Solid sorbent materials functionalized with polyamines having oxygen-containing units selected from carbonyl units, hydroxyl units, and combinations thereof

Abstract

To provide sorbents that exhibit low adsorption capacity for water, high adsorption capacity for carbon dioxide, and low desorption residuals under mild desorption conditions, as well as methods for producing and using the sorbents.SOLUTION: A functionalized sorbent is provided, comprising a sorbent and at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof.SELECTED DRAWING: Figure 48

Description

[Technical Field]

[0001] Described herein are sorbents functionalized with polyamines having oxygen-containing units selected from carbonyl units, hydroxyl units, and combinations thereof. These sorbents may be metal-organic framework sorbents or non-metal-organic framework sorbents. The sorbent materials developed in this disclosure exhibit low adsorption capacity for water, high adsorption capacity for carbon dioxide, and low desorption residues under mild desorption conditions. [Background technology]

[0002] The use of solid sorbent materials for carbon capture offers a viable and superior techno-economic alternative to conventional liquid amine-based carbon dioxide (CO2) capture processes. Solid sorbents tend to have better adsorption capacity for activated liquid amines, lower regeneration energy requirements, lower system complexity, and lower environmental and safety risks.

[0003] Based on the underlying adsorption mechanism, two types of sorbent materials exist: physical sorbents and chemical sorbents. Physical sorbents, such as activated carbon and zeolites, rely on van der Waals interactions to adsorb gaseous species such as CO2 and water (HO). Chemical sorbents, such as amine-functionalized silica particles and metal-organic frameworks (MOFs), adsorb CO2 through reversible chemical reactions and the formation of ammonium carbamate, ammonium carbonate, and / or ammonium bicarbonate. Although physical sorbent materials are more mature than chemical sorbent materials, one of their major drawbacks is the significantly reduced CO2 adsorption capacity due to interference from other polar molecules, such as HO, which are inevitably present in atmospheric and flue gases. In contrast, as a result of chemical bonding, chemisorbent materials generally exhibit superior CO adsorption selectivity over other interfering species such as nitrogen (N), oxygen (O), methane, and carbon monoxide (CO) relative to their physisorbent counterparts.

[0004] An ideal chemisorbent material should have good CO2 adsorption capacity, fast adsorption kinetics, easy and rapid desorption characteristics under practical desorption conditions, and good thermal and hydrothermal stability.

[0005] However, conventional CO2 sorbents tend to have high water uptake. For example, spermine-functionalized MOF-274 has a water uptake of approximately 35 wt% under conditions relevant to direct air capture, such as 25 °C and 50% RH. The impact of water uptake on techno-economic analyses has generally not been emphasized enough because the amount of water adsorption and desorption can add significant energy costs to any large-scale CO2 capture plant. For example, given the heat of sorption of HO of 47 kJ / mol, every ton of HO adsorbed per ton of CO2 captured adds at least 725 kWh of energy cost due to the latent heat associated with HO desorption. Thus, there is a need for sorbents with low water uptake.

[0006] In this disclosure, we have developed and demonstrated solid sorbent materials functionalized with polyamines having oxygen-containing units selected from carbonyl units, hydroxyl units, and combinations thereof. The sorbent materials developed in this disclosure exhibit high adsorption capacities for carbon dioxide, low adsorption capacities for water, and low desorption residues under mild desorption conditions. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] PCT / US2023 / 082729 publication [Patent Document 2] PCT / US2022 / 082243 publication Summary of the Invention

[0008] In one aspect, a functionalized sorbent is provided that includes a sorbent and at least one functionalizing ligand that includes a polyamine that includes at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof.

[0009] In another aspect, a method of making a functionalized sorbent is provided, the method comprising the steps of (I) forming a mixture comprising a sorbent, at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, optionally at least one functionalizing ligand not comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, optionally a solvent, and optionally a non-solvent, and (II) functionalizing the sorbent.

[0010] In another aspect, a method for modifying a functionalized sorbent is provided, comprising the steps of: (I) forming a mixture comprising a sorbent functionalized with at least one functionalizing ligand that does not include a polyamine that includes at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; and (II) reacting the reactant with the sorbent functionalized with at least one functionalizing ligand that does not include a polyamine that includes at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof to produce a sorbent functionalized with at least one functionalizing ligand that includes a polyamine that includes at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0011] In yet another aspect, a method for recovering at least one gas is provided, the method comprising the steps of: (I) receiving a gas source comprising at least one gas in a functionalized sorbent, the functionalized sorbent comprising a sorbent and at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof; and (II) recovering a quantity of the at least one gas with the functionalized sorbent. [Brief explanation of the drawings]

[0012] These and other features, aspects, and advantages of the present disclosure will be more fully understood from the following detailed description taken in conjunction with the accompanying drawings, in which like characters represent like parts throughout.

[0013] [Figure 1] FIG. 1 shows a H NMR analysis for Mg(dobpdc)(IPA) after digestion with 20 μL of 20% DCl in DO, 200 μL DO, and 600 μL DMSO-d according to the present disclosure. [Figure 2] FIG. 1 shows scanning electron microscope (SEM) images of exemplary MOF-274 prepared using salicylic acid (left) and fluorosalicylic acid (right) as crystal growth inhibitors in accordance with the present disclosure. [Figure 3] FIG. 1 shows the powder X-ray diffraction spectrum of MOF-274 synthesized in accordance with the present disclosure using 4,4′-biphenol as a crystal growth inhibitor. [Figure 4] FIG. 1 shows SEM images of exemplary MOF-274 prepared without (left) and with (right) 9.24 wt % 4,4′-biphenol incorporation in accordance with the present disclosure. [Figure 5] FIG. 1 shows the powder X-ray diffraction spectrum of MOF-274 synthesized in accordance with the present disclosure using BPYDC as a crystal growth inhibitor. [Figure 6]FIG. 1 shows SEM images of exemplary MOF-274 prepared with incorporation of BPYDC as a crystal growth inhibitor (0.13 wt%, 2.29 wt%, and 24.78 wt%) in accordance with the present disclosure. [Figure 7] FIG. 1 shows the powder X-ray diffraction spectrum of MOF-274 synthesized in accordance with the present disclosure using BPYDM as a crystal growth inhibitor. [Figure 8] FIG. 1 shows SEM images of exemplary MOF-274 prepared using BPYDM as a crystal growth inhibitor (incorporation of 1.17 wt %, 3.43 wt %, and 6.80 wt %) in accordance with the present disclosure. [Figure 9] Figure 1 shows a H NMR analysis performed on Mg2(dobpdc)1(spermine)1.01 after digestion with 20 μL of 20% DCl in DO, 200 μL DO, and 600 μL DMSO-d in accordance with the present disclosure. H NMR (DMSO-d, DO) δ 7.84 (dd, 2H), 7.67 (dd, 2H), 6.98 (dd, 2H), 2.90 (m, 12H), 1.93 (m, 4H), 1.65 (s, 4H). [Figure 10] Figure 1 shows H NMR analysis of 600 μL of 1,2-epoxybutane:spermine (O / N) solution in CD3OD with residual methanol (3.35 ppm) according to the present disclosure. H NMR (CD3OD) δ 3.58 (m, 1.06H), 2.67-2.4 (m, 14.08H), 1.66 (m, 4H), 1.54 (m, 6.28H), 0.96 (m, 3.24H). [Figure 11] Figure 1 shows H NMR analysis of a 600 μL solution of β-methylhydroxyltetraamine in DO according to the present disclosure. H NMR (DO) δ 3.6-3.5 (dd, 1.91H), 3.01 (m, 0.99H), 2.55-2.95 (m, 9.94H), 1.82 (m, 2H), 1.65 (m, 4.10H). [Figure 12]Figure 1 shows a H NMR analysis of 600 μL of a HC:spermine solution in CD3OD with residual methanol (3.35 ppm) according to the present disclosure. Peaks used to estimate the amount of functionalization are H NMR (CD3OD) δ 2.94-2.74 (10H, spermine) and 0.94 (t, 3H, HC). The structure is drawn in a simplified manner. The O / N ratio is 0.38 (see calculation below). [Figure 13] Figure 1 shows a H NMR analysis performed on Mg(dobpdc)(0.48HC:spermine) after digestion with 20 μL of 20% DCl in DO, 200 μL of DO, and 600 μL of DMSO-d according to the present disclosure. H NMR (DMSO-d, DO) δ 7.87 (dd, 2H), 7.71 (dd, 2H), 7.01 (d, 2H), 2.99-2.87 (m, 12H), 1.97-1.91 (m, 4H), 0.79-0.75 (6H). Peak integrations used to estimate amine loading are shown. Peaks due to the solvent toluene (*), spermine fragments of the amine (#), and -CH peaks from the hexyl chain (▲) are labeled as indicated. [Figure 14] FIG. 1 shows a synthetic scheme for the covalent functionalization of amines to γ-AlO in accordance with the present disclosure. [Figure 15] Figure 1 shows TGA curves of γ-AlO and GLYMO-functionalized γ-AlO in different solvents according to the present disclosure. In toluene, the GLYMO functionalization is approximately 14 wt% (green line). In ethanol, varying the GLYMO loading (25, 50, and 100 wt%) showed loadings of GLYMO between 18 wt% and 20 wt%. [Figure 16] FIG. 1 shows TGA curves of pure γ-Al2O3 and γ-Al2O3 functionalized with different amines according to the present disclosure. [Figure 17] FIG. 1 shows TGA curves of pure γ-AlO and one-pot synthesized γ-AlO (GE324-1A) modified with GLYMO and further functionalized with spermine according to the present disclosure. [Figure 18]FIG. 1 shows water isotherms (g HO / g sorbent) at 25° C. for sorbents functionalized with pristine amine 2-3-2 and 1,2-epoxybutane-modified amine 2-3-2 according to the present disclosure. [Figure 19] FIG. 1 shows water isotherms (number of H 2 O per amine group) at 25° C. for sorbents functionalized with unmodified amine 2-3-2 and 1,2-epoxybutane-modified amine 2-3-2 according to the present disclosure. [Figure 20] FIG. 1 shows water isotherms (g HO / g sorbent) at 25° C. for sorbents functionalized with unmodified amine 2-3-2 and (2,2,2-trifluoroethyl)oxirane (TFEO)-modified amine 2-3-2 according to the present disclosure. [Figure 21] FIG. 1 shows water isotherms (number of H2O per amine group) at 25° C. for sorbents functionalized with unmodified amine 2-3-2 and TFEO-modified amine 2-3-2 according to the present disclosure. [Figure 22] FIG. 1 shows water isotherms (g HO / g sorbent) at 25° C. for sorbents functionalized with spermine and epoxide-modified spermine according to the present disclosure. [Figure 23] FIG. 1 shows water isotherms (expressed as number of HO per amine group) at 25° C. for sorbents functionalized with spermine and epoxide-modified spermine according to the present disclosure. [Figure 24] FIG. 1 shows water isotherms (g HO / g sorbent) at 25° C. for a sorbent functionalized with spermine and a sorbent functionalized with post-synthetic modification with epoxide according to the present disclosure. [Figure 25] FIG. 1 shows water isotherms (number of HO per amine group) at 25° C. for a sorbent functionalized with spermine and a sorbent functionalized with post-synthetic modification with epoxide according to the present disclosure. [Figure 26] FIG. 1 shows the water isotherm (g HO / g sorbent) at 25° C. for a sorbent functionalized with β-methylhydroxyltetraamine according to the present disclosure (GE327-A3117D). [Figure 27] FIG. 1 shows the IUPAC classification of isotherms. [Figure 28] FIG. 1 shows the water isotherm (g HO / g sorbent) at 25° C. for γ-AlO (GE320-184A) functionalized with spermine according to the present disclosure. [Figure 29] FIG. 1 shows the water isotherm (g HO / g sorbent) at 25° C. for spermine-functionalized γ-AlO (GE321-184B) modified with 1,2-epoxybutane according to the present disclosure. [Figure 30] FIG. 1 shows the water isotherm (g HO / g sorbent) at 25° C. for one-pot synthesized γ-AlO (GE324-1A) modified with GLYMO and further functionalized with spermine according to the present disclosure. [Figure 31] FIG. 1 shows the dry CO isotherm of GE302 (amine 2-3-2): filled circles (25° C.) and open circles (120° C.) versus the dry CO isotherm of GE314 (—OH containing amine 2-3-2): filled squares (25° C.) and open squares (120° C.) in accordance with the present disclosure. [Figure 32] FIG. 1 shows CO isotherms (gCO / g sorbent) at 25° C. for sorbents functionalized with spermine and epoxide-modified spermine according to the present disclosure. [Figure 33] FIG. 1 shows CO2 isotherms (expressed as number of CO2 per amine group) at 25° C. for sorbents functionalized with spermine and epoxide-modified spermine according to the present disclosure. [Figure 34] FIG. 1 shows CO isotherms (g CO / g sorbent) at 25° C. for sorbents functionalized with unmodified amine 2-3-2 and 1,2-epoxybutane-modified amine 2-3-2 according to the present disclosure. [Figure 35] FIG. 1 shows CO isotherms (expressed as number of CO per amine group) at 25° C. for sorbents functionalized with unmodified amine 2-3-2 and 1,2-epoxybutane-modified amine 2-3-2 according to the present disclosure. [Figure 36] FIG. 1 shows CO isotherms (g CO / g sorbent) at 25° C. for sorbents functionalized with unmodified amine 2-3-2 and TFEO-modified amine 2-3-2 according to the present disclosure. [Figure 37] FIG. 1 shows CO isotherms (expressed as number of CO per amine group) at 25° C. for sorbents functionalized with unmodified amine 2-3-2 and TFEO-modified amine 2-3-2 according to the present disclosure. [Figure 38] FIG. 1 shows CO isotherms (gCO / g sorbent) at 25° C. for γ-AlO (GE320-184A) functionalized with spermine according to the present disclosure. [Figure 39] FIG. 1 shows the CO isotherm 25° C. (g CO / g sorbent) for spermine-functionalized γ-AlO (GE321-184B) modified with 1,2-epoxybutane according to the present disclosure. [Figure 40] FIG. 10 shows CO2 uptake and H2O uptake versus adsorption time for GE314 thin films according to the present disclosure. [Figure 41] FIG. 1 shows the desorption curve of a MOF-based sorbent (GE5-A369) functionalized with unmodified spermine according to the present disclosure. [Figure 42] FIG. 1 shows the desorption curve of a MOF-based sorbent (GE296-A366A) functionalized with —OH-containing spermine according to the present disclosure. [Figure 43] FIG. 1 shows the desorption curve of a MOF-based sorbent (GE301-A370A) functionalized with —OH-containing spermine according to the present disclosure. [Figure 44] FIG. 1 shows the desorption curve of a MOF-based sorbent (GE302-A377) functionalized with unmodified amine 2-3-2 according to the present disclosure. [Figure 45] FIG. 1 shows the desorption curve of a MOF-based sorbent (GE314) (powder) functionalized with —OH-containing amine 2-3-2 according to the present disclosure. [Figure 46] FIG. 1 shows the desorption curve of a MOF-based sorbent (GE314) (thin film) functionalized with —OH-containing amine 2-3-2 according to the present disclosure. [Figure 47] 1 is a flow diagram of an exemplary method according to the present disclosure. [Figure 48] 1 is a flow diagram of an exemplary method according to the present disclosure. [Figure 49] 1 is a flow diagram of an exemplary method according to the present disclosure. [Figure 50] 1 is a flow diagram of an exemplary method according to the present disclosure. [Figure 51] 1 is a flow diagram of an exemplary method according to the present disclosure.

