxy is -O-C(O)-Ak, where Ak is an aliphatic or alkyl group as defined herein. In some embodiments, unsubstituted alkanoyloxy is C 2~7 is an alkanoyloxy group. Non-limiting examples of alkanoyloxy groups include acetoxy.

[0295] "Halogenated acyl" means -C(O)X, where X is a halogen, for example, Br, F, I, or Cl.

[0296] "Aliphatic" means a hydrocarbon group having from at least 1 carbon atom to 50 carbon atoms (C 1~50 ), for example, from 1 to 25 carbon atoms (C 1~25 ), or from 1 to 10 carbon atoms (C 1~10 ), including alkanes (or alkyls, such as those described herein), alkenes (or alkenyls), alkynes (or alkynyls), including their cyclic versions, and further including straight-chain and branched-chain configurations, as well as all stereoisomers and positional isomers. Such hydrocarbons may be unsubstituted or may be substituted with one or more groups, such as the groups described herein for alkyl groups.

[0297] "Aliphatic aryl" means an aryl group that is coupled to or can be coupled to a compound disclosed herein, where the aryl group is coupled to or can couple via an aliphatic group as defined herein. In some embodiments, the aliphatic aryl group is -L-R, where L is an aliphatic group as defined herein and R is an aryl group as defined herein.

[0298] "Aliphatic heteroaryl" means a heteroaryl group that is coupled to or can be coupled to a compound disclosed herein, and the heteroaryl group is coupled or can be coupled via an aliphatic group as defined herein. In some embodiments, the aliphatic heteroaryl group is -L-R, where L is an aliphatic group as defined herein and R is a heteroaryl group as defined herein.

[0299] "Alkenyl" means an optionally substituted C having one or more double bonds 2~24 alkyl group. The alkenyl group can be cyclic (e.g., C 3~24 cycloalkenyl) or acyclic. The alkenyl group can also be optionally substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more substituents described herein for alkyl. Non-limiting unsubstituted alkenyl groups include allyl and vinyl. In some embodiments, the unsubstituted alkenyl group is C 2~6 , C 2~8 , C 2~10 , C 2~12 , C 2~16 , C 2~18 , C 2~20 , C 2~24 , C 3~8 , C 3~10 , C 3~12 , C 3~16 , C 3~18 , C 3~20 , or C 3~24 alkenyl group. Non-limiting examples of alkenyl groups include vinyl or ethenyl (-CH=CH2), 1-propenyl (-CH=CHCH3), allyl or 2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CH=CHCH3), 3-butenyl (-CH2CH2CH=CH2), 2-butenylidene (=CH-CH=CHCH3), and the like.

[0300] "Alkenylene" means an optionally substituted C having one or more double bonds 2~24It means a polyvalent (e.g., divalent) form of an alkenyl group that is an alkyl group. An alkylene group can be cyclic (e.g., C 3~24 cycloalkenyl) or acyclic. The alkylene group may be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more substituents described herein for alkyl. Non-limiting examples of alkylene include -CH=CH- or -CH=CHCH2-.

[0301] "Alkoxy" means -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, e.g., trifluoromethoxy, etc. The alkoxy group may be substituted or unsubstituted. For example, the alkoxy group can be substituted with one or more substituents described herein for alkyl. Non-limiting examples of unsubstituted alkoxy include C 1~3 C 1~6 C 1~12 C 1~16 C 1~18 C 1~20 or C 1~24 alkoxy groups.

[0302] "Alkoxyalkyl" means an alkyl group as defined herein substituted with an alkoxy group as defined herein. Non-limiting examples of unsubstituted alkoxyalkyl groups include 2 to 12 carbons (C 2~12 alkoxyalkyl), and those having an alkyl group having 1 to 6 carbons and an alkoxy group having 1 to 6 carbons (i.e., C 1~6 alkoxy-C 1~6 alkyl). In some embodiments, the alkoxyalkyl group is -L-O-R, where L is an alkylene group as defined herein and R is an alkyl group as defined herein.

[0303] "Alkyl" and the prefix "alki" mean a branched or unbranched saturated hydrocarbon group having 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, etc. The alkyl group can be cyclic (e.g., C 3~24 cycloalkyl) or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can be 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., =O), etc. In another example, the alkyl group can be substituted with 1, 2, 3 substituents, or in the case of an alkyl group of 2 or more carbons, 4 substituents, and the substituents are independently, hereinafter, (1) C 1~6 alkoxy (e.g., -O-R, wherein R is C 1~6 alkyl); (2) C 1~6 alkylsulfinyl (e.g., -S(O)-R, wherein R is C 1~6 alkyl); (3) C 1~6 alkylsulfonyl (e.g., -SO2-R, wherein R is C 1~6 alkyl); (4) amine (e.g., -C(O)NR 1 R 2 or -NHCOR 1 , wherein R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2which, together with the nitrogen atom to which each is attached, can form a heterocyclyl group as defined herein); (5) aryl (e.g., C 4~18 aryl); (6) arylalkoxy (e.g., -O-L-R, wherein L is C 1~6 alkylene and R is C 4~18 aryl); (7) aroyl (e.g., -C(O)-R, wherein R is C 4~18 aryl); (8) azide (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C 3~8 cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -O-R, wherein R is a heterocyclyl as defined herein); (15) heterocyclylcarbonyl (e.g., -C(O)-R, wherein R is a heterocyclyl as defined herein); (16) hydroxy (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =O); (20) C 1~6 thioalkoxy (e.g., -S-R, wherein R is alkyl); (21) thiol (e.g., -SH); (22) -CO2R 1 [wherein R 1 is selected from the group consisting of (a) hydrogen, (b) C 1~6 alkyl, (c) C 4~18 aryl, and (d) C 1~6 alkyl-C 4~18 aryl (e.g., -L-R, wherein L is C 1~6 alkylene and R is C 4~18 aryl); (23) -C(O)NR 1 R 2 [wherein each of R 1 and R 2 is independently selected from the group consisting of (a) hydrogen, (b) C 1~6 alkyl, (c) C 4~18 aryl, and (d) C 1~6 alkyl-C4~18 Aryl (for example, -L-R, where L is C 1~6 alkylene and R is C 4~18 aryl) selected from the group consisting of]; (24) -SO2R 1 [wherein R 1 is (a) C 1~6 alkyl, (b) C 4~18 aryl, and (c) C 1~6 alkyl-C 4~18 aryl (for example, -L-R, where L is C 1~6 alkylene and R is C 4~18 aryl) selected from the group consisting of]; (25) -SO2NR 1 R 2 [wherein R 1 and R 2 each independently is (a) hydrogen, (b) C 1~6 alkyl, (c) C 4~18 aryl, and (d) C 1~6 alkyl-C 4~18 aryl (for example, -L-R, where L is C 1~6 alkylene and R is C 4~18 aryl) selected from the group consisting of]; and (26) -NR 1 R 2 [wherein R 1 and R 2 each independently is (a) hydrogen, (b) an N-protecting group, (c) C 1~6 alkyl, (d) C 2~6 alkenyl, (e) C 2~6 alkynyl, (f) C 4~18 aryl, (g) C 1~6 alkyl-C 4~18 aryl (for example, -L-R, where L is C 1~6 alkylene and R is C 4~18 aryl), (h) C 3~8 cycloalkyl, and (i) C 1~6 alkyl-C 3~8 cycloalkyl (for example, -L-R, where L is C 1~6 alkylene and R is C 3~8selected from the group consisting of) cycloalkyl), and in one embodiment, the two groups are not bonded to the nitrogen atom via a carbonyl or sulfonyl group. The alkyl group can be 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 C 1~3 , C 1~4 , C 1~6 , C 1~8 , C 1~10 , C 1~12 , C 1~16 , C 1~18 , C 1~20 , C 1~24 , C 2~6 , C 2~8 , C 2~10 , C 2~12 , C 2~16 , C 2~18 , C 2~20 , C 2~24 , C 3~8 , C 3~10 , C 3~12 , C 3~16 , C 3~18 , C 3~20 , or C 3~24 alkyl group.

[0304] "Alkylene" means the polyvalent (e.g., divalent) form of an aliphatic or alkyl group as described herein. Non-limiting examples of alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, the alkylene group is C 1~3 , C 1~4 , C 1~6 , C 1~12 , C 1~16 , C 1~18 , C 1~20 , C 1~24 , C 2~3 , C 2~6 , C 2~12 , C 2~16 , C 2~18 , C 2~20 , or C 2~24It is an alkylene group. The alkylene group can be branched or unbranched. The alkylene group may also be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more substituents described herein for alkyl.

[0305] As used herein, the term "alkylsilyl" refers to a -SiR 1 R 2 R 3 group, wherein R 1 is optionally substituted alkyl, and each of R 2 and R 3 is independently selected from H and optionally substituted alkyl. Alkylsilyl includes mono, bis, and trisalkylsilyl. Examples of alkylsilyl include trimethylsilyl, dimethylsilyl, methylsilyl, triethylsilyl, diethylsilyl, ethylsilyl, and the like.

[0306] "Alkylsulfinyl" means an alkyl group as defined herein attached to the parent molecular group via an -S(O)- group. In some embodiments, the unsubstituted alkylsulfinyl group is a C 1~6 or C 1~12 alkylsulfinyl group. In other embodiments, the alkylsulfinyl group is -S(O)-R, wherein R is an alkyl group as defined herein.

[0307] "Alkylsulfinylalkyl" means an alkyl group as defined herein substituted with an alkylsulfinyl group. In some embodiments, the unsubstituted alkylsulfinylalkyl group is a C 2~12 or C 2~24 alkylsulfinylalkyl group (e.g., C 1~6 alkylsulfinyl-C 1~6 alkyl or C 1~12 alkylsulfinyl-C 1~12(alkyl). In other embodiments, the alkylsulfinylalkyl group is -L-S(O)-R, where L is an alkylene as defined herein and R is an alkyl group as defined herein.

[0308] "Alkylsulfonyl" means an alkyl group as defined herein attached to the parent molecular group via an -SO2- group. In some embodiments, the unsubstituted alkylsulfonyl group is C 1~6 or C 1~12 alkylsulfonyl group. In other embodiments, the alkylsulfonyl group is -SO2-R, where R is optionally substituted alkyl (e.g., optionally substituted C 1~12 alkyl, haloalkyl, or perfluoroalkyl as described herein).

[0309] "Alkylsulfonylalkyl" means an alkyl group as defined herein substituted by an alkylsulfonyl group. In some embodiments, the unsubstituted alkylsulfonylalkyl group is C 2~12 or C 2~24 alkylsulfonylalkyl group (e.g., C 1~6 alkylsulfonyl-C 1~6 alkyl or C 1~12 alkylsulfonyl-C 1~12 alkyl). In other embodiments, the alkylsulfonylalkyl group is -L-SO2-R, where L is an alkylene as defined herein and R is an alkyl group as defined herein.

[0310] "Alkynyl" means an optionally substituted C 2~24 alkyl group having one or more triple bonds. The alkynyl group can be cyclic or acyclic and is exemplified by ethynyl, 1-propynyl, etc. The alkynyl group can also be optionally substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substituents described herein for alkyl. A non-limiting unsubstituted alkynyl group is C 2~8Alkynyl, C 2~6 Alkynyl, C 2~5 Alkynyl, C 2~4 Alkynyl, or C 2~3 contains 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 (-CH2CH2C≡CH), and the like. In some embodiments, the unsubstituted alkynyl group is C 2~6 , C 2~8 , C 2~10 , C 2~12 , C 2~16 , C 2~18 , C 2~20 , C 2~24 , C 3~8 , C 3~10 , C 3~12 , C 3~16 , C 3~18 , C 3~20 , or C 3~24 is an alkynyl group.