[0014] Unless otherwise indicated, the drawings provided herein are intended to illustrate features of the disclosed embodiments. These features are believed to be applicable in a wide variety of systems incorporating one or more of the disclosed embodiments. As such, the drawings do not include all conventional features known to those skilled in the art as required to practice the embodiments disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0015] Described herein are solid sorbent materials functionalized with polyamines having oxygen-containing units selected from carbonyl units, hydroxyl units, and combinations thereof. The sorbent materials developed in this disclosure exhibit high adsorption capacities for carbon dioxide, low adsorption capacities for water, and low desorption residues under mild desorption conditions.

[0016] In general, functionalized sorbents according to the present disclosure can be used with any suitable compositions, systems, and methods known in the art to aid in functionalizing sorbents. The functionalized sorbents are not limited to any particular embodiment disclosed herein. Exemplary compositions, systems, and methods are found in PCT / US2023 / 082729, the contents of which are incorporated by reference.

[0017] In some embodiments, the functionalized sorbent comprises a first type of functionalizing ligand, wherein the first type of functionalizing ligand comprises at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof. Generally, the at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof can comprise any suitable ligand that facilitates the functionalized sorbents described herein. The at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof may comprise only one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, or may comprise two or more functionalizing ligands, each comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof.

[0018] In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof comprises at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof comprises at least one primary amine or at least one secondary amine.

[0019] In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentaamines, hexaamines, polyamines, and combinations thereof.

[0020] Generally, the polyamine may contain any number of amine groups known in the art to be suitable for supporting a functionalized sorbent. In some embodiments, the polyamine contains a total number of amine groups ranging from about 2 to about 10. In some embodiments, the polyamine contains a total number of amine groups ranging from about 2 to about 6. In some embodiments, the polyamine contains a total number of amine groups ranging from about 2 to about 4. In some embodiments, the polyamine contains 2, 3, 4, 5, 6, 7, 8, 9, or 10 amine groups.

[0021] In some embodiments, the at least one oxygen-containing unit is selected from the group consisting of a primary hydroxyl unit, a secondary hydroxyl unit, a tertiary hydroxyl unit, and combinations thereof.

[0022] In some embodiments, the at least one functionalized ligand is a reaction product comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof. In some embodiments, the reaction product comprises a primary hydroxyl unit and is formed from the reaction between a polyamine and an oxetane. In some embodiments, the reaction product comprises a secondary hydroxyl unit and is formed from the reaction between a polyamine and an epoxide. In some embodiments, the reaction product comprises a tertiary hydroxyl unit and is formed from a Direct Synthesis reaction.

[0023] In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof is obtained prior to MOF functionalization by pre-loading modification (PLM). In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof is obtained after MOF functionalization by post-synthesis modification (PSM).

[0024] In some embodiments, the functionalized sorbent has a Type II, or Type III, or Type IV isotherm with pure water. In some embodiments, the functionalized sorbent has a Type II isotherm with pure water. In some embodiments, the functionalized sorbent has a Type III isotherm with pure water. In some embodiments, the functionalized sorbent has a Type IV isotherm with pure water.

[0025] In some embodiments, the functionalized sorbent has an average water uptake of <1 HO molecule per amine at high relative humidity. In some embodiments, high relative humidity refers to 50% or greater relative humidity at ambient temperatures, such as, but not limited to, -20°C to 40°C. In some embodiments, high relative humidity refers to 60% or greater relative humidity at ambient temperatures, such as, but not limited to, -20°C to 40°C. In some embodiments, high relative humidity refers to 70% or greater relative humidity at ambient temperatures, such as, but not limited to, -20°C to 40°C. In some embodiments, high relative humidity refers to 60% or greater relative humidity at temperatures ranging from 40°C to 60°C. In some embodiments, high relative humidity refers to 70% or greater relative humidity at temperatures ranging from 40°C to 60°C. In some embodiments, high relative humidity refers to 70% or greater relative humidity at temperatures of 60°C or greater.

[0026] In some embodiments, the functionalized sorbent has a desorption temperature of 120°C or less, preferably 110°C or less, or more preferably 100°C or less.

[0027] In some embodiments, at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof has a LogP of -1.0 or greater. In some embodiments, at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof has a LogP of -0.5 or greater. In some embodiments, at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof has a LogP of 0 or greater. In some embodiments, at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof has a LogP of 0.5 or greater. As used herein, LogP is the logarithm (base 10) of the partition coefficient (P), defined as the ratio of a substance's organic (oil) to aqueous phase concentrations.

[0028] In some embodiments, the functionalized sorbent comprises a second type of functionalizing ligand, the second type of functionalizing ligand comprising at least one functionalizing ligand that is free of a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof. In some embodiments, the functionalized sorbent also comprises at least one functionalizing ligand that is free of a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof. Generally, the at least one functionalizing ligand that is free of a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof can comprise any suitable ligand that is compatible with the functionalized sorbents described herein. The at least one functionalized ligand that does not contain a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof may contain only one functionalized ligand that does not contain a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, or it may contain two or more functionalized ligands that each do not contain a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof.

[0029] In some embodiments, the at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof is selected from the group consisting of a polyamine ligand containing at least one cyclic unit, an aminosilicone ligand, an amine ligand, a monoamine ligand, a diamine ligand, a triamine ligand, a tetraamine ligand, a pentaamine ligand, a hexaamine ligand, a polyamine ligand, an alkylamine ligand, and an aminoalcohol ligand. Exemplary ligands include, but are not limited to, ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, di(N-methyl)ethylenediamine, N-isopropylethylenediamine, N,N-dimethyl-N-methylethylenediamine, di(N,N-dimethyl)ethylenediamine, N,N-diisopropylethylenediamine, 2,2-dimethyl-1,3-diaminopropane, 1,3-diaminopentane, diethylenetriamine, N-(2-amino-1,3-diaminopropane), N-(2-amino-1,3-diaminopent ... N,N'-bis(2-aminoethyl)-1,3-propanediamine, bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane (spermidine), triethylenetetramine, N,N'-bis(2-aminoethyl)-1,3-propanediamine, 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, N,N'-bis(3-aminopropyl)-1,4-diaminobutane (spermine), tetraethylenepentamine, and / or combinations thereof.

[0030] In some embodiments, the at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit can be any suitable at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit known in the art to aid in the functionalized sorbents described herein.

[0031] In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises at least one amine selected from the group consisting of a primary amine, a secondary amine, a tertiary amine, and combinations thereof. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises at least one primary amine or at least one secondary amine.

[0032] In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentaamines, hexaamines, polyamines, and combinations thereof.

[0033] In some embodiments, at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises a symmetric structure. In some embodiments, at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises an asymmetric structure.

[0034] In some embodiments, the at least one cyclic unit is selected from the group consisting of an alicyclic unit, an aromatic unit, and combinations thereof.

[0035] In some embodiments, described herein are polyamines comprising at least one cyclic unit. In some embodiments, the polyamines comprising at least one cyclic unit are functionalized ligands. In some embodiments, the polyamines comprising at least one cyclic unit are functionalized ligands that functionalize sorbents.

[0036] In many embodiments, the polyamine-containing functionalized ligand comprises at least one cyclic unit according to formula (CI).

[0037] [ka] During the ceremony, B, C, and D each independently comprise at least one amine group; x, y, and z are each independently 0 or 1; A comprises an aromatic ring structure according to formula (C-II) or an alicyclic structure according to formula (C-III).

[0038] [ka]

[0039] [ka] During the ceremony, n is an integer ranging from about 3 to about 8; m is an integer ranging from about 3 to about 5; A 1 , A 2 , A 3 , and A 4 each independently comprises at least one of carbon, oxygen, and silicon.

[0040] In some embodiments, A 1 , A 2 , A 3 , and A 4 are each individually, Carbon substituted with at least one substituent selected from the group consisting of hydrogen, B, C, D, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; Unsubstituted oxygen, Silicon substituted with at least one substituent selected from the group consisting of hydrogen, B, C, D, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; and A combination of these is selected from the group consisting of:

[0041] In some embodiments, B, C, and D each independently comprise a structure according to formula (C-IV).

[0042] E t -F u -G v -H w (Formula C-IV) During the ceremony, t, u, v, and w are each independently an integer ranging from about 0 to about 10; E, F, G, and H are each individually substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; NH2, NHR1, and NR1R2, R1 and R2 are each independently selected from the group consisting of substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; and A combination of these is selected from the group consisting of:

[0043] In some embodiments, the polyamine comprises at least two cyclic units, and the polyamine comprises multiple ring structures linked by at least one linking group selected from the group consisting of substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl.

[0044] In some embodiments, the polyamine comprises at least one bicyclic unit.

[0045] In some embodiments, the polyamine comprises at least two cyclic units, and the polyamine comprises a bridged polycyclic structure comprising at least one bridging group selected from the group consisting of substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl.

[0046] In some embodiments, the polyamine comprises at least one bridging cyclic unit.

[0047] In some embodiments, t, u, v, and w are each independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0048] In some embodiments, n is 3, 4, 5, 6, 7, or 8.

[0049] In some embodiments, m is 3, 4, or 5.

[0050] In some embodiments, at least one of x, y, and z is 1. In some embodiments, at least two of x, y, and z are 1. In some embodiments, x, y, and z are each 1.

[0051] Generally, each of B, C, and D can be attached to any suitable atom of A that aids in functionalizing sorbents according to the present disclosure. In many embodiments, each of B, C, and D is attached to a separate atom of a cyclic unit of A. In some embodiments, each of B, C, and D is attached to a ring unit of A. 1 , A 2 , A 3 , and A 4 are bonded to separate atoms of

[0052] In some embodiments, the polyamine comprises at least one substituent at a substituent position selected from the group consisting of the 1,2 (ortho) positions, the 1,3 (meta) positions, the 1,4 (para) positions, and combinations thereof.

[0053] In some embodiments, at least two of B, C, and D are located at the ortho positions of the cyclic unit of A. In some embodiments, at least two of B, C, and D are located at the meta positions of the cyclic unit of A. In some embodiments, at least two of B, C, and D are located at the para positions of the cyclic unit of A.

[0054] In some embodiments, the polyamine comprises an isomer selected from the group consisting of a cis-isomer, a trans-isomer, an R-enantiomer, an S-enantiomer, and combinations thereof.

[0055] In some embodiments, at least two of B, C, and D are different. In some embodiments, B, C, and D are different.

[0056] In some embodiments, at least two of B, C, and D are the same. In some embodiments, B, C, and D are the same.

[0057] In some embodiments, the polyamine comprises at least one heteroalicyclic ring unit. In some embodiments, the polyamine comprises at least one heteroalicyclic ring unit that does not contain nitrogen. In some embodiments, the polyamine comprises at least one heteroalicyclic ring unit, and the heteroatom is not nitrogen.

[0058] Generally, the polyamine can contain any number of amine groups known in the art to be suitable for supporting a functionalized sorbent. In some embodiments, the polyamine contains a total number of amine groups ranging from about 2 to about 10. In some embodiments, the polyamine contains a total number of amine groups ranging from about 2 to about 6. In some embodiments, the polyamine contains a total number of amine groups ranging from about 2 to about 4. In some embodiments, the polyamine contains 2, 3, 4, 5, 6, 7, 8, 9, or 10 amine groups.

[0059] In some embodiments, the polyamine is

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

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[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] [ka] and A combination of these The compound is selected from the group consisting of:

[0088] The following exemplary polyamines have cyclic units according to the present disclosure:

[0089] Aliphatic cyclic (6-membered ring) amines:

[0090] GE201 (mixture of cis and trans); GE182 (trans); GE200 (cis); 1,4-cyclohexanediamine (p-CHD) (molecular weight 114; boiling point 197°C).

[0091] [ka]

[0092] GE181; GE187 (mixture of cis and trans); GE199 (cis); 1,3-cyclohexanediamine (m-CHD) (molecular weight 114; boiling point 194°C).

[0093] [ka]

[0094] GE202 (mixture of cis and trans); GE203 (cis); GE209 (trans); 1,2-cyclohexanediamine (o-CHD) (molecular weight 114; boiling point 194°C)

[0095] [ka]

[0096] Di- / tri- / tetraamines:

[0097] GE221-A2109; 1,3,5-cyclohexanetriyltrimethanamine (CHTM) (molecular weight 171.316; boiling point 309°C)

[0098] [ka]

[0099] GE254;GE255(BPDCH)

[0100] [ka]

[0101] 3-ring-3

[0102] [ka]

[0103] Primary / secondary / tertiary amines:

[0104] N,N-dimethylcyclohexanediamine (N2MCHD) (molecular weight 142.24; boiling point 80°C at 18 mmHg)

[0105] [ka]

[0106] Cis or trans isomers and chirality:

[0107] (R,R)-1,2-Cyclohexanediamine(trans)

[0108] [ka]

[0109] (S,S)-Cyclohexanediamine(trans)

[0110] [ka]

[0111] (R,S)-Cyclohexanediamine(cis)

[0112] [ka]

[0113] Different lengths:

[0114] GE193 (mixture of isomers); 1,4-bis-(aminomethyl)-cyclohexane (BAMCH) (molecular weight 142.24; boiling point 239°C)

[0115] [ka]

[0116] GE206 (mixture of isomers); 1,3-bis-(aminomethyl)-cyclohexane (mBAMCH) (molecular weight 142.24; boiling point 240°C)

[0117] [ka]

[0118] GE248;GE249(BEDCH)

[0119] [ka]

[0120] Structures with multiple cyclic units:

[0121] GE216; 4,4'-methylenebis(2-methylcyclohexylamine) (mixture of isomers) (MCHA)

[0122] [ka]

[0123] Asymmetrical structure:

[0124] GE205 (mixture of isomers); 4-(aminomethyl)cyclohexanamine (AMCHA)

[0125] [ka]

[0126] GE240; 4-(2-aminoethyl)cyclohexylamine (mixture of cis and trans) (ACHEA)

[0127] [ka]

[0128] GE256; N-(3-aminopropyl)cyclohexylamine (BPDCH)

[0129] [ka]

[0130] Mixed amines:

[0131] GE234; GE235; a mixture of 1,4-bis-(aminomethyl)-cyclohexane (BAMCH) and spermine

[0132] [ka]

[0133] [ka]

[0134] GE236; GE237; a mixture of 1,4-bis-(aminomethyl)-cyclohexane (BAMCH) and spermidine

[0135] [ka]

[0136] [ka]

[0137] GE285; GE291; BEDCH and spermine mixture

[0138] [ka]

[0139] [ka]

[0140] Substitute:

[0141] GE208: Isophoronediamine (IPRDA) (molecular weight 170.3; boiling point 252.9°C)

[0142] [ka]

[0143] Bridged bicyclic structure:

[0144] GE214 Bis(aminomethyl)norbornane (BAMNB) (mixture of multiple isomers) (molecular weight 154.25; boiling point 259°C)

[0145] [ka]

[0146] [ka]

[0147] Heterocyclic amines:

[0148] GE204; [(2S,5R)-5-(aminomethyl)oxolan-2-yl]methanamine; tetrahydrofuran-2,5-diamine (AMTHF) (molecular weight 130.18)

[0149] [ka]

[0150] Aromatic (6) Amines / Substituted

[0151] GE183, GE184: meta-xylylenediamine (m-XYD) (molecular weight 136; boiling point 265°C)

[0152] [ka]

[0153] GE185; GE186; GE189; para-xylylenediamine (p-XYD) (molecular weight 136; boiling point 230°C)

[0154] [ka]

[0155] Primary / secondary / tertiary amines:

[0156] GE225; N-methyl-1-[4-(methylaminomethyl)phenyl]methanamine (Me-p-XYD) (molecular weight 164.20)

[0157] [ka]

[0158] Mixed amines:

[0159] GE226; GE227; Mixture of para-xylylenediamine (p-XYD) and 1,3,5-benzenetriyltrimethanamine (BTM)

[0160] [ka]

[0161] [ka]

[0162] GE247; GE251; para-xylylenediamine (p-XYD) and N 1 ,N 1 Mixture with '-((1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(propane-1,3-diamine) (APAP)

[0163] [ka]

[0164] [ka]

[0165] Heteroaromatic amines:

[0166] GE195: 2,5-bis(aminomethyl)furan (molecular weight 126.16 g / mol, boiling point 230°C).

[0167] [ka]

[0168] GE217; Tetrafluoro-p-xylylenediamine (TF-p-XYD) (molecular weight 2018.16)

[0169] [ka]

[0170] Di- / tri- / tetra- / penta- / hexa-amines:

[0171] GE220-A2107; 1,3,5-benzenetriyltrimethanamine (BTM) (molecular weight 165.24; boiling point 329°C)

[0172] [ka]

[0173] GE222;GE223(Ph-3-ED)

[0174] [ka]

[0175] GE252;GE253(Ph-3-PD)

[0176] [ka]

[0177] In some embodiments, the polyamine is

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181] [ka]

[0182] [ka] cyclohexanediamine, and A combination of these is selected from the group consisting of:

[0183] In some embodiments, the at least one functionalizing ligand comprising a polyamine free of at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof comprises at least one aminosilicone selected from the group consisting of linear aminosilicones, cyclic aminosilicones, branched aminosilicones, amino-substituted siloxanes, linear amino-substituted disiloxanes, cyclic amino-substituted disiloxanes, linear amino-substituted trisiloxanes, cyclic amino-substituted trisiloxanes, linear amino-substituted tetrasiloxanes, cyclic amino-substituted tetrasiloxanes, linear amino-substituted polysiloxanes, cyclic amino-substituted polysiloxanes, silsesquioxanes, polyoctahedral silsesquioxanes, and combinations thereof.

[0184] In some embodiments, at least one functionalized ligand comprising an aminosilicone group comprises a symmetric structure. In some embodiments, at least one functionalized ligand comprising an aminosilicone group comprises an asymmetric structure.

[0185] In some embodiments, when at least one functionalized ligand containing an aminosilicone group contains a disiloxane group, the at least one functionalized ligand containing an aminosilicone group contains the same amine on either side of the disiloxane group. In some embodiments, when at least one functionalized ligand containing an aminosilicone group contains a disiloxane group, the at least one functionalized ligand containing an aminosilicone group contains different amines on either side of the disiloxane group.

[0186] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group is an amino-substituted siloxane of Formula (AI), Formula (A-II), Formula (A-III), Formula (A-IV), Formula (AV), or Formula (A-VI).

[0187] [ka]

[0188] [ka]

[0189] [ka]

[0190] [ka]

[0191] [ka]

[0192] [ka] During the ceremony, R1, R2, R3, R4, R9, R 10 , R 13 , R 14 , and R 18 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R5, R6, R 11 , R 15 , and R17 are each independently selected from the group consisting of a direct bond, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; R7, R8, R 12 , and R 16 each independently represents a direct bond, a substituted or unsubstituted C1-C6 linear alkyl, a substituted or unsubstituted C3-C6 branched alkyl, a C1 alkyl, a C2 alkyl, a C3 alkyl, a C4 alkyl, a C5 alkyl, a C6 alkyl, and a substituent of formula (A-VII).

[0193] [ka] and wherein the formula (A-VII) is selected from the group consisting of: The wavy bond indicates the bond position relative to formula (AI) or formula (A-II) or formula (A-III) or formula (A-IV) or formula (AV) or formula (A-VI), R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted C1-C6 linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R 25 and R 26are each independently selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C1-C3 straight chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, and substituted or unsubstituted C4-C6 cycloalkyl, or R 25 and R 26 taken together form a monocyclic ring selected from the group consisting of heterocycloalkyl and heteroaryl; R 27 , R 28 , and R 29 are each independently selected from the group consisting of a direct bond, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-; R 30 is selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C1-C3 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl; j is an integer ranging from 0 to 20, k is an integer ranging from 0 to 20; m is an integer ranging from 0 to 20; n is an integer ranging from 0 to 20.

[0194] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group is:

[0195]

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[0227] [ka] is selected from the group consisting of:

[0228] Generally, the at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, and the at least one functionalizing ligand not comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, can be present in any suitable ratio known in the art to facilitate the functionalized sorbents described herein. In some embodiments, the ratio is selected from the group consisting of a molar ratio, a weight ratio, and a volume ratio. In some embodiments, the at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, and the at least one functionalizing ligand not comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, are present in a ratio ranging from about 10:1 to about 1:10. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, and the at least one functionalized ligand not comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, are present in a ratio ranging from about 9:1 to about 1:9. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, and the at least one functionalized ligand not comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, are present in a ratio ranging from about 8:1 to about 1:8.In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, and the at least one functionalized ligand not comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, are present in a ratio ranging from about 7:1 to about 1:7. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, and the at least one functionalized ligand not comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, are present in a ratio ranging from about 6:1 to about 1:6. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, and the at least one functionalized ligand not comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, are present in a ratio ranging from about 5:1 to about 1:5. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, and the at least one functionalized ligand not comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, are present in a ratio ranging from about 4:1 to about 1:4. In some embodiments, the at least one functionalized ligand that includes a polyamine that includes at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, and the at least one functionalized ligand that does not include a polyamine that includes at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, are present in a ratio ranging from about 3:1 to about 1:3.In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, and the at least one functionalized ligand not comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, are present in a ratio ranging from about 2:1 to about 1:2. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, and the at least one functionalized ligand not comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, are present in a ratio of about 1:1.

[0229] In some embodiments, the at least one functionalizing ligand that includes a polyamine that includes at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof is present in a lesser amount than the at least one functionalizing ligand that does not include a polyamine that includes at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof.

[0230] In some embodiments, the at least one functionalized ligand that includes a polyamine that includes at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, and the at least one functionalized ligand that does not include a polyamine that includes at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, are present in a ratio of about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, or about 1:10.

[0231] In general, the sorbent may be any suitable sorbent known in the art to support the functionalized sorbents described herein. In some embodiments, the sorbent is selected from the group consisting of coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCPs), covalent organic framework (COF) compounds, zeolitic imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open frameworks, reticular chemistry, silica particles, zeolites, silicoaluminophosphates (SAPOs), aluminophosphates (AlPOs), polyaromatic frameworks (PAFs), activated carbons, molecular organic solids, and combinations thereof.

[0232] As used herein, MOF compounds are a class of compounds that contain metal ions or clusters coordinated with organic ligands to form one-, two-, or three-dimensional structures. The metal ions or clusters are connected by multidirectional organic ligands that act as junctions and binders in the network. MOF compounds have a modular nature that allows for tunability in synthesis, providing fine chemical and structural control. Properties such as porosity, stability, particle morphology, and conductivity can be tailored for specific applications.

[0233] In many embodiments, the sorbent is a MOF compound comprising a MOF metal or metal-containing cluster and a MOF linking agent.

[0234] In some embodiments, the MOF metal can be any suitable MOF metal known in the art to support the functionalized sorbents described herein. In other embodiments, the MOF metal is a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof. In some embodiments, the MOF metal comprises Mg.

[0235] In some embodiments, the MOF metal-containing cluster can be any suitable MOF metal-containing cluster known in the art to support the functionalized sorbents described herein. In some embodiments, the MOF metal-containing cluster comprises MOF metal nodes and linking agent pillars, where the MOF metal and linking agent are each defined as described herein. In other embodiments, the MOF metal-containing cluster comprises a MOF metal oxide cluster.

[0236] In some embodiments, the MOF linking agent can be any suitable MOF linking agent known in the art that aids in the functionalization of sorbents described herein. Generally, the geometry and linking configuration of the linking agent contribute to the structure of the resulting MOF compound. By adjusting the geometry, length, ratio, and functional groups of the linking agent, the size, shape, and internal properties of the MOF compound can be tailored for a desired application.

[0237] In some embodiments, the MOF linker is a linker selected from the group consisting of polytopic linkers, bidentate linkers, tridentate linkers, tetradentate linkers, pentadentate linkers, hexadentate linkers, heptadentate linkers, octadentate linkers, mixed linkers, desymmetrized linkers, metal linkers, N-heterocyclic linkers, and combinations thereof.

[0238] In some embodiments, the MOF linking agent is a multidentate linking agent, 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H4dobpdc), 4,4′-dioxidobiphenyl-3,3′-dicarboxylate (dobpdc 4- ), 4,4′-dioxide-[1,1′:4′,1′-terphenyl]-3,3′-dicarboxylate (dotpdc 4- ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-DOBDC 4- ), 3,3′-dioxide-biphenyl-4,4′-dicarboxylate (para-carboxylate-dobpdc 4- ), 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), their protonated, partially deprotonated, and fully deprotonated forms, and combinations thereof. As another example, in some embodiments, the MOF linker is a linker selected from the group consisting of dicarboxylates (e.g., terephthalic acid), tricarboxylates (e.g., 1,3,5-benzenetricarboxylic acid), azolates, tetrazolates, and combinations thereof.

[0239] As another example, in some embodiments, the MOF linking agent is selected from the group consisting of 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, and 2-methylquinoline-3,4-dicarboxylic acid. , Quinoline-2,4-dicarboxylic acid, Quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4′-diaminophenylmethane-3,3′-dicarboxylic acid, Quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, Diimidedicarboxylic acid, Pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, Thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, Tetrahydropyran-4,4-dicarboxylic acid, Perylene-3,9-dicarboxylic acid, Perylene dicarboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-carboxylic acid, 4,4′-diamino-1,1′-diphenyl-3,3′-dicarboxylic acid, 4,4′-diaminodiphenyl-3,3′-dicarboxylic acid, benzidine-3,3′-dicarboxylic acid, 1,4-bis-(phenylamino)benzene-2,5-dicarboxylic acid, 1,1′-dinaphthyl-8,8′-dicarboxylic acid carboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4′-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-Dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cisdicarboxylic acid, 2,2′-biquinoline-4,4′-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenonedicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E 400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4′-diaminodiphenyletherdiimidedicarboxylic acid, 4,4′-diaminodiphenylmethanediimidedicarboxylic acid, 4,4′-diaminodiphenylsulfonediimidedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2′-3′-diphenyl-p-terphenyl-4,4″-dicarboxylic acid, diphenylether-4,4′-dicarboxylic acid Acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4′-dihydroxydiphenylmethane-3,3′-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,The dicarboxylic acid linking agent is selected from the group consisting of 1,3-dicarboxylic acid, 2,9-dichlorofluorubin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, and combinations thereof.

[0240] As another example, in some embodiments, the MOF linking agent is a tricarboxylic acid linking agent selected from the group consisting of 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurintricarboxylic acid, and combinations thereof.