[0311] "Alkynylene" means an optionally substituted C 2~24 alkyl group having one or more triple bonds, the polyvalent (e.g., divalent) form of an alkynyl group. The alkynylene group can be cyclic or acyclic. The alkynylene group may be substituted or unsubstituted. For example, the alkynylene group can be substituted with one or more substituents described herein for alkyl. Non-limiting examples of alkynylene groups include -C≡C- or -C≡CCH2-.

[0312] "Amide" means -C(O)NR 1 R 2 or -NHCOR 1 , wherein each of R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R2 can, together with the nitrogen atom to which each is attached, form a heterocyclyl group as defined herein.

[0313] "Amine" or "amino" means -NR N1 R N2 group, -NR N1 - group, or a compound having such a group, wherein R N1 and R N2 each independently is H, optionally substituted aliphatic, alkyl, hydroxyalkyl, heteroaliphatic, heteroalkyl, aromatic, or aryl, or R N1 and R N2 together with the nitrogen atom to which each is attached, form a heterocyclyl group as defined herein.

[0314] "Aminoalkyl" means an aliphatic or alkyl group as described herein substituted with one, two, three, or more amine groups. Aminoalkyl can include internal or terminal amine groups. The aminoalkyl group can be further substituted. For example, the aminoalkyl group can be substituted with one or more substituents as described herein for alkyl. Non-limiting examples of unsubstituted aminoalkyl groups include C 1~3 、C 1~6 、C 1~12 、C 1~16 、C 1~18 、C 1~20 、or C 1~24 aminoalkyl groups. In some embodiments, the aminoalkyl group is -L-NR 1 R 2 wherein L is an aliphatic or alkylene group as defined herein and each of R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2can, together with the nitrogen atom to which each is attached, form a heterocyclyl group as defined herein. In other embodiments, the aminoalkyl group is -L-C(NR 1 R 2 )(R 3 )-R 4 , wherein L is a covalent bond, an aliphatic group, or an alkylene group as defined herein, and each of R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 can, together with the nitrogen atom to which each is attached, form a heterocyclyl group as defined herein, and each of R 3 and R 4 is independently H or alkyl as defined herein.

[0315] "Aminoaryl" means an aromatic or aryl group as defined herein substituted by an amino group as defined herein.

[0316] "Aromatic" means, unless otherwise specified, a cyclic conjugated group or moiety of 5 to 15 ring atoms, wherein the cyclic conjugated group or moiety has a single ring (e.g., phenyl), or has a plurality of fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl), i.e., means a cyclic conjugated group or moiety in which at least one ring and optionally a plurality of fused rings have a continuous delocalized π electron system. Typically, the number of out-of-plane π electrons corresponds to the Hückel rule (4n + 2). The point of attachment to the parent structure typically passes through the aromatic portion of the fused ring system.

[0317] "Aryl" means at least 5 carbon atoms to 15 carbon atoms (C 5~15 ), e.g., 5 to 10 carbon atoms (C 5~10An aromatic carbocyclic group that contains ) and has a single ring or multiple fused rings, where the fused rings may or may not be aromatic, provided that the attachment points to the remaining positions of the compounds disclosed herein are via the atoms of the aromatic carbocyclic group. An aryl group can be substituted with one or more groups other than hydrogen, such as alkyl, and any of the substituents described herein for alkyl. Non-limiting examples of aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, etc. The term "aryl" also includes heteroaryl, which is defined as a group containing an aromatic group, where the aromatic group 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. Similarly, the term "non-heteroaryl", which is also included in the term "aryl", defines a group containing an aromatic group that does not contain a heteroatom. An aryl group can be substituted with 1, 2, 3, 4, or 5 substituents provided herein for alkyl. In certain embodiments, the unsubstituted aryl group is a C 4~18 C 4~14 C 4~12 C 4~10 C 6~18 C 6~14 C 6~12 C 6~10 aryl group.

[0318] "Arylene" means a polyvalent (e.g., divalent) form of an aromatic or aryl group described herein. Non-limiting examples of arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is a C 4~18 C 4~14 C 4~12 C 4~10 C 6~18 C 6~14 C 6~12 C 6~10It is an arylene group. The arylene group can be branched or unbranched. The arylene group may also be substituted or unsubstituted. For example, the arylene group can be substituted with one or more substituents described herein for alkyl or aryl.

[0319] "Aryloxy" means -OR, wherein R is an optionally substituted aromatic or aryl group as described herein. In some embodiments, the unsubstituted aryloxy group is C 4~18 or C 6~18 aryloxy group.

[0320] "Arylalkoxy" means an alkylaryl group as defined herein attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy group is -O-L-R, wherein L is an alkylene group as defined herein and R is an aryl group as defined herein.

[0321] "Aryloxycarbonyl" means an aryloxy group as defined herein attached to the parent molecular group through a carbonyl group. In some embodiments, the unsubstituted aryloxycarbonyl group is C 5~19 aryloxycarbonyl group. In other embodiments, the aryloxycarbonyl group is -C(O)O-R, wherein R is an aryl group as defined herein.

[0322] "Aroyl" means an aryl group attached to the parent molecular group through a carbonyl group. In some embodiments, the unsubstituted aroyl group is C 7~11 aroyl group or C 5~19 aroyl group. In other embodiments, the aroyl group is -C(O)-R, wherein R is an aryl group as defined herein.

[0323] "(Aryl)(alkyl)ene" means a divalent form containing an arylene group as described herein attached to an alkylene or heteroalkylene group. In some embodiments, the (aryl)(alkyl)ene group is -L-Ar-, or -L-Ar-L-, or -Ar-L-, where Ar is an aromatic or arylene group and each L is independently an optionally substituted aliphatic, alkylene group, heteroaliphatic, or heteroalkylene group.

[0324] "Borono" means a -B(OH)2 group.

[0325] "Carbonyl" means a -C(O)- group, which may also be represented as >C=O or -CO-.

[0326] "Carboxyl" or "carboxylic acid" means a -CO2H group or a compound containing such a group, including deprotonated and protonated forms.

[0327] "Carboxyalkyl" means an alkyl group as defined herein substituted by one or more carboxyl groups as defined herein.

[0328] "Carboxyaryl" means an aryl group as defined herein substituted by one or more carboxyl groups as defined herein.

[0329] "Cycloaliphatic" means a cyclic aliphatic group as defined herein.

[0330] "Cycloalkoxy" means a cycloalkyl group as defined herein attached to a parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -O-R, where R is a cycloalkyl group as defined herein.

[0331] "Cycloalkylalkoxy" means an alkylcycloalkyl group as defined herein attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkylalkoxy group is -O-L-R, where L is an alkylene group as defined herein and R is a cycloalkyl group as defined herein.

[0332] "Cycloalkyl", unless otherwise specified, means a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of 3 to 8 carbons, exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, etc. The cycloalkyl group may also be substituted or unsubstituted. For example, the cycloalkyl group may be substituted with one or more groups including those described herein for alkyl.

[0333] "Cycloheteroaliphatic" means a heteroaliphatic group as defined herein that is cyclic.

[0334] "Disulfide" means -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof.

[0335] "Halo" means F, Cl, Br, or I.

[0336] "Haloaliphatic" means an aliphatic group as defined herein substituted with one or more halos.

[0337] "Haloalkyl" means an alkyl group as defined herein substituted with one or more halos.

[0338] "Haloalkenyl" means an alkenyl group as defined herein substituted with one or more halos.

[0339] "Haloalkynyl" means an alkynyl group as defined herein that is substituted with one or more halos.

[0340] "Haloalkylene" means an alkylene group as defined herein that is substituted with one or more halos.

[0341] "Haloheteroaliphatic" means a heteroaliphatic as defined herein in which one or more hydrogen atoms, for example, from 1 to 10 hydrogen atoms, are independently replaced by halogen atoms, for example, fluoro, bromo, chloro, or iodo.

[0342] "Heteroaliphatic" means an aliphatic group as defined herein that contains from at least 1 heteroatom to 20 heteroatoms, for example, from 1 to 15 heteroatoms, or from 1 to 5 heteroatoms, wherein the heteroatoms can be selected from, but are not limited to, boron, halo, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and, where applicable, their oxidized forms within the group.

[0343] "Heteroalkyl", "heteroalkenyl", and "heteroalkynyl" each mean an alkyl, alkenyl, or alkynyl group (which can be branched, straight-chain, or cyclic) as defined herein that contains from at least 1 heteroatom to 20 heteroatoms, for example, from 1 to 15 heteroatoms, or from 1 to 5 heteroatoms, wherein the heteroatoms can be selected from, but are not limited to, boron, halo, nitrogen (for example, as present in an imino), oxygen, phosphorus, selenium, silicon, sulfur, and, where applicable, their oxidized forms within the group.

[0344] "Heteroalkylene" means the polyvalent (e.g., divalent) form of a heteroaliphatic or heteroalkyl group as described herein. The heteroalkylene group may or may not be substituted. For example, the heteroalkylene group can be substituted with one or more substituents as described herein for alkyl.

[0345] "Heteroalkenylene" means a polyvalent (e.g., divalent) form of a heteroalkenyl group that is an optionally substituted heteroalkyl group having one or more double bonds. The heteroalkenylene group can be cyclic or acyclic. The heteroalkenylene group may be substituted or unsubstituted. For example, the heteroalkenylene group can be substituted with one or more of the substituents described herein for alkyl.

[0346] "Heteroalkynylene" means a polyvalent (e.g., divalent) form of a heteroalkynyl group that is an optionally substituted heteroalkyl group having one or more triple bonds. The heteroalkynylene group can be cyclic or acyclic. The heteroalkynylene group may be substituted or unsubstituted. For example, the heteroalkynylene group can be substituted with one or more of the substituents described herein for alkyl.

[0347] "Heteroaromatic" means an aromatic group as defined herein that contains at least 1 to 20 heteroatoms, such as 1 to 15 heteroatoms, or 1 to 5 heteroatoms, where the heteroatoms can be selected from, but are not limited to, boron, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and their oxidized forms within the group.

[0348] "Heteroaryl" means an aryl group containing at least 1 to 6 heteroatoms, for example, 1 to 4 heteroatoms, where the heteroatoms can be selected from boron, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and their oxidized forms within the ring, but are not limited thereto. Such a heteroaryl group can have a single ring or multiple fused rings, and the fused rings can be aromatic, non-aromatic, or contain heteroatoms, provided that the point of attachment is through an atom of an aromatic heteroaryl group. The heteroaryl group can be substituted with one or more groups other than hydrogen, for example, alkyl and any of the substituents described herein for alkyl. Non-limiting examples of heteroaryl include a subset of the heterocyclyl groups defined herein that are aromatic, i.e., a subset of heterocyclyl groups containing 4n + 2 pi electrons in a monocyclic or polycyclic ring system.