[0241] As another example, in some embodiments, the MOF linking agent is 1,1-dioxide-perillo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, meso-1,2,3,4-butane tetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid. and a tetracarboxylic acid linking agent selected from the group consisting of 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, and combinations thereof.

[0242] In an exemplary embodiment, the MOF linking agent is 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H4dobpdc) and / or 4,4′-dioxidobiphenyl-3,3′-dicarboxylate (dobpdc 4- In some embodiments, dobpdc comprises 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid, its monocarboxylate form, its dicarboxylate form, its monophenoxide form, its diphenoxide form, and combinations thereof.

[0243] In some embodiments, the MOF linking agent is one or more of the following linking agents:

[0244] [ka] 4,4'-Dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid

[0245] [ka] 4,4'-Dioxidobiphenyl-3,3'-dicarboxylate

[0246] [ka] 4,4"-Dioxide-[1,1':4',1"-terphenyl]-3,3"-dicarboxylate

[0247] [ka] 2,5-Dioxidobenzene-1,4-dicarboxylate

[0248] [ka] 4,6-dihydroxyisophthalic acid

[0249] [ka] 3,3′-Dioxide-biphenyl-4,4′-dicarboxylate

[0250] [ka] 4,4'-[Oxalylbis(imino)]bis(2-hydroxybenzoic acid)

[0251] [ka] 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) and / or

[0252] [ka] 4,4′-Dihydroxyazobenzene-3,3′-dicarboxylic acid.

[0253] In some embodiments, the MOF compound is a MOF compound of the MOF-74 family. In some embodiments, the MOF compound is a MOF compound of the MOF-274 family. In some embodiments, the MOF compound is a MOF compound of the MOF-303 family. In some embodiments, the MOF compound is Mg2(dobpdc).

[0254] In some embodiments, the functionalized sorbent has the formula (SI): M x L y F A a F B b (Eq. SI) is a functionalized MOF compound of the formula: M is a MOF metal or metal-containing cluster; L is a MOF linking agent; F A is at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof; F B is at least one functionalized ligand free of polyamines, comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof; x is a value ranging from 1 to 6, y is a value ranging from 1 to 6, a is a value greater than 0 and less than or equal to 2, b is a value in the range of 0 to 2.

[0255] In some embodiments, the functionalized sorbent comprises a metal-organic framework (MOF) in which a first amine of a polyamine is bound to a first metal site of the MOF, and optionally a second amine of the polyamine is bound to a second metal site of the MOF.

[0256] In some embodiments, the functionalized sorbent does not include a MOF.

[0257] In some embodiments, the functionalized sorbent comprises a non-MOF sorbent. In some embodiments, the functionalized sorbent comprises a mesoporous oxide support. In some embodiments, the functionalized sorbent comprises a mesoporous oxide support selected from the group consisting of silica, alumina, zirconia, and combinations thereof. In some embodiments, the functionalized sorbent comprises a porous polymer.

[0258] In some embodiments, the functionalized sorbent does not include non-MOFs.

[0259] In general, amine-functionalized MOFs tend to have better CO2 capacity, expressed as CO2 capture per weight of sorbent, such as gCO2 / g sorbent or mmolCO2 / g sorbent, under low CO2 concentrations, such as DAC-relevant conditions, compared to other sorbents. Non-MOFs, such as mesoporous silica and alumina, may potentially have lower cost and improved reaction kinetics compared to other sorbents.

[0260] Depending on the amine chosen, the amine can be physically impregnated or chemically grafted, with physical impregnation resulting in lower stability and chemical grafting resulting in higher stability but lower CO2 capacity.

[0261] One or more of reducing the sorbent particle size, increasing the sorbent aspect ratio, and aqueous sorbent synthesis results in sorbents with significantly improved CO2 uptake kinetics.

[0262] Generally, the sorbent can include any suitable particle size known in the art to support the functionalized sorbents described herein. In some embodiments, the sorbent has an average particle length of ≦5 μm. In some embodiments, the sorbent has an average particle length of ≦3 μm, ≦2.9 μm, ≦2.8 μm, ≦2.7 μm, ≦2.6 μm, ≦2.5 μm, ≦2.4 μm, ≦2.3 μm, ≦2.2 μm, ≦2.1 μm, ≦2 μm, ≦1.9 μm, ≦1.8 μm, ≦1.7 μm, ≦1.6 μm, ≦1.5 μm, ≦1.4 μm, ≦1.3 μm, ≦1.2 μm, ≦1.1 μm, ≦1 μm, ≦0.9 μm, ≦0.8 μm, ≦0.7 μm, ≦0.6 μm, ≦0.5 μm, ≦0.4 μm, ≦0.3 μm, ≦0.2 μm, or ≦0.1 μm. In some embodiments, the sorbent has an average particle length of ≧5 μm. In some embodiments, the sorbent has an average particle length of ≧3 μm, ≧2.9 μm, ≧2.8 μm, ≧2.7 μm, ≧2.6 μm, ≧2.5 μm, ≧2.4 μm, ≧2.3 μm, ≧2.2 μm, ≧2.1 μm, ≧2 μm, ≧1.9 μm, ≧1.8 μm, ≧1.7 μm, ≧1.6 μm, ≧1.5 μm, ≧1.4 μm, ≧1.3 μm, ≧1.2 μm, ≧1.1 μm, ≧1 μm, ≧0.9 μm, ≧0.8 μm, ≧0.7 μm, ≧0.6 μm, ≧0.5 μm, ≧0.4 μm, ≧0.3 μm, ≧0.2 μm, or ≧0.1 μm.

[0263] Generally, the sorbent can include any suitable aspect ratio known in the art to aid in the functionalized sorbents described herein. As used herein, aspect ratio is the ratio between the average width of the sorbent and the average length of the sorbent. In some embodiments, the sorbent has an aspect ratio in the range of about 0 to about 1. In some embodiments, the sorbent has an aspect ratio of ≦1, ≦0.9, ≦0.8, ≦0.7, ≦0.6, ≦0.5, ≦0.4, ≦0.3, ≦0.2, or ≦0.1. In some embodiments, the sorbent has an aspect ratio of ≧0.9, ≧0.8, ≧0.7, ≧0.6, ≧0.5, ≧0.4, ≧0.3, ≧0.2, ≧0.1, or ≧0.

[0264] In some embodiments, the particle size is the size of individual particles. Measuring the size of individual particles can be done according to any suitable means known in the art, such as by measuring particle size in SEM images.

[0265] In some embodiments, the particle size measurement is an average particle size measurement. The average particle size measurement may be performed according to any suitable means known in the art, such as by analyzing particle size distribution information.

[0266] In general, the particle size of the sorbent can be controlled, modified, or reduced according to any suitable technique known in the art to aid in the functionalization of sorbents described herein. In some embodiments, suitable techniques for controlling, modifying, or reducing particle size include mechanical comminution (e.g., grinding (mortar and pestle)), dry milling using a microfluidizer, wet milling, chemical size reduction (e.g., incorporating crystal growth inhibitors), acoustic cavitation, fluid cavitation, and combinations thereof.

[0267] Generally, the sorbent may be in any suitable form known in the art to support the functionalized sorbents described herein, hi some embodiments, the sorbent is in a form selected from the group consisting of a powder, a pellet, a composite, a composite mixed with a binder, a thin film, a coating, an aqueous coating, a packed bed, a column, a monolith, and combinations thereof.

[0268] Exemplary embodiments described herein include a sorption system. Generally, the sorption system can be any suitable sorption system known in the art that supports the functionalized sorbents described herein. In some embodiments, the sorption system includes a functionalized sorbent and, optionally, a binder. In some embodiments, the sorption system is disposed on a thin polymer film.

[0269] In some embodiments, the sorption system is in the form of a coating composition. The coating composition may be in the form of a solution, an emulsion, or a combination thereof. When in the form of a solution, the binder is water-soluble. When in the form of an emulsion, the binder is not water-soluble. The coating composition may include a binder and optionally at least one additive. In some embodiments, the at least one additive is selected from the group consisting of silica particles, clay particles, alumina particles, and combinations thereof. In some embodiments, the binder includes at least one water-based binder selected from the group consisting of a water-based epoxy, a water-based acrylic resin, a water-soluble polymer, and combinations thereof.

[0270] In some embodiments, the sorption system includes at least one contactor. In some embodiments, the sorption system includes more than one contactor. In some embodiments, the sorption system includes a contactor configured for an adsorption cycle and a contactor configured for a desorption cycle. The contactor may be any suitable contactor known in the art to support the functionalized sorbents described herein. In some embodiments, the sorbent is integrated into at least one channel of the contactor. In some embodiments, the contactor is made from the sorbent itself. In some embodiments, the contactor is coated with a sorption system. In some embodiments, the contactor includes more than one sorbent coating, with at least one sorbent coating as the sorption system.

[0271] In some embodiments, the sorption system includes a frame. The frame can be any suitable frame known in the art that supports the functionalized sorbents described herein. The frame can be contained within a contact body or between two contact bodies. The frame can be comprised of one member or more than one member. In some embodiments, the frame is an air frame. In some embodiments, the frame is in a configuration selected from the group consisting of a polygonal configuration, a rectangular configuration, a square configuration, a circular configuration, an asymmetric configuration, and combinations thereof. In some embodiments, the sorption system is mounted on the frame.

[0272] In some embodiments, the sorption system includes at least one concentrator. The concentrator may be any suitable concentrator known in the art that supports the functionalized sorbents described herein. The concentrator may be a passive or active concentrator.

[0273] In some embodiments, the sorption system includes at least one component configured to drive a fluid flow. The component configured to drive a fluid flow may be any suitable component configured to drive a fluid flow known in the art to support the functionalized sorbents described herein. In some embodiments, the component configured to drive a fluid flow is selected from the group consisting of a pump, a fan, and combinations thereof.

[0274] In some embodiments, the sorption system includes at least one component configured to alter temperature. The component configured to alter temperature may be any suitable component configured to alter temperature known in the art to aid in the functionalized sorbents described herein. In some embodiments, the component configured to alter temperature is selected from the group consisting of a heater, a cooler, and combinations thereof.

[0275] In some embodiments, the sorption system includes at least one component configured to transport a fluid. The component configured to transport a fluid may be any suitable component configured to transport a fluid known in the art to support the functionalized sorbents described herein. In some embodiments, the component configured to transport a fluid is selected from the group consisting of a pipe, a perforated pipe, a plastic perforated pipe, a polymer perforated pipe, a metal perforated pipe, a composite perforated pipe, and combinations thereof.

[0276] In general, the functionalized sorbent may be used according to any suitable purpose known in the art that facilitates utilization of the functionalized sorbents described herein. In some embodiments, the functionalized sorbent is used in a sorption system. In some embodiments, the functionalized sorbent is used in a carbon capture sorption system. In some embodiments, the functionalized sorbent is used in a moisture sorption system. In some embodiments, the functionalized sorbent is used in a carbon capture sorption system in the presence of water. In some embodiments, the functionalized sorbent is used for gas capture. In some embodiments, the functionalized sorbent is used for post-combustion capture of CO2 and / or direct air capture of CO2.

[0277] Exemplary embodiments described herein include methods of making sorption systems. Generally, the functionalized sorbents can be made according to any suitable synthetic method known in the art that supports the functionalized sorbents described herein.

[0278] In many embodiments, a method of making a sorption system includes making a sorbent and optionally functionalizing the sorbent with at least one functionalizing ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof.

[0279] In some embodiments, a method of making a sorption system includes functionalizing a sorbent with at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof. In some embodiments, a method of making a sorption system includes functionalizing a sorbent with at least two functionalizing ligands, each comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, wherein the polyamines comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof are different from each other. In some embodiments, a method of making a sorption system further includes functionalizing the sorbent with at least one functionalizing ligand that does not comprise a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof. In some embodiments, a method of making a sorption system includes controlling the ratio between at least one functionalized ligand that includes a polyamine that includes at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof, and at least one functionalized ligand that does not include a polyamine that includes at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0280] In some embodiments, the method of making the sorption system further includes annealing the functionalized sorbent. Annealing the sorption system may remove excess ligands. In some embodiments, annealing the functionalized sorbent includes annealing the functionalized sorbent at an elevated temperature. In some embodiments, annealing the sorbent includes annealing the sorbent at a temperature ranging from about 50°C to about 400°C. In some embodiments, annealing the sorbent includes annealing the sorbent at a temperature ranging from about 100°C to about 300°C. In some embodiments, annealing the sorbent includes annealing the sorbent at a temperature ranging from about 150°C to about 250°C.

[0281] 47 is an exemplary method flow diagram 4710. In this exemplary embodiment, method flow diagram 4710 illustrates exemplary steps of method embodiments described herein and is not intended to limit the method embodiments. In the exemplary embodiment, the method includes step 4712 of forming a mixture including a sorbent precursor, a crystal growth inhibitor, optionally a solvent, and optionally a non-solvent. The method also includes step 4714 of reacting the mixture. The sorbent has an average particle length of ≦3 μm.

[0282] Forming the mixture step 4712 may occur by any suitable means known in the art. In some embodiments, all of the ingredients are added at the same time. In some embodiments, at least one ingredient is added at a different time than the other ingredients.

[0283] In some embodiments, the sorbent precursor comprises a MOF linking agent and a MOF metal or metal-containing cluster. The sorbent precursor may be formed before the mixture is formed in step 4712 and added as a single component to the mixture, or it may be formed "in situ" in the mixture during the mixture formation step 4712. For example, the MOF linking agent may be separately deprotonated and then added, or it may be deprotonated "in situ." Similarly, the MOF metal or metal-containing cluster may be preformed and then added, or it may be formed "in situ."