[0349] "Heteroarylene" means the polyvalent (e.g., divalent) form of a heteroaromatic or heteroaryl group described herein. Non-limiting examples of heteroarylene groups include pyridinylene and the like. In some embodiments, the heteroarylene group is a C 4~18 、C 4~14 、C 4~12 、C 4~10 、C 6~18 、C 6~14 、C 6~12 、or C 6~10 heteroarylene group. The heteroarylene group can be branched or unbranched. The heteroarylene group can also be substituted or unsubstituted. For example, the heteroarylene group can be substituted with one or more of the substituents described herein for alkyl or aryl.

[0350] "Heterocyclyl", unless otherwise specified, means a 3-, 4-, 5-, 6-, or 7-membered ring (e.g., 5-, 6-, or 7-membered ring) containing 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, selenium, silicon, or sulfur). The 3-membered ring has 0 to 1 double bond, the 4- and 5-membered rings have 0 to 2 double bonds, and the 6- and 7-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, tetracyclic, or other polycyclic groups. Heterocycles include acridinyl, adenyl, alloxazinyl, azadamantanyl, benzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl, benzodioxocinyl, benzodioxolyl, benzodithiepinyl, benzodithinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzquinolinyl, benzquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiadinonyl, benzothiadinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl, benzoxadiazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsulfamyl, benzylsulfthiamyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbonyl (e.g., β-carbonyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl,Cytosinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diazirinonyl, 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, dioxyindolyl, dioxolanyl, dioxenyl, dioxinyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithinyl, furanyl, furazanyl, furoyl, furyl, guanylinyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indolenyl, indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazolyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidinyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthylindazolyl, naphthylindolyl, naphthyridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxyindolyl, naphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidinonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanonyl, oxetanyl, oxetyl, oxytenail, oxyindolyl, oxolanylOxobenzisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidizinyl, 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, pyrrolidizinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrilium, quinazolinyl, quinolinyl, quinolidinyl (e.g., 4H-quinolidinyl), quinoxalinyl, quinuclidinyl, selenadininyl, 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-1,5,2-dithiadiazinyl, thiadiazolyl, thianthrenyl, thianyl, thianaphthalenyl, thiazepinyl, thiadazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thietyl, thiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiadiazinyl, thiadiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, urethidinyl, urethinyl, uracil, uridinyl, xanthenyl, xanthinyl, xanthionyl, etc., and their modified forms (e.g.,Those containing one or more oxo and / or amino and their salts are included. The heterocyclyl group may be substituted or unsubstituted. For example, the heterocyclyl group may be substituted with one or more substituents described herein for alkyl.

[0351] "Heterocyclyloxy" means a heterocyclyl group as defined herein attached to the parent molecular group via an oxygen atom. In some embodiments, the heterocyclyloxy group is -O-R, where R is a heterocyclyl group as defined herein.

[0352] "Heterocyclylcarbonyl" means a heterocyclyl group as defined herein attached to the parent molecular group via a carbonyl group. In some embodiments, the heterocyclylcarbonyl group is -C(O)-R, where R is a heterocyclyl group as defined herein.

[0353] "Hydroxy" means -OH.

[0354] "Hydroxyalkyl" means an alkyl group as defined herein substituted by 1 to 3 hydroxy groups, provided that no more than 1 hydroxy group can be attached to a single carbon atom of the alkyl group, and is exemplified by hydroxymethyl, dihydroxypropyl, etc.

[0355] "Hydroxyaryl" means an aryl group as defined herein substituted by 1 to 3 hydroxy groups, provided that no more than 1 hydroxy group can be attached to a single carbon atom of the aryl group, and is exemplified by hydroxyphenyl, dihydroxyphenyl, etc.

[0356] "Imide" means =NR group, where R is selected from H, aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, or aryl as defined herein, or any combination thereof.

[0357] "Imino" means -NR-, where R can be H, optionally substituted aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, or aryl.

[0358] "Nitro" means a -NO2 group.

[0359] "Nitroalkyl" means an alkyl group as defined herein substituted with one to three nitro groups. In some embodiments, the nitroalkyl group is -L-NO, where L is an alkylene group as defined herein. In other embodiments, the nitroalkyl group is -L-C(NO)(R 1 )-R 2 where L is a covalent bond or an alkylene group as defined herein, and each of R 1 and R 2 is independently H or alkyl as defined herein.

[0360] "Oxo" or "oxide" means a =O group.

[0361] "Oxy" means -O-.

[0362] "Phosphono" or "phosphonic acid" means a -P(O)(OH)2 group or a compound containing such a group, including deprotonated and protonated forms.

[0363] "Perfluoroalkyl" means an alkyl group as defined herein having each hydrogen atom substituted with a fluorine atom. Non-limiting examples of perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2) n CF3, where n is an integer in the range of 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.

[0364] "Perfluoroalkoxy" means an alkoxy group as defined herein having each hydrogen atom substituted with a fluorine atom. In some embodiments, the perfluoroalkoxy group is -O-R, where R is a perfluoroalkyl group as defined herein.

[0365] "Salt" means an ionic form of a compound or structure (e.g., any of the formulas, compounds, or compositions described herein) that includes a cationic or anionic compound for forming 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 "Handbook of Pharmaceutical Salts: Properties, Selection, and Use," Wiley-VCH, April 2011 (2nd rev. ed., eds. P.H. Stahl and C.G. Wermuth). Salts may be prepared during the final isolation and purification of the compounds of the invention in situ, or separately, by reacting the free base with a suitable organic acid (thereby producing an anionic salt), or by reacting an acid group with a suitable metal or organic salt (thereby producing a cationic salt).Representative anion 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, methyl bromide salt, methyl nitrate salt, methyl sulfate salt, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, basic acetate, succinate, sulfate, tannate, tartrate, theophyllinate salt, thiocyanate, triethiodide salt, toluenesulfonate, undecanoate, valerate, etc. Representative cation salts include metal salts, such as alkali or alkaline earth salts, such as barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, etc.; other metal salts, such as aluminum, bismuth, iron, and zinc; and ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, etc., including, but not limited to, non-toxic ammonium, quaternary ammonium, and amine cations. Other cation salts include organic salts, such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine.Other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphaziniium, phosphazenium, pyridinium, etc., and 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 indolidinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinum, optionally substituted quinolidinium, optionally substituted dehydroquinolidinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0366] "Silane" means -SiR S1 R S2 R S3 ,-SiRS1 R S2 - or a compound having such a group, wherein R S1 , R S2 , and R S3 each independently is H, optionally substituted aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, aryl, amine, or other as described herein, or R S1 and R S2 together with the silicon atom to which each is attached form a heterocyclyl group.

[0367] "Silyl ether" means a functional group containing a silicon atom covalently bonded to an alkoxy group as defined herein. In some embodiments, the silyl ether is -Si-O-R or Si-O-R, wherein R is an alkyl group as defined herein.

[0368] "Sulfinyl" means a -S(O)- group.

[0369] "Sulfo" or "sulfonic acid" means a -S(O)2OH group or a compound containing such a group, including the deprotonated and protonated forms.

[0370] "Sulfonyl" or "sulfonate" means a -S(O)2- group or -SO2R, wherein R is selected from hydrogen, aliphatic, alkyl, heteroaliphatic, heteroalkyl, haloaliphatic, haloheteroaliphatic, aromatic, aryl, or any combination thereof as defined herein.

[0371] "Thio" means -S-.

[0372] "Thiol" means a -SH group.

[0373] "Thioalkoxy" means an alkyl group as defined herein attached to a parent molecular group via a sulfur atom. Non-limiting examples of unsubstituted thioalkoxy groups include C 1~6Thioalkoxy is included. In some embodiments, the thioalkoxy group is -S-R, where R is an aliphatic or alkyl group as defined herein.

[0374] "Thioalkoxyalkyl" means an alkyl group as defined herein substituted with a thioalkoxy group as defined herein. Non-limiting examples of unsubstituted thioalkoxyalkyl groups include those having 2 to 12 carbons (C 2~12 thioalkoxyalkyl), as well as those having an alkyl group having 1 to 6 carbons and a thioalkoxy group having 1 to 6 carbons (i.e., C 1~6 thioalkoxy-C 1~6 alkyl). In some embodiments, the thioalkoxyalkyl group is -L-S-R, where L is an alkylene as defined herein and R is an alkyl group as defined herein.

[0375] II. Method for Forming Functionalized Materials The functionalized material can be prepared in any useful manner. In some embodiments, a functionalization mixture is prepared, which mixture includes a substrate, a solvent, and one or more compounds for providing a functional moiety. 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 certain embodiments, at least one compound includes both an amine moiety and a silane moiety.

[0376] The functionalization mixture can be prepared in any useful manner. In a non-limiting example, a suspension mixture including a substrate and a solvent can be prepared. To this suspension mixture, a compound (for providing a functional moiety) can be added to provide a functionalization mixture. Non-limiting examples of the compound include silane coupling materials, aminosilanes, polyamines, or any combination of these compounds. In some embodiments, the functionalization is carried out using solution-based reaction conditions.

[0377] Various methods can be used to provide the functionalized materials described herein. In some embodiments, the functionalized material (e.g., functionalized porous silica) can be produced using a solution-based reaction method, in which an aminosilane compound (e.g., a compound having an amine moiety and a silane moiety) is solvated and a substrate is added. The silane moiety binds to the surface and the amine moiety extends from the silane moiety. The functionalized substrate can be filtered from the solvent, washed, and subjected to drying. Such methods (e.g., the processes in FIGS. 5A, 5B, and 5E) can provide any of the functionalized materials described herein (e.g., the functionalized materials 100A-100C in FIGS. 1A-1C).

[0378] In some embodiments, a pre-functionalized material (e.g., functionalized porous silica) can be produced using a solution-based reaction method, in which a silane-containing compound (e.g., an aminosilane compound having an amine moiety and a silane moiety) is solvated and a substrate is added. The silane moiety (e.g., an alkoxysilane moiety) binds to the surface and the amine moiety extends from the silane moiety. The pre-functionalized substrate can be filtered from the solvent, washed, and subjected to drying. A polymer / oligomer amine compound can be solvated and the pre-functionalized substrate can be added. The mixture can be stirred and then subjected to drying, thereby functionalizing the substrate with both the silane-containing compound and the polymer / oligomer amine. Such methods (e.g., the processes in FIGS. 5B and 5E) can provide any of the functionalized materials described herein (e.g., the functionalized materials 100A-100C in FIGS. 1A-1C).

[0379] In some embodiments, the functionalized material (e.g., functionalized porous silica) can be produced using an aqueous-based reaction method, in which a polyamine (e.g., a compound having multiple amine moieties) and an aminosilane compound (e.g., a compound having an amine moiety and a silane moiety) are solvated in water and a substrate is added. The polyamine and the aminosilane compound react to form a composite network, which then binds to the surface of the substrate. The resulting material can be filtered from water, optionally washed, and subjected to drying. Such a method (e.g., the process in FIG. 5F) can provide any of the functionalized materials described herein (e.g., the functionalized materials 100A-100C in FIGS. 1A-1C).

[0380] In some embodiments, the functionalized material (e.g., functionalized porous silica) can be produced using a solvent-based reaction method, in which a polyamine (e.g., a compound having multiple amine moieties) is solvated and a substrate is added. In some embodiments, the polyamine has an increased number of amine moieties for increased carbon capture (e.g., greater than 2 mol / kg) in the functionalized material. The resulting material can be stirred, optionally filtered, optionally washed, and subjected to drying. Such a method (e.g., the process in FIG. 5G) can provide any of the functionalized materials described herein (e.g., the functionalized materials 100A-100C in FIGS. 1A-1C).