[0284] In some embodiments, the solvent comprises an aqueous solvent. In some embodiments, the solvent comprises water. The use of an aqueous solvent offers several advantages. Specifically, the use of an aqueous solvent offers scalability, safety, cost, and waste disposal advantages compared to at least some known methods of preparing MOF compounds. In addition, MOF compounds prepared with an aqueous solvent are generally easier to purify, for example, via solvent washing, than the same MOF compounds prepared according to known methods. This improved purification stems from the relative ease of removing solvent molecules (e.g., water) from the MOF compounds described herein compared to the removal of strongly bound solvent molecules (e.g., DMF) used to prepare the same MOF compounds according to known methods. In addition, the purified MOF compounds are free of strongly bound solvent molecules that reduce gas uptake, surface area, and / or total pore volume. Finally, purification is improved by requiring less toxic purification methods.

[0285] In some embodiments, the solvent is an organic solvent. In some embodiments, the solvent is a mixture of an organic solvent and an aqueous solvent.

[0286] Generally, a non-solvent is a substance incapable of dissolving a given component of a solution or mixture. In some embodiments, the non-solvent is a liquid-based component included in the reaction mixture. In some embodiments, the non-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, the non-solvent is selected from the group consisting of organic solvents, aqueous solvents, and combinations thereof.

[0287] In some embodiments, the crystal growth inhibitor is selected from the group consisting of salicylic acid, 4-fluorosalicylic acid, 4,4'-biphenol, 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC), 2,2'-bipyridine-5,5'-dimethanol (BPYDM), benzoic acid, biphenol, bipyridine, and combinations thereof.

[0288] 48 is an exemplary method flow diagram 4810. In this exemplary embodiment, method flow diagram 4810 illustrates exemplary steps of method embodiments described herein and is not intended to limit the scope of the method embodiments. In the exemplary embodiment, the method includes step 4812 of forming a mixture including a sorbent, at least one functionalizing ligand including a polyamine including at least one oxygenated unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof, optionally at least one functionalizing ligand that does not include a polyamine including at least one oxygenated unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof, optionally a solvent, and optionally a non-solvent. The method also includes step 4814 of functionalizing the sorbent.

[0289] In some embodiments, functionalizing the sorbent step 4814 includes agitating the mixture.

[0290] In some embodiments, functionalizing the sorbent 4814 includes functionalizing the sorbent 4814 in the presence of an inert gas.

[0291] In some embodiments, functionalizing the sorbent 4814 comprises functionalizing the sorbent 3514 at a temperature ranging from about 0° C. to about 100° C. In some embodiments, functionalizing the sorbent 4814 comprises functionalizing the sorbent 3514 at a temperature ranging from about 20° C. to about 80° C. In some embodiments, functionalizing the sorbent 4814 comprises functionalizing the sorbent 3514 at a temperature ranging from about 20° C. to about 60° C.

[0292] In some embodiments, functionalizing the sorbent 4814 includes functionalizing the sorbent for a time ranging from about 1 minute to about 7 days 4814. In some embodiments, functionalizing the sorbent 4814 includes functionalizing the sorbent for a time ranging from about 1 hour to about 3 days 4814.

[0293] In some embodiments, the sorbent is desolvated prior to functionalization 4814. In some embodiments, the sorbent is dried prior to functionalization.

[0294] In some embodiments, the sorbent is annealed after functionalization 4814. In some embodiments, annealing the sorbent comprises annealing the sorbent at an elevated temperature. In some embodiments, annealing the sorbent comprises annealing the sorbent at a temperature in the range of about 50°C to about 400°C. In some embodiments, annealing the sorbent comprises annealing the sorbent at a temperature in the range of about 100°C to about 300°C. In some embodiments, annealing the sorbent comprises annealing the sorbent at a temperature in the range of about 150°C to about 250°C.

[0295] In some embodiments, the solvent is an organic solvent. In some embodiments, the solvent is an aqueous solvent. In some embodiments, the solvent is a mixture of an organic solvent and an aqueous solvent.

[0296] Generally, a non-solvent is a substance incapable of dissolving a given component of a solution or mixture. In some embodiments, the non-solvent is a liquid-based component included in the reaction mixture. In some embodiments, the non-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, the non-solvent is selected from the group consisting of organic solvents, aqueous solvents, and combinations thereof.

[0297] In some embodiments, the non-solvent aids in functionalization. In some embodiments, the selectivity of functionalization is controlled by relative solubility. For example, one or more of the sorbents or amines may possess different solubility in the liquid-based reaction mixture compared to another sorbent or amine, or the functionalized sorbent. In this way, relative solubility introduces limiting reaction and / or reagent characteristics.

[0298] In many embodiments, the methods may also include any additional suitable processing steps known in the art that facilitate the success of the methods described herein. Such processing steps may include, but are not limited to, washing, drying, filtering, purifying, separating, centrifugation, and any combination thereof. In some embodiments, the methods further include washing the functionalized sorbent. In some embodiments, the methods further include purifying the functionalized sorbent. In some embodiments, the purification includes distillation, vacuum distillation, and / or the use of heat.

[0299] Exemplary embodiments described herein include methods for modifying functionalized sorbents.

[0300] 49 shows an exemplary method flow chart 4910. In this exemplary embodiment, method flow chart 4910 illustrates exemplary steps of an embodiment of a method described herein and is not intended to limit the embodiments of the method. In the exemplary embodiment, the method includes step 4912 of forming a mixture including a reactant and a sorbent functionalized with at least one functionalizing ligand that does not comprise a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof. The method also includes step 4914 of reacting the reactant with a sorbent functionalized with at least one functionalizing ligand that does not comprise a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof to produce a sorbent functionalized with at least one functionalizing ligand that does not comprise a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0301] Generally, the reactant can include any suitable reactant known in the art to aid in the functionalization of the sorbents described herein. In many embodiments, the reactant includes at least one functional group capable of reacting with a polyamine to form at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0302] In some embodiments, the reactant comprises at least one functional group selected from the group consisting of an epoxide group, an epoxide group comprising a fluorine atom, a three-membered ring epoxide group, a monoepoxide group, a diepoxide group, an oxetane group, a four-membered ring oxetane group, and combinations thereof.

[0303] In some embodiments, the reactant is selected from the group consisting of ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 2,2,2-(trifluoroethyl)oxirane, diepoxybutane, 4-aminooxetane, 4-(aminomethyl)oxetane, and combinations thereof.

[0304] In some embodiments, reacting step 4914 includes agitating the mixture.

[0305] In some embodiments, reacting 4914 includes reacting 4914 in the presence of an inert gas.

[0306] In some embodiments, reacting 4914 includes reacting 4914 at a temperature ranging from about 0° C. to about 100° C. In some embodiments, reacting 4914 includes reacting 4914 at a temperature ranging from about 20° C. to about 80° C. In some embodiments, reacting 4914 includes reacting 4914 at a temperature ranging from about 20° C. to about 60° C.

[0307] In some embodiments, reacting 4914 includes reacting for a time period ranging from about 1 minute to about 7 days 4914. In some embodiments, reacting 4914 includes reacting for a time period ranging from about 1 hour to about 3 days 4914.

[0308] In some embodiments, the sorbent is desolvated prior to reacting step 4914. In some embodiments, the sorbent is dried prior to reacting step 4914.

[0309] In some embodiments, the sorbent is annealed after reacting 4914. In some embodiments, annealing the sorbent includes annealing the sorbent at an elevated temperature. In some embodiments, annealing the sorbent includes annealing the sorbent at a temperature in the range of about 50°C to about 400°C. In some embodiments, annealing the sorbent includes annealing the sorbent at a temperature in the range of about 100°C to about 300°C. In some embodiments, annealing the sorbent includes annealing the sorbent at a temperature in the range of about 150°C to about 250°C.

[0310] In some embodiments, reacting 4914 includes reacting 4914 in the presence of a solvent or non-solvent.

[0311] In some embodiments, the solvent is an organic solvent. In some embodiments, the solvent is an aqueous solvent. In some embodiments, the solvent is a mixture of an organic solvent and an aqueous solvent.

[0312] Generally, a non-solvent is a substance incapable of dissolving a given component of a solution or mixture. In some embodiments, the non-solvent is a liquid-based component included in the reaction mixture. In some embodiments, the non-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, the non-solvent is selected from the group consisting of organic solvents, aqueous solvents, and combinations thereof.

[0313] In some embodiments, the non-solvent aids in functionalization. In some embodiments, the selectivity of functionalization is controlled by relative solubility. For example, one or more of the sorbents or amines may possess different solubility in the liquid-based reaction mixture compared to another sorbent or amine, or the functionalized sorbent. In this way, relative solubility introduces limiting reaction and / or reagent characteristics.

[0314] In many embodiments, the method may also include any additional suitable processing steps known in the art that facilitate the success of the methods described herein. Such processing steps may include, but are not limited to, washing, drying, filtering, purifying, separating, centrifugation, and any combination thereof. In some embodiments, the method further includes washing the functionalized sorbent. In some embodiments, the method further includes purifying the functionalized sorbent. In some embodiments, the purifying step includes distillation, vacuum distillation, and / or the use of heat.

[0315] SUMMARY OF THE INVENTION Exemplary embodiments described herein include a method for recovering at least one gas.

[0316] FIG. 50 shows an exemplary method flow diagram 5010. In this exemplary embodiment, method flow diagram 5010 illustrates exemplary method steps of embodiments of methods described herein and is not intended to limit the scope of the method embodiments. The method includes step 5012 of receiving a gas source comprising at least one gas in a functionalized sorbent, the functionalized sorbent comprising a sorbent and at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof. In some embodiments, the functionalized sorbent includes at least two functionalizing ligands, each comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, wherein the polyamines comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof are different from each other. In some embodiments, the functionalized sorbent further includes at least one functionalizing ligand that does not comprise a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof. The method also includes recovering a quantity of at least one gas with the functionalized sorbent 5014. The sorbent may have an average particle length of ≦3 μm.

[0317] In some embodiments, the method includes (I) receiving 5012 a gas source comprising at least one gas in a functionalized sorbent, the functionalized sorbent comprising a sorbent and at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof; and (II) recovering 5014 a quantity of the at least one gas with the functionalized sorbent.

[0318] Generally, the gas source may be any suitable gas source known in the art that facilitates the methods described herein. In some embodiments, the gas source is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0319] Generally, the at least one gas may be any suitable gas known in the art that facilitates the methods described herein, hi some embodiments, the at least one gas is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0320] In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 100% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 40% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 15% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount greater than 10% (v / v).

[0321] In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 100 ppmv to about 1000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 200 ppmv to about 1000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 300 ppmv to about 5000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 200 ppmv to about 500 ppmv.

[0322] In some embodiments, the at least one gas does not include water vapor.

[0323] In some embodiments, at least one gas contains water vapor. In some embodiments, at least one gas contains water vapor in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, at least one gas contains water vapor in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, at least one gas contains water vapor in an amount ranging from about 0.5% (v / v) to about 15% (v / v). In some embodiments, at least one gas contains water vapor in an amount ranging from about 0.5% (v / v) to about 4% (v / v). In some embodiments, at least one gas contains water vapor in an amount ranging from about 4% (v / v) to about 15% (v / v).

[0324] In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v) and in the presence of water vapor. In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v) and in the presence of water vapor. In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v) and in the presence of water vapor. In some embodiments, at least one gas is present in the source gas in an amount greater than about 10% (v / v) and in the presence of water vapor. In some embodiments, water vapor is present in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.5% (v / v) to about 10% (v / v).

[0325] In some embodiments, recovering 5014 a quantity of the at least one gas with the functionalized sorbent comprises adsorbing the quantity of the at least one gas with the functionalized sorbent. In some embodiments, recovering 5014 a quantity of the at least one gas with the functionalized sorbent comprises adsorbing the quantity of the at least one gas with the functionalized sorbent in the presence of water vapor.

[0326] In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 1% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 10% (v / v) to about 90% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 20% (v / v) to about 80% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 30% (v / v) to about 70% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 40% (v / v) to about 60% (v / v) of the at least one gas present in the source gas.

[0327] In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 1% (v / v) to about 25% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 1% (v / v) to about 20% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 1% (v / v) to about 15% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 1% (v / v) to about 10% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 1% (v / v) to about 5% (v / v) of the at least one gas present in the source gas.

[0328] In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 80% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 85% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 90% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas recovered 5014 by the functionalized sorbent ranges from about 95% (v / v) to about 100% (v / v) of the at least one gas present in the source gas.

[0329] In some embodiments, the source gas is reformulated to vary the amount of water vapor. In some embodiments, varying the amount of water vapor comprises increasing the amount of water vapor. In some embodiments, varying the amount of water vapor comprises decreasing the amount of water vapor. In some embodiments, increasing the amount of water vapor comprises adding or injecting water vapor into the source gas. In some embodiments, decreasing the amount of water vapor comprises removing water vapor from the source gas by evaporation, condensation, and / or pre-adsorption. In some embodiments, varying the amount of water vapor comprises exhaust gas recirculation (EGR) and / or blending.

[0330] In many embodiments, the functionalized sorbent, the source gas, the at least one gas, or a combination thereof is at a predetermined temperature. The temperature of each can be varied to facilitate the methods described herein. The temperature of each can have a uniform temperature curve, a graded temperature curve, a discrete temperature curve, or a combination thereof.

[0331] In some embodiments, the method includes an adsorption cycle. In some embodiments, the method includes a desorption cycle. In some embodiments, at least one of the functionalized sorbent, the source gas, the at least one gas, or a combination thereof is at a temperature ranging from about −40° C. to about 150° C. during the gas adsorption cycle. In some embodiments, at least one of the functionalized sorbent, the source gas, the at least one gas, or a combination thereof is at a temperature ranging from about 60° C. to about 250° C. during the gas desorption cycle. Each adsorption module or sub-module can have a uniform temperature profile, a graded temperature profile, or a discrete temperature profile.

[0332] In some embodiments, the method includes controlling the temperature. The temperature can be controlled for the functionalized sorbent, the source gas, the at least one gas, or a combination thereof.

[0333] SUMMARY OF THE INVENTION Exemplary embodiments described herein include a method for collecting at least one gas from a gas source.

[0334] Figure 51 illustrates an exemplary method flow diagram 5110. In this exemplary embodiment, method flow diagram 5110 illustrates exemplary method steps of embodiments of methods described herein and is not intended to limit the scope of the method embodiments. The method includes step 5112 of receiving a gas source comprising at least one gas in a functionalized sorbent, the functionalized sorbent comprising a sorbent and at least one functionalizing ligand comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof. In some embodiments, the functionalized sorbent includes at least two functionalizing ligands, each comprising a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, wherein the polyamines comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof are different from each other. In some embodiments, the functionalized sorbent further includes at least one functionalizing ligand that does not comprise a polyamine comprising at least one oxygenated unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof. The method also includes recovering 5114 a quantity of the at least one gas with the functionalized sorbent. The method also includes 5116 releasing the at least one gas from the functionalized sorbent. The sorbent can have an average particle length of ≦3 μm.

[0335] In some embodiments, the method includes (I) receiving 5112 a gas source comprising at least one gas in a functionalized sorbent, the functionalized sorbent comprising a sorbent and at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof; (II) recovering 5114 a quantity of the at least one gas with the functionalized sorbent; and (III) releasing 5116 the at least one gas from the functionalized sorbent.

[0336] In some embodiments, releasing 5116 the at least one gas from the functionalized sorbent comprises purging the at least one gas from the functionalized sorbent with a purge gas. In some embodiments, releasing 5116 the at least one gas from the functionalized sorbent comprises subjecting the functionalized sorbent to a change in temperature or pressure.

[0337] In some embodiments, the at least one gas is released from the functionalized sorbent to the receiving gas 5116. In some embodiments, the receiving gas is selected from the group consisting of air, N2, steam, and combinations thereof. In some embodiments, the receiving gas is removed from the presence of the functionalized sorbent after receiving the at least one gas. In some embodiments, the receiving gas has a higher concentration of the at least one gas compared to the source gas. [Example]

[0338] Without further elaboration, it is believed that one skilled in the art, having access to the foregoing description, can utilize the present invention to its fullest extent. EXAMPLES Accordingly, the following examples are merely illustrative and are not intended to limit the present disclosure in any way. The starting materials in the following examples may not necessarily have been prepared by the particular preparative workup whose procedures are described in other examples. Also, any numerical range recited should be understood to include all values ​​from the lower value to the upper value. For example, if a range is stated as 10 to 50, values ​​such as 12 to 30, 20 to 40, or 30 to 50, etc., are expressly recited herein. These are merely examples of what is specifically intended, and all possible combinations of numerical values ​​between and including the lowest and highest recited values ​​are considered to be expressly recited in this application.

[0339] (MOF sorbent synthesis)

[0340] Example A1. General procedure for MOF and sorbent synthesis.

[0341] First, MOFs are synthesized via aqueous preparation and washed three times with water and three times with isopropyl alcohol. The reaction can be carried out using either a non-aqueous solvent, such as a dimethylformamide (DMF) / methanol (MeOH) mixture, an aqueous solvent, or both, as disclosed in PCT / US2022 / 082243 (Patent Document 2), the contents of which are incorporated by reference. The material is then dried via vacuum filtration to yield approximately 70% to 75% solvated material. To prepare the material for formulation, it is desolvated overnight in a vacuum oven at 120°C to reduce the alcohol content to 0.5 to 1 equivalent of isopropyl alcohol (IPA) per metal site, protecting the released metal sites from oxidation while simultaneously removing excess solvent from the MOF pores. As shown in Figure 1, 1 HNMR (e.g., Mg2(dobpdc)1(alcohol) x The exact molar amount of MOF can be determined by determining how much residual solvent is still present in the MOF via the reaction. Thus, adding 1 to 4 equivalents of amine in a non-polar solvent can result in a composition of Mg2(dobpdc)1(amine). x Figure 2 shows an SEM image of exemplary MOF-274 (specimen ID #A2111) prepared according to standard aqueous procedures.

[0342] Example A2 General method for analyzing amine content via NMR.

[0343] To digest the amine-tagged MOF, 10 mg of material was added to a vial along with 20 μL of 35% DCl in DO, 200 μL of DO, and 600 μL of DMSO-d. The vial was sonicated to dissolve the structure. 1 HNMR was performed. The structural ligand peak (H4dobpdc) 1 Loading was determined by comparing 1 H NMR integrals to the amine peak.

[0344] [Example A3] Reduction of particle size.

[0345] The size or length of the rod-shaped crystals can be reduced by many options, including but not limited to, mechanical comminution such as crushing, using a microfluidizer, dry or wet milling, or through chemical means such as the incorporation of crystal growth inhibitors. Table 1 summarizes the particle size and aspect ratio of MOF-274 prepared according to several embodiments.

[0346] [Table 1]

[0347] Example A4 General synthesis procedure for small diameter MOF-274 using crystal growth inhibitors.

[0348] Mg2(dobpdc) was first synthesized by dissolving x moles of H4dobpdc, y moles of synthetic crystal growth inhibitor, and (x x 4 + y x 2) moles of NaOH in water by heating to 60 °C. Exemplary synthetic crystal growth inhibitors include, but are not limited to, salicylic acid (SA), 4-fluorosalicylic acid (FSA), 4,4'-biphenol (BP), 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC), and 2,2'-bipyridine-5,5'-dimethanol (BPYDM). The molar number of crystal growth inhibitors can range from 0.1 mol% to 50 mol% relative to 99.9 mol% to 50 mol% of H4dobpdc. A deprotonated solution of the linking agent and crystal growth inhibitor was added with NO3 - , Cl - , Br - , SO4 -2 , OAc - , O -2 , Otf - Mg with one of the following as a counter anion 2+ Add an aqueous solution of salt to make a solution. Mg 2+The salt can be added rapidly (e.g., <1 min) or dropwise over an extended period (e.g., >1 h). The heat is increased to 97°C and refluxed under N2 for 12 to 16 h. The white precipitate is washed three times with water and three times with isopropyl alcohol, solvated, and stored for later use.

[0349] Example A5: Exemplary synthesis procedure for small-diameter MOF-274 using salicylic acid as a crystal growth inhibitor.

[0350] Mg2(dobpdc) was prepared on a 300 mL scale. First, the linking agent, crystal growth inhibitor, and base were added to a 500 mL round-bottom flask and heated to dissolve in water. In this example, sodium hydroxide (76 mmol, 3.04 g), H4dobpdc (18 mmol, 4.94 g), and salicylic acid (2 mmol, 0.276 g) were dissolved in water (220 mL) in a flask by stirring and heating to 60 °C under N2 until the solution became clear. Next, Mg(NO3)2 hexahydrate (45 mmol, 11.54 g) was dissolved in 80 mL of water in a separate container and rapidly added to the deprotonated linking agent solution to precipitate the MOF. This mixture was then heated to 97 °C under gentle reflux at ambient pressure in an open-necked flask for 12 to 16 hours. The reaction produces the MOF compound Mg2(dobpdc)(salicylate). x was subsequently washed three times with water and three times with isopropanol and stored in alcohol. For surface area measurements, the material was activated at 250 °C to obtain the highest loading. The reaction yielded between 4.2 g and 4.7 g (72% to 81% yield) of Mg2(dobpdc)(salicylate) for each of the separate batches. x was produced. The material was desolvated at 85°C and can be formulated as standard MOF-274 in the usual way. Figure 3 shows SEM images of exemplary MOF-274 made with salicylic acid (left) and fluorosalicylic acid (right) as crystal growth inhibitors.

[0351] Example A6: Exemplary synthesis procedure for small-diameter MOF-274 using 4,4'-biphenol as a crystal growth inhibitor.

[0352] Mg2(dobpdc) was prepared in a 20 mL scale. First, the linking agent, crystal growth inhibitor, and base were added to a 20 mL scintillation vial and heated to dissolve in water. In this example, sodium hydroxide (4 mmol, 0.160 g), H4dobpdc (0.9 mmol, 0.247 g), and 4,4′-biphenol (0.1 mmol, 0.019 g) were dissolved in water (10 mL) in a vial by stirring and heating to 60 °C until the solution became clear. Next, Mg(NO3)2 hexahydrate (2 mmol, 0.512 g) was dissolved in 5 mL of water in a separate container and rapidly added to the deprotonated linking agent solution to precipitate the MOF. This mixture was then heated to 97 °C under gentle reflux at ambient pressure in the vial for 12 to 16 hours. The reaction produced the MOF compound Mg2(dobpdc)(BP) x was subsequently washed three times with water and three times with isopropanol and stored in alcohol. For surface area measurements, the material was activated at 250 °C to obtain the highest uptake. The reaction afforded Mg2(dobpdc)(BP) in yields between 37% and 72% based on the amount of inhibitor used. x The material was desolvated at 85 °C and can be formulated as standard MOF-274 in the usual way. Figure 4 shows the powder X-ray diffraction spectrum of MOF-274 synthesized using 4,4'-biphenol as a crystal growth inhibitor, which indicates that the MOF-274 phase is preserved at 50 mol% BP loading. The incorporation of 4,4'-biphenol clearly reduces the particle size, as shown in Figure 5.

[0353] [Table 2]

[0354] Example A7: Exemplary synthesis procedure for small-diameter MOF-274 using BPYDC as a crystal growth inhibitor.

[0355] Mg2(dobpdc) was prepared in a 20 mL scale. First, the linking agent, crystal growth inhibitor, and base were added to a 20 mL scintillation vial and heated to dissolve in water. In this example, sodium hydroxide (4 mmol, 0.160 g), H4dobpdc (0.9 mmol, 0.247 g), and 2,2′-bipyridine-5,5′-dicarboxylic acid (0.1 mmol, 0.024 g) were dissolved in water (10 mL) in a vial by stirring and heating to 60 °C until the solution became clear. Next, Mg(NO3)2 hexahydrate (2 mmol, 0.512 g) was dissolved in 5 mL of water in a separate container and rapidly added to the deprotonated linking agent solution to precipitate the MOF. This mixture was then heated to 97 °C under gentle reflux at ambient pressure in the vial for 12 to 16 hours. The reaction produced the MOF compound Mg2(dobpdc)(BPYDC) x was subsequently washed three times with water and three times with isopropanol and stored in alcohol. For surface area measurements, the material was activated at 250 °C to obtain the highest uptake. The reaction yielded Mg2(dobpdc)(BPYDC) in yields between 68% and 74% based on the amount of inhibitor used. x was produced. The material was desolvated at 85 °C and can be formulated as standard MOF-274 in the usual way. Figure 5 shows the powder X-ray diffraction spectrum of MOF-274 synthesized using 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC) as a crystal growth inhibitor. The MOF-274 phase is retained up to 50 mol% loading of BPYDC. The incorporation of BPYDC clearly reduces the particle size, as shown in Figure 6.

[0356] [Table 3]

[0357] Example A8: Exemplary synthesis procedure for small-diameter MOF-274 using BPYDM as a crystal growth inhibitor.

[0358] Mg2(dobpdc) was prepared in a 20 mL scale. First, the linking agent, crystal growth inhibitor, and base were added to a 20 mL scintillation vial and heated to dissolve in water. In this example, sodium hydroxide (4 mmol, 0.160 g), H4dobpdc (0.9 mmol, 0.247 g), and 2,2′-bipyridine-5,5′-dimethanol (0.1 mmol, 0.022 g) were dissolved in water (10 mL) in a vial by stirring and heating to 60 °C until the solution became clear. Next, Mg(NO3)2 hexahydrate (2 mmol, 0.512 g) was dissolved in 5 mL of water in a separate container and rapidly added to the deprotonated linking agent solution to precipitate the MOF. This mixture was then heated to 97 °C under gentle reflux at ambient pressure in the vial for 12 to 16 hours. The reaction produced the MOF compound Mg2(dobpdc)(BPYDM) x was subsequently washed three times with water and three times with isopropanol and stored in alcohol. For surface area measurements, the material was activated at 250 °C to obtain the highest uptake. The reaction afforded Mg2(dobpdc)(BPYDM) in yields between 53% and 81% based on the amount of inhibitor used. x Figure 7 shows the powder X-ray diffraction spectrum of MOF-274 synthesized using 2,2'-bipyridine-5,5'-dimethanol (BPYDM) as a crystal growth inhibitor. The particle length of MOF-274 initially decreases with increasing BPYDM incorporation. However, further increase in BPYDM loading leads to an increase in particle length and a decrease in aspect ratio, as shown in Figure 8.

[0359] [Table 4]

[0360] Example A9: Example of bare MOF: improved reaction kinetics of CO2 uptake.

[0361] Comparative Example 1 (Comparative Example 1) Following the general procedure described in Example A1, a MOF specimen of the basic structure with ID A2173 was prepared using aqueous solvent (H2O).

[0362] Comparative Example 2 (Comparative 2) A MOF specimen of the basic structure with ID A315B was prepared following the general procedure described in Example A5, but using the non-aqueous solvent DMF.

[0363] [Invention Example 1] (Invention 1) Following the general procedure described in Example A1, a MOF specimen of the basic structure with ID A2177 was prepared using aqueous solvent (H2O).

[0364] Inventive Example 2 (Inventive Example 2) Following the general procedure described in Example A5, but using salicylic acid (SA) as a crystal growth inhibitor and aqueous solvent (HO), a MOF specimen with an ID of A316 was prepared.

[0365] [Invention Example 3] (Invention 3) Following the general procedure described in Example A5, but using salicylic acid (SA) as a crystal growth inhibitor and aqueous solvent (HO), a MOF specimen with an ID of A39C was prepared.

[0366] Table 2 (Table 5) summarizes the synthesis details, particle size, aspect ratio, and CO2 uptake performance measured under a dry CO2 concentration of 4.5v%. The combination of decreasing particle size, increasing aspect ratio, and aqueous MOF synthesis clearly significantly improves the CO2 uptake kinetics of the MOFs.

[0367] [Table 5]

[0368] Polyamine-functionalized solid sorbent materials having oxygen-containing units selected from carbonyl units, hydroxyl units, and combinations thereof.

[0369] Example B1 General procedure for making oxygenated amines.

[0370] Oxygenated amines can be prepared by direct synthesis. Non-limiting approaches to direct synthesis include modifying non-oxygenated amines before MOF functionalization and modifying non-oxygenated amines after MOF functionalization. These approaches of modifying non-oxygenated amines before and after MOF functionalization are referred to as pre-compound modification (PLM) and post-synthesis modification (PSM), respectively.