[0381] In some embodiments, a functionalized material (e.g., a functionalized porous silica) can be produced using a solvent-based reaction method, in which an oligomeric ethyleneamine compound (e.g., a compound having multiple ethylene groups and amine moieties, and mixtures of such compounds including any of those described herein) is solvated and a substrate is added. In some embodiments, the oligomeric ethyleneamine compound or mixture thereof has an increased number of amine moieties for increased carbon capture (e.g., greater than 1 mol / kg) in the functionalized material. The resulting material can be stirred, optionally filtered, optionally washed, and subjected to drying. Such methods (e.g., the process in FIG. 5H) can provide any of the functionalized materials described herein (e.g., the functionalized materials 100A - 100C in FIGS. 1A - 1C).

[0382] In some embodiments, a functionalized material (e.g., a functionalized MOF) can be produced using a reactor-based solvothermal (e.g., hydrothermal) synthesis method, in which a metal source, a ligand, and a competitor react together to form a substrate, and then an aminosilane is solvated in a solvent medium and provided to the substrate. The silane moiety reacts with the hydroxy groups on the surface of the MOF, and the amine moiety extends from the silane moiety. The powder can be filtered from the solvent, washed, and subjected to drying. Such methods (e.g., the process in FIG. 5C) can provide any of the functionalized materials described herein (e.g., the functionalized materials 100A - 100C in FIGS. 1A - 1C).

[0383] In some embodiments, a functionalized material (e.g., a functionalized resin) can be produced using solution-based reaction conditions in which an amine (e.g., a compound having one, two, or more amine moieties which can include a polyamine) is solvated and a resin is added. The amine moiety interacts with reactive sites present on the surface of the resin (e.g., binds to acidic reactive sites), thereby providing a functionalized resin having an adsorbed moiety (e.g., an amine moiety). The functionalized resin can be purified, subjected to drying, and optionally, activated. Such a method (e.g., the process in FIG. 5D) can provide any of the functionalized materials described herein (e.g., the functionalized materials 100A-100C in FIGS. 1A-1C).

[0384] For any substrate in this specification and in some non-limiting embodiments, an aminosilane compound having a longer carbon chain length and a high amino group density can be used to increase the carbon capture potential, and an additional silane moiety can increase the binding strength of the silane-amine compound to the surface of the substrate. This can produce a functionalized material capable of a high carbon dioxide capture capacity even at low CO2 concentrations, e.g., direct air capture.

[0385] Desorption can be carried out at laboratory temperature (e.g., above 70 °C) and below 0.3 psi, whereby the functionalized material is reintroduced into the gas mixture containing carbon dioxide to allow repeated re-capture. In some implementations, a high adsorption / desorption cycle count is achieved (e.g., more than 100 cycles or more than 1000 cycles).

[0386] In other embodiments, the functionalized material can be produced by using at least two compounds. For example, without limitation, a first layer of covalently bonded silane can enable further surface modification of the substrate for binding a polymer / oligomer amine compound with increased stability. In some embodiments, the first compound can be a silane or an aminosilane, and the second compound can be a polymer / oligomer amine, such as polyethyleneimine (PEI), having an increased number of amine moieties for increased carbon capture (e.g., greater than 2 mol of CO2 / kg). The functionalized porous material can be produced using a solution-based reaction method in which a silane-containing compound is solvated and a substrate (e.g., silica powder) can be added. The silane moiety covalently bonds to the surface of the substrate where the amine moieties extend. The pre-functionalized powder can be filtered from the solvent, washed, and subjected to drying.

[0387] The polymer / oligomer amine compound can then be solvated, and the pre-functionalized powder can be added to form a functionalized mixture. The mixture can be agitated and then subjected to drying to functionalize the substrate with both the silane-containing compound and the polymer / oligomer amine. Desorption can be carried out at laboratory temperature (e.g., greater than 70 °C), thereby reintroducing the functionalized porous material to carbon dioxide to enable re-capture. High adsorption / desorption cycle counts can be achieved (e.g., greater than 100 cycles). In some embodiments, the adsorbent achieves a CO2 uptake of up to 1.5 - 1.8 mol of CO2 / kg or 0.5 - 1.8 mol of CO2 / kg under ambient air conditions of 420 ppm of CO2. Such a method (e.g., the process in FIGS. 5B, 5E, or 5H) can provide any of the functionalized materials described herein (e.g., the functionalized material 100A in FIG. 1A or the functionalized material 100C in FIG. 1C).

[0388] After functionalization, the resulting material can be further purified, subjected to drying, and / or activated. Activation can include any process for removing residual solvents within the functionalized material. Activation can include the use of heat, heated air, vacuum heating, etc. (e.g., to a temperature of about 70 °C).

[0389] i. Functionalization The method herein can include forming a suspension mixture that includes a substrate and a solvent medium. The solvent medium can include one or more solvents. Then, a compound (for providing a functional moiety) can be included in the suspension mixture, thereby forming a functionalized material.

[0390] Any useful reagent or compound can be used to provide a functional moiety to the substrate. Non-limiting reagents and compounds include silane coupling materials (e.g., aminosilanes), multiple silane coupling materials (e.g., multiple aminosilanes), polyamines, multiple polyamines, monoamines, multiple monoamines, silane coupling materials (e.g., aminosilanes) in combination with an amine compound (e.g., a polyamine or a monoamine), polyamines in combination with a monoamine, etc. Such reagents and compounds can be provided in a single solution (e.g., a single suspension mixture) or in separate solutions (e.g., separate suspension mixtures).

[0391] In some embodiments, the suspension mixture can include reagents that can react to form a substrate. For example, without limitation, the method herein can include forming a suspension mixture that includes one or more reagents to provide a substrate and a solvent medium. The solvent medium can include one or more solvents. Then, a compound (for providing a functional moiety) can be included in the suspension mixture, thereby forming a functionalized material.

[0392] In some embodiments, the methods herein can include forming a functionalized mixture that includes a solvent medium and at least one compound for providing a functional moiety. In some embodiments, the functionalized mixture can include additional components (e.g., a substrate), and the additional components can then provide a functionalized material.

[0393] In other embodiments, the methods herein can include forming a pre-functionalized mixture that includes a first solvent medium and a first compound to provide a portion of the functional moiety (e.g., thereby providing a pre-functionalized material), and then forming a functionalized mixture that includes one or more components from the pre-functionalized mixture and a second solvent medium. In some embodiments, the pre-functionalized mixture can include additional components (e.g., a substrate), and the additional components can then provide a pre-functionalized material, the functionalized mixture can include additional components (e.g., a substrate or a pre-functionalized substrate), and the additional components can then provide a functionalized material. In any of the embodiments herein, the pre-functionalized mixture can provide a pre-functionalized material (e.g., optionally further reactive), and the functionalized mixture can provide a functionalized material.

[0394] Optionally, the suspension mixture, pre-functionalized mixture, and / or functionalized mixture can be formed by a stirring method that minimizes changes in particle size or distribution or minimizes particle breakdown. Non-limiting stirring methods can include overhead stirring.

[0395] Any useful solvent can be used in the mixture (e.g., suspension mixture, pre-functionalized mixture, or functionalized mixture). In some embodiments, the solvent is an organic solvent that dissolves the compound for providing the functional moiety. In some embodiments, the solvent does not hydrolyze the siloxane bond. In some examples, the solvent medium is a neutral aprotic organic solvent (e.g., toluene, hexane, cyclohexane, or tetrahydrofuran (THF)) or a mixture of these solvents. In some embodiments, the solvent medium can include methanol, cyclohexane, ethanol, water, or a mixture of these solvents. In some embodiments, the liquid can include cyclohexane and ethanol in a mixture ratio in the range of 1:1 to 5:1 by volume.

[0396] In some embodiments, one or more solvents having a boiling point in the range of 50° to 100°C may be desirable.

[0397] In some embodiments, the amount of the solvent medium (e.g., in the suspension mixture, pre-functionalized mixture, or functionalized mixture) can be minimized. For example, without limitation, the solvent medium can be dispensed such that it entirely covers the substrate in the vessel, e.g., by dispensing a solvent medium in an amount greater than 0.5 mL / g (e.g., 1 mL / g, 2 mL / g, 5 mL / g, 8 mL / g, 10 mL / g, or 15 mL / g, or in the range of 0.5 to 10 mL / g, 0.5 to 5 mL / g, 1 to 5 mL / g, or 1 to 3 mL / g) with respect to the substrate.

[0398] The mixture (e.g., suspension mixture, pre-functionalized mixture, or functionalized mixture) can be further processed in any useful manner. For example, without limitation, the mixture can be heated (e.g., to provide desired dissolution, adsorption, or reaction conditions). In some embodiments, the mixture is heated to a temperature of about 20° to 90°C. Other processing methods can include stirring, cooling, etc.

[0399] In some embodiments, the pre-functionalized mixture can be processed to separate the pre-functionalized material from the solvent. In some cases, the pre-functionalized material can be used to prepare the functionalized mixture. In some embodiments, the functionalized mixture (e.g., prepared with or without using the pre-functionalized mixture) can be processed to separate the functionalized material from the solvent. Such processes can include filtration, washing, etc. Filtration can be performed using methods known in the art for separating a solid phase from a liquid phase. This can include, but is not limited to, vacuum filtration, centrifugation, vacuum evaporation, or combinations of these or other methods.

[0400] Washing can be performed in the presence of one or more solvents to remove any unreacted compounds. Any solvent can be used (e.g., any neutral aprotic solvent as a washing solvent). In some embodiments, a single washing step can include immersing the functionalized material in a fresh solvent medium of a washing volume, whereby the functionalized material is overall immersed in the fresh solvent medium. In some implementations, one or more washing steps (e.g., two washings, three washings, four washings, or more) can be performed. The volume of the solvent medium separated from the functionalized material or used to wash the functionalized material can be discarded, stored, or recycled.

[0401] The functionalized material can be subjected to drying before use. Drying the functionalized silica material can include increasing the temperature, reducing the atmospheric pressure, passing an inert drying gas over the sample, or combinations thereof.

[0402] In some non-limiting embodiments, the functionalized material is subjected to drying at a temperature of about 30°-80° C. for a period of 6-12 hours (e.g., in a vacuum oven) for laboratory-scale processes (e.g., less than 500 g). Further conditions can be optimized for larger-scale processing, and the drying process can depend on the mass, temperature, pressure, and other conditions of the functionalized material, as will be understood by those skilled in the art. Any conditions can be used to provide a sample having a weight loss of about 15% (e.g., weight loss for solvent removal) or a minimal weight loss (e.g., less than about 5% at 100° C. over a period of about 2 hours) as measured, for example, in thermogravimetric analysis (TGA) with an inert gas flow through the sample (e.g., a N2 flow of 50 mL / min).

[0403] ii. Preparation of Functionalized Silica As described herein, the methods herein can include preparing a suspension mixture, which then includes silica and a reagent for functionalizing the surface of the silica. Such a suspension mixture can then be used in combination with at least one compound to provide a functional moiety, thereby forming a pre-functionalized mixture (e.g., one having components for providing a portion of the functional moiety) or a functionalized mixture (e.g., one having components for providing a fully organized functional moiety).