[0371] Example B2 General method for pre-formulation modification (PLM) of functionalized amines with epoxides.

[0372] In a 20 mL scintillation vial, one equivalent of amine was placed in a 17 wt% aqueous solution of methanol. Then, 0.01 to 4 equivalents of functionalized oxirane (epoxide) were added to the methanol solution. The solution was stirred overnight at room temperature. The solvent was removed via rotary evaporation after at least 12 hours. The amine was dried in a vacuum oven at 80 °C for 4 hours. NMR samples were prepared in deuterated methanol (CD3OD) to determine the functionalization ratio. For example, 1 equivalent of spermine (2 mmol, 0.405 g) was added to a 20 mL scintillation vial and dissolved in 3 mL of methanol. Then, 1 equivalent of 1,2-epoxybutane (2 mmol, 174 μL) was added, and the solution was stirred at room temperature for 18 hours. The methanol was removed via rotary evaporation to produce a quantitative yield of 0.27 1,2-epoxybutane:spermine.

[0373] Example B3: Typical formulation of PLM amines containing secondary alcohol units (eg via epoxides).

[0374] The following examples were prepared using mechanically ground MOF [Mg2(dobpdc)] with an average particle size of 0.48 μm (D50) as measured by a Malvern Zetasizer unless otherwise noted. Exemplary amines containing secondary alcohol units were prepared by reacting the amine with an epoxide through ring opening. Amines containing secondary alcohol units can also be prepared by other means, such as by direct synthesis.

[0375] A 20 mL scintillation vial was charged with 1 to 2.2 equivalents of functionalized amine at an O / N ratio of 0.01 to 1, dissolved in 5 mL of toluene, and then desolvated overnight in a vacuum oven at 120 °C with 1 equivalent of Mg(dobpdc)(IPA). x was added to the vial. The suspension was then heated to 60°C on a water heater and stirred at 300-400 rpm overnight. The material was cooled to room temperature and transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was dried in a vacuum oven at 120°C overnight to obtain β-alcohol functionalized amine-incorporated Mg2(dobpdc). If excess or surface amines are present, these can be removed by annealing at elevated temperatures. In addition, annealing can also potentially help the amine chains rearrange to eventually reach a stable configuration and bond to the metal site. The material was then digested to obtain 1 H NMR was used to determine the initial composition and the final composition after annealing.

[0376] Example B4: General method for analyzing amine content via NMR.

[0377] To digest the amine-tagged MOF, 10 mg of material was added to a vial along with 20 μL of 20% deuterium chloride (DCl) in heavy water (DO), 200 μL of DO, and 600 μL of DMSO-d. The vial was sonicated to dissolve the structure. 1 HNMR was performed. The structural ligand peak (H4dobpdc)1 The loading was determined by comparing the H NMR integrals to the amine peak. In the example spectrum shown in Figure 9 for GE5-A369, all of the ligand peaks at δ 7.9 ppm to 7.0 ppm were integrated to give 2H. The peaks corresponding to spermine at δ 1.65 ppm and 1.93 ppm were integrated to give a total of 8.22. Dividing the total integral by the theoretical number of protons (8) gave the ratio of loading product to one ligand, Mg2(dobpdc)(spermine). 1.01 This becomes:

[0378] Example B5 General method for analyzing oxygen to amine (O / N) ratio using NMR.

[0379] Typically, the functionalized amine is dissolved in 600 μL of CD3OD. 1 The oxygen to nitrogen ratio was determined based on the parent amine via H NMR. In the case of the NMR in Figure 10, the peak at 1.66 ppm was assigned to 4H (c). The amount of functionalization can be determined by the CH peak at δ 0.96 ppm (a) or the hydrogen attached to the beta (β)-alcohol at δ 3.58 ppm (e). Epoxide functionalization ratio (O) = (integral of CH3 peak) / (theoretical integral) = 3.24 / 3 = 1.08 Epoxide functionalization ratio (O) = (Integral of hydrogen [β alcohol] peak) / (Theoretical integral) = 1.06 / 1 = 1.06 O / N ratio = (ratio of epoxide functionalization [O]) / (number of amines [N]) =1.08 / 4 or 1.06 / 4 = 0.27 (O / N)

[0380] Example B6 General method for pre-formulation modification (PLM) of functionalized amines with oxetanes.

[0381] A 20 mL scintillation vial was charged with 1 equivalent of amine and 0.01 to 4 equivalents of functionalized oxetane, dissolved in 3 mL of anhydrous toluene. Then, 0.01 to 4 equivalents of a lanthanide-based Lewis acid catalyst, such as ytterbium(III) trifluoromethanesulfonate [Yb(OTf)3], was added and stirred at 80 °C for 24 to 48 hours. The product precipitated from the solvent to form a viscous liquid. The solvent was decanted, and 5 mL of DI water was added to dissolve the product and precipitate the catalyst by-product. The solution was filtered, and the aqueous layer was removed via rotary evaporation. The amine was dried in a vacuum oven at 120 °C for 24 hours. NMR samples were prepared in deuterium oxide (DO) to determine the functionalization ratio.

[0382] The reaction formula is shown below.

[0383] [ka]

[0384] For example, unsymmetrical β-methylhydroxyltetraamines (2-4-3 or 2-3-4 carbon spacers) were synthesized via ring-opening and reaction of 4-aminooxetane with spermidine. One equivalent of spermidine (2 mmol, 314 μL) and one equivalent of 4-aminooxetane (2 mmol, 140 μL) were dissolved in 3 mL of anhydrous toluene in a 20 mL scintillation vial. Next, 0.5 equivalents of Yb(OTf)3 (1 mmol, 0.620 g) were added to the vial and stirred at 80 °C for 24 h. The toluene was decanted, and 5 mL of DI water was added to dissolve the product and precipitate the catalyst by-products. The precipitate was filtered through a filter disk, and the aqueous layer was reduced in volume on a rotary evaporator. The β-methylhydroxyltetraamine was then dried in a vacuum oven at 120° C. for 24 hours to produce the product in 92% yield (FIG. 11).

[0385] [Example B7] Synthesis of hexanoyl chloride-modified spermine.

[0386] In a 20 mL scintillation vial, spermine (0.5 g, 2.47 mol) was dissolved in a dichloromethane / toluene (4 mL / 1 mL) solvent mixture and cooled to 0 °C. To the cooled reaction mixture, hexanoyl chloride (HC) (0.332 g, 2.47 mol) was added dropwise, resulting in the formation of a white precipitate. After 30 min, the ice bath was removed, and the reaction mixture was left stirring at room temperature overnight. After the reaction, the solvent was evaporated to dryness to give the product as the protonated salt of HC:spermine. This salt was used in the next step without purification.

[0387] The reaction formula is shown below.

[0388] [ka]

[0389] The as-synthesized protonated salt (0.757 g, 0.0025 mol) was dissolved in 3 mL of methanol along with potassium hydroxide (KOH) (0.42 g, 0.0075 mol). After stirring overnight at room temperature, the solvent was evaporated under vacuum. To remove the remaining potassium chloride (KCl) salt, the resulting solid was further treated with tetrahydrofuran (THF), and the resulting residual salt was filtered, after which the solvent was evaporated under vacuum. The product was obtained in 94% yield.

[0390] Example B8 General method for analyzing oxygen to amine (O / N) ratio of hexanoyl chloride (HC) modified amines by NMR.

[0391] Typically, the functionalized amine is dissolved in 600 μL of CD3OD. 1 The oxygen-to-nitrogen ratio was determined based on the parent amine via H NMR. In the case of the NMR in Figure 12, the peak between 2.6 ppm and 2.7 ppm was set to an integration value of 10, as highlighted by one of the blue circles. The amount of functionalization can be determined by the CH peak at δ 0.94 ppm. Based on the above equation, the O / N ratio is approximately 0.38.

[0392] Example B9: Exemplary functionalized sorbent materials.

[0393] Some exemplary sorbent materials functionalized with different amines are shown in Table 3.

[0394] [Table 6]

[0395] [Example B10] Synthesis of GE296-A366A.

[0396] A 20 mL scintillation vial was charged with 1.2 equivalents of 1,2-epoxybutane (EB) 0.25:spermine (0.1229 g, 0.43 mmol) dissolved in 5 mL of toluene. 0.160 g (1 equivalent, 0.36 mmol) of Mg(dobpdc)(IPA) was then desolvated overnight in a vacuum oven at 120 °C. 2.05 was added to the vial. The suspension was then heated to 60°C on a water heater and stirred at 300-400 rpm overnight. The material was cooled to room temperature and transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was dried in a vacuum oven at 120°C overnight to give 0.201 g of GE296. (85% yield, Mg2(dobpdc)(0.22EB spermine) 1.01 )

[0397] [Example B11] Synthesis of GE301-A370A.

[0398] A 20 mL scintillation vial was charged with 1.5 equivalents of 1,2-epoxyoctane (EO) 0.25:spermine (0.1795 g, 0.54 mmol) dissolved in 5 mL of toluene. 0.160 g (1 equivalent, 0.36 mmol) of Mg(dobpdc)(IPA) was then desolvated overnight in a vacuum oven at 120 °C. 2.05was added to the vial. The suspension was then stirred at 300-400 rpm overnight at 17°C on a water heater. The material was cooled to room temperature and transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was dried in a vacuum oven at 120°C overnight to give 0.248 g of GE301 (84% yield, Mg2(dobpdc)(0.17EO:spermine) 1.04 ).

[0399] [Example B12] Synthesis of GE308-A385B.

[0400] A 20 mL scintillation vial was charged with 1.5 equivalents of (2,2,2-trifluoroethyl)oxirane (TFEO) 0.46:N,N'-bis(2-aminoethyl)-1,3-propanediamine (0.1555 g, 0.54 mmol) dissolved in 5 mL of toluene. 0.160 g (1 equivalent, 0.36 mmol) of Mg2(dobpdc)(IPA) was then desolvated overnight in a vacuum oven at 120 °C. 2.05 was added to the vial. The suspension was then heated to 60°C on a water heater and stirred at 300-400 rpm overnight. The material was cooled to room temperature and transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was dried in a vacuum oven at 120°C overnight to give 0.219 g of GE308 (81% yield, Mg2(dobpdc)(0.36TFEO2-3-2) 1.06 ).

[0401] [Example B13] Synthesis of GE314-A3107.

[0402] The MOF used to make GE314 was prepared using salicylic acid as a crystal growth inhibitor and had an average particle size of 0.24 μm as determined by a Malvern Zetasizer. A 250 mL round-bottom flask was charged with 1.2 equivalents of 1,2-epoxybutane (EB) 0.10:N,N'-bis(2-aminomethyl)-1,3-propanediamine (2.149 g, 10.9 mmol), hereafter referred to as "amine 2-3-2," dissolved in 90 mL of toluene. 4.5 g (1 equivalent, 9.1 mmol) of the MOF Mg2(dobpdc)(IPA) was then desolvated overnight in a vacuum oven at 120 °C. 2.9 was added to the flask. The suspension was then brought to 60°C in an oil bath and stirred at 300-400 rpm under N2 overnight. The material was cooled to room temperature and filtered via vacuum filtration. The material was collected and dried in a vacuum oven at 120°C overnight to give 4.71 g of GE314 (86% yield, Mg2(dobpdc)(0.11EB:2-3-2) 1.12 ).

[0403] Example B14: Typical formulation of PLM amines containing primary alcohol units (eg via oxetane).

[0404] The following examples were prepared using mechanically ground MOF [Mg2(dobpdc)] with an average particle size of 0.48 μm (D50) as measured by a Malvern Zetasizer unless otherwise noted. Exemplary amines containing primary alcohol units were prepared through ring opening by reacting the amine with oxetane. Amines containing primary alcohol units can also be prepared by other means, such as by direct synthesis.

[0405] A 20 mL scintillation vial was charged with 1 to 2.2 equivalents of the new amine synthesized via the reaction of functionalized oxetanes with amines, dissolved in 5 mL of solvent, and then desolvated overnight in a vacuum oven at 120 °C with 1 equivalent of Mg(dobpdc)(IPA). xThe suspension was then heated to 50-60°C on a water heater and stirred at 300-400 rpm overnight. The material was cooled to room temperature and either transferred to a conical tube or rotary evaporated, depending on the formulation used. The material in the conical tube was spun down at 4000 rpm for 2 minutes and the solvent was removed by decantation, or by rotary evaporation of the material in the vial. The sample was then dried overnight in a vacuum oven at 120°C to yield β-alcohol-functionalized amine-formulated Mg2(dobpdc). If excess or surface amines are present, these can be removed by annealing at elevated temperatures. Additionally, annealing can potentially aid in the rearrangement of the amine chains to ultimately reach a stable configuration and binding to the metal site. The material was then digested to 1 H NMR was used to determine the initial composition and the final composition after annealing.

[0406] [Example B15] Synthesis of GE327-A3117D.

[0407] A 20 mL scintillation vial was charged with 1.2 equivalents of β-methylhydroxyltetramine (2-4-3 or 2-3-4) (0.0886 g, 0.50 mmol) dissolved in 5 mL of methanol. Then, 0.160 g (1 equivalent, 0.34 mmol) of Mg2(dobpdc)(IPA) was desolvated overnight in a vacuum oven at 120 °C. 2.56 was added to the vial. The suspension was then heated to 50 °C on a water heater and stirred at 300 to 400 rpm overnight. The material was cooled to room temperature, and the solvent was removed via rotary evaporation. The sample was dried overnight in a vacuum oven at 120 °C to give 0.245 g of GE327-A3117D (99% yield, Mg2(dobpdc)(β-methylhydroxyltetraamine)3).

[0408] Example B16: Typical formulation of PLM amines containing carbonyl units.