[0404] Any useful reagent or compound can be used to provide a functional moiety to the silica. Non-limiting reagents and compounds include silane coupling materials (e.g., aminosilanes), multiple silane coupling materials (e.g., multiple aminosilanes), polyamines, multiple polyamines, monoamines, multiple monoamines, silane coupling materials (e.g., aminosilanes) in combination with amine compounds (e.g., polyamines or monoamines), polyamines in combination with monoamines, and the like. Such reagents and compounds can be provided in a single solution (e.g., a single suspension mixture) or in separate solutions (e.g., separate suspension mixtures).

[0405] In some embodiments, the method comprises introducing a first reagent comprising a first compound having a silane moiety and an amine moiety into a liquid mixture under conditions sufficient to cause the silane moiety of the first compound to chemically bond to the surface of a substrate (e.g., porous silica particles) to form a functionalized material (e.g., functionalized silica particles), the liquid mixture comprising a liquid and the substrate, and removing the functionalized material from the liquid.

[0406] In some embodiments, the method comprises introducing a first reagent comprising a first compound having a silane moiety and an amine moiety into a first liquid mixture under conditions sufficient to cause the silane moiety of the first compound to chemically bond to the surface of a substrate (e.g., porous silica particles) to form a functionalized material (e.g., functionalized silica particles), the first liquid mixture comprising a liquid and the substrate, removing the functionalized material from the liquid, drying the functionalized material (e.g., in a vacuum oven) until it reaches its hydration threshold, and introducing a second reagent comprising a second compound having a polyamine moiety into a second liquid mixture under conditions sufficient to cause the second compound to interact with the first compound to form a composite network or surface functionalized layer, the second liquid mixture comprising a second liquid and the functionalized material, and removing the further functionalized material from the second liquid. In some embodiments, the further functionalized material comprises functionalized silica oxide particles.

[0407] The first reagent can comprise a silane moiety. In some embodiments, the silane moiety comprises an alkoxysilane moiety. Non-limiting examples of alkoxysilane moieties include methoxysilane (e.g., -Si(OMe) d (X) 3~d wherein each X is independently a side group, a reactive group, or a leaving group as described herein, and d is an integer of 1, 2, or 3), or ethoxysilane (e.g., -Si(OEt) d(X) 3~d wherein each X is independently a side group, reactive group, or leaving group as described herein, and d is an integer of 1, 2, or 3). Compounds for providing an alkoxysilane moiety are R A Si(OMe) d (X) 3~d or R A Si(OEt) d (X) 3~d and can include, wherein each R A is independently an amine moiety, each X is independently a side group, reactive group, or leaving group as described herein, and d is an integer of 1, 2, or 3). Non-limiting examples of compounds include (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, [3-(2-aminoethylamino)propyl]trimethoxysilane, N1-(3-trimethoxysilylpropyl)diethylenetriamine, or an aminosilane oligomer (e.g., VPS SIVO 280, a modified organofunctional polysiloxane from Evonik Industries AG, Essen, Germany). In some embodiments, the aminosilane oligomer is an oligomer of an aminosilane (e.g., an oligomer of any aminosilane herein, e.g., an oligomer of R A Si[OMe] d [X] 3~d or an oligomer of R A Si[OEt] d [X] 3~d wherein each R A is independently an amine moiety, each X is independently a side group, reactive group, or leaving group as described herein, and d is an integer of 1, 2, or 3). In some embodiments, the aminosilane oligomer has the formula [-SiR S1 R S2 -L-NR N1 -] n or [-SiR S1 R S2 -NR N1 -L-NR N2 -]n comprises the structure, wherein R S1 and R S2 each independently is a leaving group, a reactive group, hydrogen (H), an optionally substituted aliphatic, heteroaliphatic, aromatic, or heteroaromatic (e.g., any of those described herein), each L is a linker (e.g., any of those described herein), R N1 and R N2 each independently is any of those described herein, and n is an integer of 1 or more.

[0408] In some embodiments, the silane moiety comprises a hydroxysilane moiety. Non-limiting examples of the hydroxysilane moiety include silanol, silanediol, or silanetriol. In some embodiments, the hydroxysilane moiety comprises -Si(OH)R S1 R S2 , -Si(OH)2R S1 , or -Si(OH)3, wherein R S1 and R S2 each independently is a leaving group, a reactive group, hydrogen (H), an optionally substituted aliphatic, heteroaliphatic, aromatic, or heteroaromatic. In some embodiments, the compound comprising a hydroxysilane moiety has the structure of formula R A Si[OH] d [R S1 3~d , wherein R A is an amine moiety (e.g., any of those described herein), R S1 is a leaving group, a reactive group, hydrogen (H), an optionally substituted aliphatic, heteroaliphatic, aromatic, or heteroaromatic, and d is an integer of 1, 2, or 3. Non-limiting examples of the compound include 3-aminopropylsilanetriol or N-(2-aminoethyl)-3-aminopropylsilanetriol.

[0409] ​In some embodiments, the silane moiety includes a halosilane moiety. Non-limiting examples of the halosilane moiety include chlorosilane, fluorosilane, bromosilane, or iodide silane. In some embodiments, the compound containing a halosilane moiety has the structure of formula [R A d Si[X] 3~d , where R A is an amine moiety (e.g., any of those described herein), X is a halo, and d is an integer of 1, 2, or 3. Non-limiting examples of the compound include tris(ethylmethylamino)chlorosilane or tris(dimethylamino)chlorosilane.

[0410] The first reagent can include a silane moiety and an amine moiety (e.g., those in an aminosilane, e.g., any of those described herein). The second reagent can include two or more amine moieties. In some embodiments, the second reagent is a polyamine (e.g., any of those described herein). Non-limiting examples of the second compound include linear or branched polyamines, polyethyleneimine (PEI), polypropyleneimine, tetraethylenepentamine (TEPA), triethylenetetramine (TETA), diethanolamine (or polymeric forms of diethanolamine), high molecular weight amine mixture (BASF Amix 1000), or other polyamines described herein.

[0411] ​In some embodiments, the method comprises introducing a first reagent comprising a first compound having an alkoxysilane moiety and an amine moiety into a first liquid mixture comprising a liquid and a substrate (e.g., porous silica particles) under conditions sufficient to cause the alkoxysilane moiety of the first compound to chemically bond to the surface of the substrate to form a pre-functionalized material (e.g., pre-functionalized or modified silica particles), removing the pre-functionalized material from the liquid, drying the pre-functionalized material (e.g., in a vacuum oven) until it can reach a hydration threshold, introducing a second reagent comprising a second compound having a polyamine into a second liquid mixture comprising a second liquid and the pre-functionalized material under conditions sufficient to cause the amine moiety of the second compound to chemically bond to the amine moiety of the first compound to form a functionalized material (e.g., functionalized silica particles), and removing the functionalized material (e.g., functionalized silica particles or functionalized silica oxide particles) from the second liquid.

[0412] In non-limiting implementations, a water-based reaction can be used. In some embodiments, the functionalized material is produced using a water-based reaction method in which a polyamine and an aminosilane are dissolved in water to form a solution. The aminosilane hydrolyzes to form aminosilane oligomers. The polyamine and the aminosilane react at room temperature in water to form a composite network via binding interactions (e.g., non-covalent binding interactions, e.g., ionic and / or hydrogen bonds). A substrate can be added to the solution and enabled to react with the bound polyamine and silane. The aminosilane can condense on the surface of the substrate (e.g., siloxane bonds can be formed with a silica substrate). Without wishing to be limited by theory, the bound aminosilane can interact with the polyamine via polymer complexation, ionic interactions, and / or hydrogen bonds, thereby binding the network to the substrate and creating a functionalized material.

[0413] In some embodiments, the method comprises introducing a first reagent comprising a polyamine, a second reagent comprising a silane moiety and an amine moiety, and a substrate (e.g., porous silica particles) into a volume of water under conditions sufficient to cause the amine moiety of the polyamine to interact with the surface of the substrate (e.g., by ionic interaction, hydrogen bonding interaction, etc.) and to cause the silane moiety of the second reagent to chemically bond to the surface of the substrate, thereby forming a functionalized material (e.g., functionalized silica particles), and removing the functionalized material from the water. In some embodiments, the method can further comprise drying the functionalized material in a vacuum oven at 80 °C until it reaches a hydration threshold (e.g., less than 5% (weight / weight) water relative to the functionalized material).

[0414] In some embodiments, the method comprises introducing a first reagent comprising polyethyleneimine and a second reagent comprising a silane moiety and an amine moiety into a volume of water to create a suspension, stirring the suspension for a first duration ranging from 5 to 10 minutes, introducing a substrate (e.g., porous silica particles) into the suspension to create a functionalization mixture, stirring the functionalization mixture for a second duration ranging from 5 to 20 minutes to create a functionalized material, recovering the functionalized material by filtration or evaporation, and drying the functionalized material at 120 °C for 20 minutes or less. Without wishing to be bound by mechanism or theory, drying can be performed under conditions that minimize oxidation of the functionalized material (e.g., conditions of heating to drying as measured by TGA or other methods herein, at a temperature high enough to dry, within a period of less than 20 minutes, without a vacuum).

[0415] Any useful concentration may be used. In some embodiments, the substrate comprises porous silica particles, and the porous silica particles may be added to the water of the above volume at a ratio of 150% to 300% (weight / weight) or 2 to 2.5 mL / g of water to porous silica particles (e.g., 150% to 250% (weight / weight), 200% to 300% (weight / weight), or 200% to 250% (weight / weight) of water to porous silica particles). The solvent-to-silica ratio can be adapted based on the coating method used. For example, non-limitingly, for a silica substrate having a pore volume of about 2.2 mL / g and a density of about 0.25 g / mL, 1 g of silica can be completely wetted (e.g., pore-filled) using 2 to 2.5 mL of solution. A lower solvent-to-silica ratio can result in incomplete wetting, and a larger solvent-to-silica ratio can result in excess solvent on the surface of the silica and between the particles. Variations based on the solvent type and the interaction between the silica and the solvent can be observed. For a given non-limiting example of silica, a solution ratio of 2 to 2.5 mL / g or less can be used for wetting or spray coating processes. In this case, the solution may be mixed or sprayed onto the silica substrate and is absorbed entirely. For a given non-limiting example of silica, a larger solution ratio of greater than 2.5 ml / g can be used for dip coating or immersion / slurry processes where the excess solution can be filtered off. For a given non-limiting example of silica, a very low solvent ratio of less than 1.5 mL / g can be used for a process where only the surface of the silica to a certain depth is coated with amine. This can be done by spray coating to achieve a uniform surface coating. Other ratios and processes may be used.

[0416] The first reagent can be added to water at a ratio of 5% - 25% (weight / weight) of the first reagent to the porous silica particles. Without wishing to be limited by mechanism and theory, a higher ratio can provide a higher CO2 uptake to a certain extent. For example, without limitation, a higher ratio (e.g., of a large MW polyamine or polymeric polyamine) can be more viscous, which can be a problem for handling, etc. In some embodiments, the maximum ratio can be limited by pore blockage by the first reagent. When the pores are completely filled or blocked by overloading, CO2 may not efficiently enter or exit the pores, thereby affecting the kinetics and performance. In some embodiments, increasing the polyamine ratio can result in a decrease in the recovery of performance after a certain point. In some embodiments, the presence of the polyamine can be synergistic with the aminosilane to a certain extent.

[0417] The second reagent can be added to water at a ratio of 20% - 80% (weight / weight) of the second reagent to the porous silica particles. Without wishing to be limited by mechanism and theory, a higher ratio can result in a higher CO2 uptake to a certain extent. For example, without limitation, a higher ratio (e.g., aminosilane) may not significantly contribute to viscosity but can contribute to pore filling or blocking. In some embodiments, the presence of the aminosilane is synergistic with the polyamine to a certain extent. In some embodiments, the aminosilane can improve the stability of the polyamine to a certain extent. In some embodiments, increasing the aminosilane ratio can result in a decrease in the recovery of performance after a certain point.

[0418] The first reagent can include two or more amine moieties. In some embodiments, the first reagent is a polyamine (e.g., any of those described herein). The second reagent may include a silane moiety and an amine moiety (e.g., as in an aminosilane, e.g., any of those described herein), or may include a polyamine (e.g., as described herein). Non-limiting examples of the second reagent include alkoxysilane, methoxysilane, silanetriol, alkoxysilanol, chlorosilane, hydrosilane, ethoxysilane, polyamine (e.g., linear or branched polyamine), or others described herein (e.g., (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, [3-(2-aminoethylamino)propyl]trimethoxysilane, N1-(3-trimethoxysilylpropyl)diethylenetriamine, 3-aminopropylsilanetriol, N-(2-aminoethyl)-3-aminopropylsilanetriol, tris(ethylmethylamino)chlorosilane, tris(dimethylamino)chlorosilane, aminosilane oligomer (e.g., VPS SIVO 280 from Evonik), polyethyleneimine (PEI), polypropyleneimine, tetraethylenepentamine (TEPA), triethylenetetramine (TETA), or high molecular weight amine mixture (e.g., BASF Amix 1000).

[0419] In some embodiments, the method includes introducing a first reagent including a first compound having a plurality of amine moieties into a liquid mixture including a liquid and a substrate (e.g., porous silica particles) under conditions sufficient to cause the plurality of amine moieties to chemically bond to the surface of the substrate to form a functionalized material (e.g., functionalized or modified silica particles), removing the functionalized material from the liquid, and drying the functionalized material (e.g., in a vacuum oven) until a hydration threshold is reached.

[0420] In some embodiments, the first compound can be a small molecule polyamine, an oligomeric amine, an oligomeric ethylene amine, an ethylene amine / oligomeric mixture, a small molecule mixture, or any combination thereof. The first compound can include Amix 1000, tetraethylenepentamine (TEPA), or triethylenetetramine (TETA).

[0421] In some embodiments, the method can further include introducing a second reagent comprising a second compound (e.g., an antioxidant) containing a sulfur-containing compound into a second liquid mixture comprising a second liquid and functionalized particles (e.g., functionalized silica oxide particles), removing the functionalized material from the second liquid, and drying the functionalized material (e.g., in a vacuum oven) until it reaches a hydration threshold. The second compound can be included in the second liquid mixture at a second compound in the range of 0.5% to 10% (weight / weight) relative to the substrate (e.g., silica oxide material).

[0422] In some embodiments, the method includes introducing a first reagent comprising a polyethyleneimine compound containing a plurality of amine moieties into a liquid mixture comprising methanol or ethanol and a substrate (e.g., porous silica particles) under conditions sufficient to cause the plurality of amine moieties of the polyethyleneimine compound to interact with the surface of the substrate (e.g., by van der Waals interactions, hydrogen bonding interactions, or ionic bonding interactions with silanol groups on the surface of the substrate) to form a functionalized material (e.g., functionalized or modified silica particles), removing the liquid from the functionalized material by evaporating the liquid from the functionalized material, and drying the functionalized material (e.g., in a vacuum oven) until it reaches a hydration threshold of 5% (weight / weight) of the first liquid relative to the functionalized material.

[0423] In some embodiments, the method includes introducing a first reagent comprising an ethyleneamine mixture compound containing a plurality of amine moieties into a liquid mixture comprising methanol or ethanol and a substrate (e.g., porous silica particles) under conditions sufficient to cause the plurality of amine moieties of the ethyleneamine mixture compound to chemically interact with the surface of the substrate to form a functionalized material (e.g., functionalized or modified silica particles), evaporating the liquid from the functionalized material to remove the functionalized material from the liquid, and drying the functionalized material (e.g., in a vacuum oven) until it reaches a hydration threshold of 5% (weight / weight) of a first liquid with respect to the functionalized material.

[0424] Further non-limiting methods of preparing functionalized silica can include any of those described herein (e.g., those in FIGS. 5A, 5B, and 5E - 5I).

[0425] iii. Preparation of Functionalized MOF As described herein, the methods herein can include preparing a suspension mixture, which then includes a reagent for providing a MOF. Such a suspension mixture can then be used in combination with at least one compound for providing a functional moiety, thereby forming a pre-functionalized mixture or a functionalized mixture (e.g., those described herein).

[0426] In some embodiments, the method can include preparing a suspension to form a MOF substrate (e.g., MOF particles), and then preparing a functionalized mixture comprising the MOF substrate and a compound for providing a functional moiety.

[0427] The suspension can be prepared in any useful manner. In some embodiments, the method comprises introducing a first reagent comprising a metal source and a second reagent comprising an organic ligand into a solvent medium (or liquid) under conditions sufficient to cause a reaction between the first reagent and the second reagent to produce a MOF substrate (e.g., MOF particles). In some embodiments, a MOF substrate having an adsorption moiety (e.g., functionalized with one or more amine-containing moieties capable of binding to the hydroxyl functional side groups of the MOF structure) can achieve reversible capture of carbon dioxide from a gas mixture (e.g., air). In some embodiments, the organic ligand can comprise at least one hydroxy group. Examples of metal sources and organic ligands, and compounds for providing such metal sources and organic ligands, can include any of those described herein.

[0428] In some embodiments, the hydroxy functional side groups can react with an interaction moiety and / or an adsorption moiety. In some embodiments, the hydroxy functional side groups can be used to form a covalent bond between the MOF substrate and the adsorption moiety (e.g., the hydroxy group reacts with the interaction moiety, thereby forming a covalent bond that exists between the MOF surface and the adsorption moiety).

[0429] The suspension (including the MOF matrix) can be further prepared to provide a functionalized mixture. In some embodiments, the method can further include introducing a third reagent comprising an adsorption moiety (e.g., an amine moiety) into the suspension. In some embodiments, the third reagent can be any of the aminosilanes described herein. Non-limiting aminosilane compounds include, for example, tris(ethylmethylamino)chlorosilane, tris(dimethylamino)chlorosilane, bis(3-(methylamino)propyl)trimethoxysilane, N-[3-(trimethoxysilyl)propyl]aniline, (N,N-dimethylaminopropyl)trimethoxysilane, 3-aminopropyl(diethoxy)methylsilane, bis[3-(trimethoxysilyl)propyl]amine, (3-aminopropyl)triethoxysilane, (3-aminopropyl)trimethoxysilane, N-[3-(trimethoxysilyl)propyl]ethylenediamine, N1-(3-trimethoxysilylpropyl)diethylenetriamine, or [3-(2-aminoethylamino)propyl]trimethoxysilane.

[0430] In some embodiments, introducing the third reagent can be done under conditions sufficient to cause the third reagent to chemically bond to the second reagent to form a modified MOF matrix (e.g., modified MOF particles). In some embodiments, the third reagent is an aminosilane compound (e.g., any of those described herein), and the silane moiety interacts with an organic ligand (e.g., a hydroxy group or other reactive group present on the organic ligand). The amine moiety of the aminosilane compound can be disposed on the surface of the MOF matrix. In the functionalized mixture, a functionalized material comprising the functionalized MOF (e.g., functionalized MOF particles) can be formed.

[0431] Optionally, the method can include providing a second solvent medium or a second liquid. In some embodiments, the method can further include removing the MOF substrate from the liquid, introducing the second liquid to the MOF substrate over a certain duration, and removing the MOF substrate from the second liquid, before introducing the third reagent. The second liquid can include a second volume of a solvent medium (e.g., any of those described herein).

[0432] The functionalized mixture can be further processed. In some embodiments, the method can include removing the functionalized MOF substrate (e.g., modified MOF particles) from the solvent medium or liquid present in the functionalized mixture. The liquid can be any useful solvent (e.g., a polar solvent). Non-limiting examples of the solvent include water, N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), methanol, ethanol, acetonitrile, dimethyl sulfoxide (DMSO), and combinations thereof.

[0433] The presence of a competitor or additive can affect ligand coordination, crystal morphology and size, nucleation, and crystal growth, etc. Non-limiting regulators or competitors and additives include inorganic acids (e.g., hydrochloric acid or hydrofluoric acid), carboxylic acids (e.g., benzoic acid, formic acid, acetic acid, trifluoroacetic acid, dodecanoic acid, or lauric acid), etc.

[0434] In some embodiments, the method can further include introducing a fourth reagent that is a competitor for the first and second reagents. The fourth reagent can include a non-coordinating base. The non-coordinating base can be 2,6-lutidine, N,N-diisopropylethylamine, triethylamine, 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorin, or 1,8-diazabicyclo[5.4.0]undec-7-ene. In some embodiments, the non-coordinating base can include a compound for deprotonating one or more hydroxy side groups present on the surface of the MOF substrate. The deprotonated side groups can then react with the silane moiety to provide a coating or surface functionalization layer.

[0435] The method can further include drying the functionalized MOF substrate (e.g., modified MOF particles) until it can reach a hydration threshold (e.g., any of those described herein).

[0436] Any useful MOF material and functionalized MOF can be prepared. In some embodiments, the method includes introducing a first reagent and a second reagent that includes a metal salt (e.g., a zinc salt, e.g., Zn(NO3)2·6H2O) into a polar solvent liquid under conditions sufficient to cause a reaction between the first and second reagents to produce a MOF substrate (e.g., MOF particles). In some embodiments, the second reagent includes an organic ligand (e.g., TPDC 2- or a derivative thereof, e.g., (X)2-TPDC 2- or (X)4-TPDC 2- ), or a compound that provides an organic ligand (e.g., a compound such as H2TPDC, H2(X)2-TPDC, or H2(X)4-TPDC).

[0437] In some embodiments, the method can further include removing the MOF substrate from the liquid, introducing a second polar solvent liquid to the MOF substrate over a period of time, removing the metal oxide structure particles from the second liquid, introducing a third polar solvent liquid to the MOF substrate over a period of time, and introducing a third reagent (e.g., an aminosilane such as tris(ethylmethylamino)chlorosilane or any of those described herein) into the third liquid under conditions sufficient to cause the third reagent to chemically bond to the second reagent to form a functionalized MOF (e.g., modified or functionalized MOF particles), and removing the functionalized MOF from the liquid. Non-limiting methods of preparing the functionalized MOF can include any of those described herein (e.g., as in FIG. 5C).

[0438] iv. Preparation of the functionalized resin As described herein, the methods herein can include preparing a suspension mixture, which then includes a resin material.

[0439] The suspension can be prepared in any useful manner. In some embodiments, the suspension can include a first agent (e.g., one that includes a resin substrate) and a second reagent (e.g., one that includes an adsorptive moiety). The second reagent can include any reactive amine(s) that can be introduced into the porous structure of the resin. Non-limiting examples of liquid amines include liquid amine-based polymers (e.g., polyethyleneimine (PEI)), liquid molecular mono-, di-, tri-, tetra-, penta-, and higher ethylamines, liquid amine-functionalized hydrocarbons, silylamines (or aminosilanes), or any combination thereof.

[0440] In some embodiments, the method includes introducing a first reagent and a second reagent by spraying the second reagent onto a resin matrix. In some embodiments, the method includes introducing a first reagent and a second reagent by forming a solution comprising the first reagent and the second reagent, and recovering the functionalized resin from the solution.

[0441] In some embodiments, the method includes combining a first reagent comprising porous resin particles and a second reagent comprising an amine moiety under conditions sufficient to cause a reaction between the first reagent and the second reagent to produce a functionalized resin (e.g., functionalized porous resin particles). In some embodiments, the method can further include introducing a liquid to the functionalized resin over a period of time and recovering the functionalized resin from the liquid. The method can further include drying the functionalized resin until a hydration threshold is reached. The liquid or a second liquid can be ethanol, methanol, or any solvent described herein.

[0442] In some embodiments, the method includes combining a first reagent comprising porous resin particles and a second reagent comprising an amine moiety under conditions sufficient to cause a reaction between the first reagent and the second reagent to produce a functionalized resin, recovering the functionalized resin from the solution, and drying the functionalized resin until a hydration threshold is reached.

[0443] In some embodiments, a polyamine is provided on the surface of the resin. In some embodiments, the polyamine includes two or more amine moieties. In some embodiments, the polyamine is ethylenediamine (H2NCH2CH2NH2), diethylenetetramine (DETA, H2N[CH2CH2NH]2H), triethylenetetramine (TETA, H2N[CH2CH2NH]3H), branched triethylenetetramine (N[CH2CH2NH]3), tetraethylenepentamine (H2N[CH2CH2NH]4H), or pentaethylenehexamine (H2N[CH2CH2NH]5H). In some implementations, the polyamine is polyethyleneimine (PEI) (e.g., linear, branched, or dendrimer form of PEI). In some implementations, the polyamine is an amine-based polymer. In some embodiments, the first amine moiety is configured to react with a reactive site (e.g., an acidic reactive site) of the resin to functionalize the resin, and the remaining amine moieties function as reactive sites for CO2 adsorption.

[0444] In some embodiments, a monoamine is provided on the surface of the resin. Non-limiting examples of the monoamine can include amine-functionalized hydrocarbons, such as ethanolamine, hexylamine, and the like.

[0445] In some embodiments, an amine-functionalized hydrocarbon is provided on the surface of the resin. The amine-functionalized hydrocarbon can include one, two, three, or more amine moieties (e.g., one, two, three, or more amine groups). Non-limiting examples of the amine-functionalized hydrocarbon include ethanolamine, hexylamine, or 1,6-hexanediamine.

[0446] In some embodiments, molecular ethylamine is provided on the surface of the resin. Non-limiting examples of molecular ethylamine include mono-, di-, tri-, tetra-, penta-, and / or larger ethylamines, as well as tetraethylenepentamine (TEPA), triethylenetetramine (TETA), or pentaethylenehexamine (PEHA).

[0447] In some embodiments, silylamine (or aminosilane) is provided on the surface of the resin. Non-limiting examples of silylamine include (3-aminopropyl)trimethoxysilane, [3-(2-aminoethylamino)propyl]trimethoxysilane, N1-(3-trimethoxysilylpropyl)diethylenetriamine, 3-aminopropylsilanetriol, N-(2-aminoethyl)-3-aminopropylsilanetriol, and any aminosilane described herein.

[0448] In some embodiments, an amine-based polymer is provided on the surface of the resin. Non-limiting examples of the polymer include polypropyleneimine, natural chitosan, polylysine, small molecule polyamine, or an ethyleneamine / oligomer mixture (BASF Amix 1000).

[0449] In some embodiments, the compound provided on the surface of the resin can include an amine-based polymer, polyethyleneimine (PEI), molecular ethylamine, amine-functionalized hydrocarbon, silylamine (or aminosilane), or any combination thereof.

[0450] Non-limiting methods for preparing the functionalized resin can include any of those described herein (e.g., those in Figure 5D).

[0451] v. Non-limiting examples of processes for forming the functionalized material Figures 5A - 5H are non - limiting flowchart diagrams showing examples of steps for generating a functionalized material. These drawings are further described below.

[0452] In any of these drawings, the process can be used to create a functionalized material for use in a reversible adsorbent material, for example, it can be used to synthesize a reversible CO2 adsorbent, such as a functionalized silica. In some implementations, the process can be performed on a large scale, for example, generating more than 1 kilogram of the functionalized material in a single process. To maintain the original particle size distribution, a stirring method in which the substrate is not contacted, such as overhead stirring, is preferred.

[0453] The process herein may refer to a silane coupling material as a compound configured to provide an adsorption moiety, but other compounds can be used. For example, without limitation, the silane coupling material can be replaced with any compound (e.g., any of the compounds described herein) that includes an adsorption moiety and / or an interaction moiety.

[0454] As shown in Figure 5A, process 500A can include preparing a suspension mixture that includes a solvent medium and a substrate (step 502A). In a suitable vessel for the total volume of the solvent medium and the substrate, such as a three - neck round - bottom flask, the solvent medium and the substrate (e.g., a silica material or a silicon oxide material) are dispensed. The substrate can be any suitable substrate (e.g., a silica substrate or any other substrate described herein). The solvent medium can be dispensed by, for example, dispensing 1 - 15 mL / g (e.g., 1 mL / g, 5 mL / g, 8 mL / g, 15 mL / g, 2 - 2 mL / g, 2 - 2.5 mL / g, or other ranges herein) of the solvent medium with respect to the substrate so as to entirely cover the substrate within the vessel. The solvent medium can be any of those described herein (e.g., a neutral aprotic organic solvent, such as toluene, hexane, cyclohexane, or tetrahydrofuran (THF), and any combination thereof).

[0455] Process 500A can include agitating a substrate in a solvent medium over a first period (step 504A). The suspension mixture can be agitated (e.g., stirred) in the vessel, for example, with a magnetic stir bar and a stirring plate, or by other suitable methods known to those skilled in the art (e.g., can be agitated) while the substrate is immersed in the solvent medium. Agitation can increase the diffusion rate to ensure a homogeneous mixture. The first period should be sufficient to ensure that the substrate has absorbed the solvent medium to its maximum capacity. For example, the first period can range from 10 minutes to 3 hours (e.g., 2 hours).

[0456] While agitating, a silane coupling material can be added to the suspension mixture to form a functionalized mixture (step 506A). The silane coupling material can include any compound having a silane moiety, for example, any of the amino silane compounds described herein. The silane coupling material can be dispensed with a loading silane in the range of 20% to 80% (weight / weight) relative to the substrate.

[0457] While agitating, the functionalized mixture can be heated to a heating temperature above ambient temperature and below 90 °C (e.g., above 25 °C and below 90 °C) (step 508A). The heating temperature to which the functionalized mixture is heated can depend on the solvent medium selected for process 500A. As an example, in an implementation where toluene is selected as the solvent medium, the heating temperature can be 70 ° or 90 °C. The temperature can preferably be below the temperature at which oxidation of the amine occurs (e.g., a temperature of 70 ° to 80 °C or a temperature below 90 °C).

[0458] Process 500A can include stirring the functionalized mixture at a heating temperature for a second period (step 510A). The second period can be sufficient to allow for maximum functionalization (e.g., bonding) of the silane coupling material to the surface of the substrate. Generally, without wishing to be bound by theory, the second period can be greater than 6 hours and depends on the solvent medium, the heating temperature, and the silane coupling material. In some implementations, the second period can be greater than 8 hours (e.g., greater than 10 hours, greater than 12 hours, greater than 18 hours, greater than 20 hours, or greater than 24 hours).

[0459] After the second period, process 500A can include cooling the functionalized mixture (step 512A). In some implementations, the cooling is performed passively (e.g., radiative cooling). For example, the vessel can be allowed to cool at ambient air temperature until the functionalized mixture is cooled to a target temperature. In some implementations, the target cooling temperature is ambient temperature (e.g., room temperature). In alternative implementations, the cooling is performed actively (e.g., heat exchange), such as with a water bath for the vessel.

[0460] Process 500A can further include filtering the functionalized material from the functionalized mixture (step 514A). The filtering can be performed using methods known in the art for separating a solid phase from a liquid phase. This can include, but is not limited to, vacuum filtration, centrifugation, vacuum evaporation, or combinations of these or other methods. The volume of solvent medium separated from the functionalized material may be discarded, stored, or recycled.

[0461] Process 500A can further include washing the functionalized material in at least one wash volume of fresh (e.g., new volume) solvent medium (step 516A). In some embodiments, a ratio similar to that of step 502A of fresh solvent medium to functionalized material (e.g., 10 mL / g of fresh solvent medium to amine-functionalized substrate) can be used. For example, the functionalized material can be immersed in a wash volume of fresh solvent medium (e.g., 40 mL of solvent for 4 g of functionalized material), and single or multiple washes can be performed. In some embodiments, the wash solvent dissolves the silane moiety and removes the unreacted moiety that is coated on the surface of the functionalized substrate.

[0462] Process 500A can further include drying the functionalized material (step 518A). Drying the functionalized material can include increasing the temperature, reducing the atmospheric pressure, passing an inert drying gas over the sample, or combinations thereof. The functionalized material can be subjected to drying to remove substantially all of the wash volume of solvent medium encapsulated within the functionalized material. For example, in some implementations, the functionalized material is subjected to drying in a vacuum oven at 50 °C for 12 hours, e.g., overnight. As a non-limiting example, the drying threshold is a 15% weight loss by the sample (e.g., weight loss for solvent removal) or a minimum weight loss (e.g., less than about 5% weight loss at 100 °C over a period of about 2 hours) as measured by, e.g., in TGA, with an inert gas flow through the sample (e.g., 50 mL / min of N2 flow). In some implementations, the functionalized material is subjected to drying until a hydration threshold is reached, e.g., until less than 5% (weight / weight) of solvent remains with respect to the functionalized material. The functionalized material can then be prepared for use as a reversible adsorbent material.

[0463] As shown in FIG. 5B, process 500B can include preparing a suspension mixture including a solvent medium and a substrate (step 502B), and stirring the substrate in the solvent medium over a first period of time (step 504B). Additional details can include any of those described herein (e.g., those for step 502A or 504A).

[0464] During stirring, a silane coupling material can be added to the suspension mixture to form a pre-functionalized mixture (step 506B). The silane coupling material can include any compound having a silane moiety, such as any of the aminosilane compounds or silane compounds described herein. The silane coupling material can be dispensed with a loading silane in the range of 20% to 80% (weight / weight) relative to the substrate.

[0465] During stirring, the pre-functionalized mixture can be heated to a heating temperature above ambient temperature and below 90° C. (e.g., above 25° C. and below 90° C.) (step 508B). The heating temperature at which the functionalized mixture is heated can depend on the solvent medium selected for process 500B. As an example, in an implementation where toluene is selected as the solvent medium, the heating temperature can be 90° C. As another example, in an implementation where hexane is selected as the solvent medium, the heating temperature is 65° C. The temperature is preferably below the temperature at which oxidation of the amine occurs (e.g., a temperature of 70°-80° C. or a temperature below 90° C.).

[0466] Process 500B can include stirring the pre-functionalized mixture at a heating temperature for a second period (step 510B). The second period can be sufficient to allow for maximum functionalization (e.g., bonding) of the silane coupling material to the surface of the substrate. After the second period, process 500B can include cooling the pre-functionalized mixture (step 512B), filtering the pre-functionalized material from the pre-functionalized mixture (step 514B), washing the pre-functionalized material in at least one wash volume of fresh (e.g., a new volume of) solvent medium (step 516B), and drying the pre-functionalized material (step 518B). In some embodiments, a ratio similar to that of step 512A of fresh solvent medium to pre-functionalized material (e.g., 10 mL / g of fresh solvent medium to pre-functionalized material) can be used. Additional details can include any of those described herein (e.g., those for steps 510A, 512A, 514A, 516A, and 518A).

[0467] Process 500B can further include preparing a second suspension mixture that includes a second solvent medium and the pre-functionalized material (step 520B). For example, dispense the pre-functionalized substrate (e.g., an amine-grafted silica material) and the second solvent medium in a vessel suitable for the total volume of the second solvent medium and the pre-functionalized material, such as a three-neck round-bottom flask. In some examples, the second solvent is methanol. In some examples, the second solvent medium is a solvent mixture, such as a 2:1 mixture of ethanol and cyclohexane. The choice of solvent mixture for the second solvent medium can affect adsorbent uptake.

[0468] In one example, the solvent medium used in step 520B, such as methanol or water, can cause hydrolysis of the first adsorption moiety (e.g., provided by a silane coupling material and deposited as a silane layer). In some embodiments, the solvent mixture is characterized in that it does not readily hydrolyze and solvate the silane layer from the surface of the substrate. The second solvent medium can be dispensed by, for example, dispensing 2 - 2.5 mL / g or 6 mL / g (e.g., 1 mL / g, 2 mL / g, 3 mL / g, or 5 mL / g) of the solvent medium per gram of the pre-functionalized substrate so as to entirely cover the pre-functionalized substrate within the vessel.

[0469] Process 500B can further include adding an amine compound into the second solvent medium (step 522B). The amine compound can be any of those described herein that includes one or more amine moieties. In some embodiments, the amine compound is a polyamine or a small molecule amine, such as any of those described herein. The amine compound can be dispensed into the second solvent medium at a ratio of 30% (weight / weight) or 5% - 25% (weight / weight) relative to the pre-functionalized substrate in the second solvent medium. In some implementations, the amine compound is dispensed into the second solvent medium at a ratio of up to 50% (weight / weight) or a ratio of 20% (weight / weight) (e.g., in the range of 20% - 50% (weight / weight) or 2% - 20% (weight / weight)).

[0470] Process 500B can include stirring the amine compound and the pre-functionalized material in the second solvent medium over a period of time (step 524B). The suspension can be stirred (e.g., agitated) in the vessel described herein while the substrate of the pre-functionalized material is immersed in the second solvent medium. The first period can be sufficient to ensure that the pre-functionalized material has absorbed the second solvent medium to its maximum capacity and / or has interacted with the amine compound to form a functionalized material. For example, without limitation, the period can be in the range of 1 hour to 3 hours (e.g., more than 1 hour, e.g., 2 hours).

[0471] Process 500B may include filtering the functionalized material from the functionalization mixture (step 526B) and drying the functionalized material (step 528B). Additional details can include any of those described herein (e.g., those for steps 514A and 518A).

[0472] In some alternative implementations, the silane coupling material and the amine compound are added in step 506B to the first solvent medium. Such implementations can reduce the time and solvent volume used to produce the functionalized mixture. Non-limiting examples of solvents for the first solvent medium can include water, methanol, ethanol, or mixtures thereof (e.g., and any others described herein).

[0473] As shown in FIG. 5C, process 500C can include preparing a suspension mixture comprising a solvent medium, a metal source (e.g., a metal ion source), and an organic ligand compound (step 502C). The metal source, the organic ligand, and the solvent medium are dispensed in a suitable vessel for the total volume of the solvent medium, the metal source, and the organic ligand compound, e.g., a sealable reactor.

[0474] The metal source can be any suitable source described herein (e.g., ZnNO3, ZrCl4, or alternative salts thereof). The organic ligand can be any suitable source described herein (e.g., 2-hydroxyterephthalic acid). The ratio of the organic ligand material to the metal source material can vary according to the specific interaction between the organic ligand and the metal atom. Generally, the ratio can be 1:1, or a non-limiting range of about 1:5 to 5:1 moles of organic ligand per mole of metal. The synthesis of the functionalized MOF can be carried out under any useful conditions, e.g., under solvothermal reactor-based reaction conditions or hydrothermal reactor-based reaction conditions.

[0475] The solvent medium can be dispensed, for example, by dispensing 50 mL / g (e.g., 10 mL / g, 15 mL / g, 20 mL / g, or 30 mL / g) of the solvent medium with respect to the metal source so as to entirely cover the metal source and the organic ligand compound within the vessel. Generally, without wishing to be bound by theory, when the MOF is synthesized under acidic conditions (e.g., those that can exist in the presence of metal chlorides that react with carboxylic acid-containing ligands), an inert high-boiling aprotic solvent may be preferred. In some non-limiting examples, when the MOF is synthesized under basic conditions or when synthesized with a nitrogen-based ligand (e.g., an imidazole ligand), a protic solvent, such as methanol, ethanol, or even water, can be used. Non-limiting examples of the solvent medium include polar solvents such as water, dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), diethylformamide (DEF), methanol, ethanol, dimethyl sulfoxide (DMSO), or any combination thereof.

[0476] Optionally, process 500C can include dispensing a modifier or competitor into the suspension mixture (step 504C). Such agents can alter the crystallization reaction kinetics that occur between the metal ion source and the organic ligand material. For example, non-limitingly, a modifier or competitor can be added to the MOF synthesis reaction mixture (e.g., the suspension mixture) and can increase the reproducibility and crystallinity of the final MOF substrate. The modifier and competitor can be selected based on the metal ion source and the organic ligand material and can include carboxylic acids such as benzoic acid. In some embodiments, the modifier or competitor includes an agent that competes with the organic ligand to coordinate to the metal centers in the MOF structure. Without wishing to be limited by mechanism or theory, the presence of such agents can enable the MOF to "regrow" or correct errors, thereby reducing defects.

[0477] Process 500C can include stirring the suspension mixture (step 506C). The suspension mixture can be stirred (e.g., agitated) within the reaction chamber, for example, with a magnetic stir bar and stir plate, or other suitable methods known to those skilled in the art, while the metal ion source and the organic l...

Claims

1. a plurality of porous silica particles, the plurality of porous silica particles comprising a plurality of pores; the plurality of porous silica particles comprises a mixture of diameters ranging from 500 μm to 3 mm; the plurality of pores comprises a mixture of diameters ranging from 70 nm to 200 nm; a plurality of porous silica particles; a surface modification layer disposed on at least a portion of a surface of at least one of the plurality of porous silica particles, the surface modification layer comprising an adsorbent moiety comprising one or more amine moieties, the amine moieties reacting with or binding to carbon dioxide, the surface modification layer comprising an interaction moiety that attaches an adsorbent moiety to the surface of at least one of the plurality of porous silica particles, the interaction moiety comprising a silane moiety; Functionalized materials.

2. 10. The material of claim 1, wherein the plurality of porous silica particles comprises 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 a granule.

3. 10. The material of claim 1, wherein the plurality of pores comprises a volume of about 0.5 mL / g.

4. 2. The material of claim 1, wherein the surface modification layer comprises 5% to 60% (wt / wt) of a polyamine relative to the plurality of porous silica particles lacking the surface modification layer, or wherein the surface modification layer comprises 5% to 80% (wt / wt) of an aminosilane relative to the plurality of porous silica particles lacking the surface modification layer.

5. The plurality of porous silica particles has a density of about 100 m per dry gram. ２ 10. The material of claim 1 comprising a total surface area of ​​greater than 1000 nm.

6. The material has greater than about 0.8 mol CO per dry kilogram. ２ or about 0.8 to 2.5 mol CO per dry kilogram ２ The material of claim 1 , which adsorbs

7. The material is CO ２ at a relative humidity in the range of about 5% to 95%.

8. 2. The material of claim 1, wherein the surface modification layer is provided by interacting one or more compounds with at least a portion of the surface of at least one of the plurality of porous silica particles, and the one or more compounds are selected from the group consisting of aminosilanes and polyamines.

9. 9. The material of claim 8, wherein the aminosilane comprises a structure having one of formulas (I), (Ia)-(If), (II), and (IIa)-(IId), and the polyamine comprises a structure having one of formulas (IIIa)-(IIIi).

10. The material is configured to adsorb atmospheric CO2 under first conditions and reversibly desorb the adsorbed CO2 under second conditions, wherein the first conditions include a first temperature range and the second conditions include a second temperature range higher than the first temperature range, or the first conditions include a first gas pressure and the second conditions include a second gas pressure lower than the first gas pressure, or the first conditions include a first CO ２ the second condition includes the first CO concentration; ２ Second CO concentration lower than ２ The material of claim 1 , comprising a concentration.

11. The material of claim 1, further comprising one or more antioxidant moieties, additives, hydrophobic silane compounds, and hydrophobic polymers.

12. 10. The material of claim 1, wherein the 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.

13. 1. A method of forming a functionalized material, comprising: introducing a first reagent and a second reagent into a solvent medium, thereby providing a functionalization mixture, wherein the first reagent comprises a polyamine and the second reagent comprises an aminosilane; introducing a plurality of porous silica particles into the functionalization mixture for a period of time, thereby forming a functionalized material, the functionalized material comprising the plurality of porous silica particles and a surface modification layer disposed on at least a portion of a surface of at least one of the plurality of porous silica particles; the plurality of porous silica particles comprises a mixture of diameters ranging from 500 μm to 3 mm; the plurality of porous silica particles comprising a plurality of pores comprising a mixture of diameters in the range of 70 nm to 200 nm; the surface modification layer comprises at least one sorbent moiety, the sorbent moiety comprising one or more amine moieties that react with or bind to carbon dioxide; the surface modification layer comprises an interaction moiety that attaches an adsorbent moiety to the surface of the at least one of the plurality of porous silica particles, the interaction moiety comprising a silane moiety. Forming and removing the functionalized material from the functionalization mixture; and drying the functionalized material.

14. 14. The method of claim 13, wherein the aminosilane comprises a structure having one of formulas (I), (Ia)-(If), (II), and (IIa)-(IId), and the polyamine comprises a structure having one of formulas (IIIa)-(IIIi).

15. 14. The method of claim 13, wherein the plurality of porous silica particles comprises an amount of at least 25 kilograms.

16. 14. The method of claim 13, wherein said drying comprises drying to a hydration threshold of about 5% (wt / wt) solvent medium relative to said functionalized material.

17. CO ２ from air, comprising: CO ２ providing ambient air containing the functionalized material to a holder containing the functionalized material, thereby providing a rich adsorbent material; CO ２ from the rich adsorbent material, thereby providing a lean material. The method of claim 13.

18. The method of claim 13, wherein the functionalization mixture comprises 5% to 60% (weight / weight) polyamine relative to the plurality of porous silica particles.

19. The method of claim 13, wherein the functionalization mixture comprises 5 to 80% (weight / weight) aminosilane relative to the plurality of porous silica particles.

20. The material described in claim 1, wherein the adsorption portion comprises polyethyleneimine.

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