[0409] The following examples were made using mechanically ground MOF [Mg2(dobpdc)] with an average particle size of 0.48 μm (D50) as measured by a Malvern Zetasizer unless otherwise noted. Exemplary amines containing carbonyl units were prepared by reacting amines with acyl-containing compounds, including acyl halides, carboxylic acids, and anhydrides, including acyl fluorides, chlorides, bromides, or iodides. Amines containing carbonyl units can also be prepared by other means, such as by direct synthesis.

[0410] [Example B17] Synthesis of GE322-SG1-176.

[0411] A 20 mL scintillation vial was charged with 1.25 equivalents of hexanoyl chloride (HC) 0.48:spermine (0.1765 g, 0.587 mmol) dissolved in 3 mL of toluene. 0.150 g (1 equivalent, 0.47 mmol) of Mg(dobpdc)(IPA) was then desolvated overnight in a vacuum oven at 120 °C. 1.76 was added to the vial. The reaction mixture was then heated to 60°C on a hotplate and stirred at 300-400 rpm overnight. The vial was cooled to room temperature, and the reaction mixture was transferred to a 15 mL centrifuge tube. The supernatant solvent was decanted, and the residue was finally dried in a vacuum oven at 120°C to give GE322-SG1-176 (90% yield, Mg2(dobpdc)(0.48HC:spermine) 0.52 ) was determined by NMR (FIG. 13).

[0412] Example B18 General procedure for post-synthetic modification (PSM) of sorbents.

[0413] A 20 mL scintillation vial was charged with one equivalent of sorbent, i.e., amine-functionalized MOF274. The sorbent was dispersed in 5 mL of hexane. 0.01 to 4 equivalents of functionalized oxirane were then added to the suspension along with 0.5 equivalents of ethanol per equivalent of functionalized oxirane to catalyze the ring-opening reaction. The suspension was heated to 50 °C on a microwave oven and stirred at 300 to 400 rpm overnight. The material was cooled to room temperature and transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was dried overnight in a vacuum oven at 80 °C to obtain secondary alcohol-functionalized amine-loaded Mg2(dobpdc). The material was then digested. 1 H NMR was used to determine the initial composition and the final composition after annealing.

[0414] [Example B19] Synthesis of GE317-PSM.

[0415] For post-synthetic modification, the formula Mg2(dobpdc)(spermine) 1.02 GE5-A369#0 was used. A 20 mL scintillation vial was charged with 0.200 g (0.97 mmol based on spermine) of GE5-A369#0 dispersed in 5 mL of hexane. Two equivalents of 1,2-epoxybutane (0.140 g, 0.169 mL, 1.94 mmol) and one equivalent of EtOH (56 μL) were then added to the vial. The suspension was then heated to 50 °C on a microwave oven and stirred at 300 to 400 rpm overnight. The material was cooled to room temperature and transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was dried overnight in a vacuum oven at 80 °C to yield 0.180 g of GE317-PSM (Mg2(dobpdc)(0.52EB:spermine)). 1.04 ).

[0416] [Example B20] Synthesis of GE319-PSM.

[0417] For post-synthetic modification, the formula Mg2(dobpdc)(spermine) 1.02GE5-A369#0 was used. A 20 mL scintillation vial was charged with 0.200 g (0.97 mmol based on spermine) of GE5-A369#0 dispersed in 5 mL of hexane. Two equivalents of 2,2,2-(trifluoroethyl)oxirane (0.2446 g, 0.191 mL, 1.94 mmol) and one equivalent of EtOH (56 μL) were then added to the vial. The suspension was then heated to 50 °C on a microwave oven and stirred at 300 to 400 rpm overnight. The material was cooled to room temperature and transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was dried overnight in a vacuum oven at 80 °C to yield 0.265 g of GE319-PSM (Mg2(dobpdc)(0.51TFEO:spermine) 1.01 ).

[0418] (Non-MOF sorbent synthesis)

[0419] Example C1 General procedure for the synthesis of amine-functionalized γ-Al2O3: amine loading by physisorption impregnation.

[0420] Prior to synthesis, γ-AlO was thermally activated at 120 °C under vacuum to remove physisorbed water. After this, the desired amount of amine was dissolved in MeOH and added to γ-AlO. The reaction mixture was stirred overnight at room temperature. The solvent was then removed by applying a gentle vacuum in a rotary evaporator. The resulting residue was further dried under vacuum at 100 °C to obtain the amine-loaded γ-AlO material.

[0421] Example C2 Synthesis of GE320-184A (alumina functionalized with spermine through impregnation).

[0422] To a 20 mL scintillation vial, preactivated γ-AlO (200 mg) was added. In a separate vial, spermine (50 wt.% relative to γ-AlO, 200 mg) was dissolved in 3 mL of MeOH and added to the γ-AlO. The suspension was then stirred at 370 rpm overnight at room temperature. After this, the solvent was removed by applying a gentle vacuum on a rotary evaporator. The resulting residue was then further dried under vacuum at 100 °C to yield GE320-184A.

[0423] Example C3 Synthesis of GE321-184B (alumina functionalized with -OH containing spermine through impregnation).

[0424] To a 20 mL scintillation vial, γ-AlO (200 mg) was added. In a separate vial, EB0.25:spermine (50 wt.% relative to γ-AlO, 235 mg) was dissolved in 3 mL of MeOH and added to the γ-AlO. The suspension was then stirred at 370 rpm overnight at room temperature. After this, the solvent was removed by applying a gentle vacuum on a rotary evaporator. The resulting residue was then further dried under vacuum at 100 °C to yield GE321-184B.

[0425] The reaction scheme is shown in Figure 14.

[0426] [Example C4] Synthesis of γ-Al2O3 modified with (3-glycidyloxypropyl)trimethoxysilane: Covalent grafting of amines

[0427] (3-Glycidyloxypropyl)trimethoxysilane (GLYMO) was dissolved in toluene or an ethanol / water / acetic acid (pH ≈ 4) solvent mixture. A sample of preactivated γ-AlO was added to the GLYMO solution and heated with stirring to 90 °C (toluene) or 40 °C (ethanol / water / acetic acid) overnight. After this, the reaction mixture was centrifuged, and the residue was washed twice with hexane. The resulting product was further dried under vacuum at 90 °C to obtain GLYMO-functionalized γ-AlO (Figure 14). The degree of grafting of GLYMO was characterized using thermogravimetric analysis (TGA) (Figure 15).

[0428] Example C5 Synthesis of SG1-177 (GLYMO functionalization in toluene).

[0429] GLYMO (500 mg) was added to a 250 mL three-necked round-bottom flask, followed by 100 mL of toluene. A sample of preactivated γ-AlO (500 mg) was added to the GLYMO solution and heated to 90 °C overnight. After this, the reaction mixture was centrifuged to remove the toluene, and the residue was washed twice with hexane to remove physisorbed GLYMO. The resulting residue was further dried under vacuum at 90 °C to obtain GLYMO-functionalized γ-AlO (Figures 14 and 15).

[0430] Example C6 Synthesis of GE323-184C (0.25EB: spermine-functionalized GLYMO-grafted γ-Al2O3).

[0431] To a 20 mL scintillation vial, SG1-177 (200 mg) was added. In a separate vial, 0.25 EB:spermine (50 wt.% relative to SG1-177, 237 mg) was dissolved in 3 mL of MeOH and added to γ-Al2O3. The suspension was then stirred at 370 rpm overnight at room temperature. After this, the solvent was removed by applying a gentle vacuum on a rotary evaporator. The resulting residue was then further dried under vacuum at 100 °C to yield GE323-184C.

[0432] TGA was used to investigate the thermal stability of three amine-functionalized γ-AlO sorbents (Figure 16). The thermal stability of spermine bonds can be enhanced by using -OH-containing spermine modified with 1,2-epoxybutane and further grafted with GLYMO.

[0433] Example C7 One-pot synthesis of (3-glycidyloxypropyl)trimethoxysilane modified γ-Al2O3: covalent grafting of amines.

[0434] To avoid cross-linking between the partially hydrolyzed GLYMO and the amine before the addition of the carrier material, a one-pot reaction was performed by sequential addition of the individual components. In a 20 mL scintillation glass vial, spermine (200 mg, 0.988 mmol) and GLYMO (234 mg, 0.988 mmol) were dissolved in 3 mL of methanol. The reaction mixture was stirred at room temperature for 30 min. After this, preactivated γ-AlO (200 mg) was added to the reaction mixture, and the combined mixture was stirred overnight at room temperature. After the reaction, MeOH was removed under gentle vacuum in a rotary evaporator. The resulting residue was further dried under vacuum at 100 °C for 12 h to obtain GE324-1A. Figure 17 shows the TGA curve of the one-pot synthesized γ-AlO modified with GLYMO and further functionalized with spermine.

[0435] (Testing and Characterization)

[0436] Example D1 General test procedure.

[0437] The performance of CO2 and HO adsorption was investigated using gravimetric methods with a dynamic vapor sorption analyzer (DVS). In the experiments presented in this disclosure, the gas and vapor used were CO2 and water, respectively. The DVS vacuum analyzer is designed to accurately measure the mass change of a sample as it adsorbs precisely controlled concentrations of water and / or gas molecules. The sample is placed in a sample pan suspended from a microbalance (usually with an empty pan suspended on the other side of the microbalance as a "reference"). The DVS Vacuum simultaneously controls and measures the inflow and outflow of sorbate while recording the sample's mass change. The main instrument, the microbalance (UltraBalance®), is housed in a precisely controlled temperature-controlled enclosure (called an incubator). This ensures a highly stable instrument baseline and precise vapor generation control at the experimental temperature.

[0438] The gravimetric DVS method can accurately measure isotherms for pure H2O and pure CO2. For wet CO2 adsorption, a two-cycle sequential adsorption test protocol is developed. At the start of each cycle, the sorbent material of interest is heated to 100°C for 60 minutes at 120°C. -5 The sample is subjected to an activation (or regeneration) step under a vacuum of less than 100 mbar. At a given temperature and without carrier gas interference, a set partial pressure of water is introduced under vacuum. The sample weight is measured directly and continuously using an Ultra precision micro-Balance from Surface Measurement Systems with a resolution of 0.1 μg. All sorption measurements in this disclosure were performed using mass balance mode with the mass balance criterion set as mass change per minute (dm / dt < 0.0035). Once water adsorption reaches equilibrium, CO2 gas is introduced at a preset partial pressure target. The partial pressure of CO2 can be adjusted to reflect the application conditions, i.e., 400 vppm for direct air capture (DAC) or 4.5 v% for post-combustion capture (PCC).

[0439] The CO2 and HO adsorption performance can also be investigated using a proprietary breakthrough test apparatus. The test apparatus has a sample chamber containing the test sample in either powder or coated form, and separate calibrated temperature, CO2, and relative humidity (RH) sensors at both the gas inlet before the sample chamber and the gas outlet after the sample chamber. The test apparatus can measure individual breakthrough curves for CO2 and HO under either dry or humid CO2 conditions at preset RH levels. Uptake can be calculated by integrating the breakthrough curves over time.

[0440] CO2 uptake or capacity is expressed as grams of CO2 adsorbed per gram of sorbent (gCO2 / g sorbent). CO2 uptake can generally be viewed as an exponential growth over time, [Q max -Q (t) ] / Q max =e -kt In the formula, Q max and Q (t) are the equilibrium uptake and the uptake at a given adsorption time t (min), respectively, and k is a characteristic value of the exponential growth in units of 1 / min.

[0441] Mathematically, the unit 1 / k is Q max This is equal to the time required for CO2 uptake to reach 63% of its original volume. In this study, we compare the kinetics or rate of CO2 uptake using 1 / k, which is more intuitive than k; the smaller 1 / k, the faster the kinetics of CO2 uptake.

[0442] Example D2: Water adsorption of exemplary MOF-based sorbents functionalized with -OH-containing amines.

[0443] Water isotherms measured at 25°C using gravimetric DVS techniques for several exemplary -OH-containing amine-functionalized sorbents are shown in Figures 18 through 26. Water uptake is expressed as mass ratio, i.e., grams of HO adsorbed per gram of sorbent (g HO / g sorbent), and number ratio per amine functional group, i.e., number of HO molecules adsorbed per amine group, measured at 25°C and 50% relative humidity. These are summarized in Table 4.

[0444] [Table 7]

[0445] The incorporation of -OH groups, whether in PLMs or PSMs, has produced a number of unexpected results, summarized below.

[0446] First, HO uptake at fixed conditions, such as 50% relative humidity, can be reduced by incorporating -OH groups. The degree of reduction in HO uptake can be tuned by varying the length of the fatty moiety, such as 1,2-epoxybutane versus 1,2-epoxyoctane, using fluorinated agents such as 2,2,2-(trifluoroethyl)oxirane (TFEO) or different degrees of incorporation (Table 4 and Figures 18 to 25), or through modification with oxetanes (Figure 26).

[0447] Second, the average number of HO adsorbed per amine group can be adjusted or significantly reduced by incorporating -OH groups. The degree of reduction in HO adsorbed per amine group can be adjusted by varying the length of the fatty moiety, such as 1,2-epoxybutane versus 1,2-epoxyoctane, using fluorinated agents such as 2,2,2-(trifluoroethyl)oxirane (TFEO), or different degrees of incorporation (Table 4 and Figures 18-25).

[0448] Third, the shape of the water isotherm can be tuned by varying the reactant, degree of incorporation, and -OH content (Figures 18 through 26). MOF-274-based sorbents functionalized with bare amines that do not contain any -OH groups tend to have Type II or Type IV isotherms as defined by IUPAC (Figure 27), with a clear transition region from monolayer HO uptake to multilayer HO uptake or even condensation. The transition region becomes less clear for sorbents functionalized with amines that comprise -OH groups. Sorbents with higher -OH content exhibit water isotherms that more closely resemble Type III rather than Type II or IV.

[0449] Example D3: Water adsorption of exemplary non-MOF based sorbents functionalized with -OH containing amines.

[0450] Water isotherms measured at 25° C. using gravimetric DVS techniques for some exemplary non-MOF-based sorbents functionalized with —OH-containing amines are shown in FIGS. 28-30.

[0451] Example D4: Dry CO2 adsorption of exemplary MOF-based sorbents functionalized with -OH-containing amines.

[0452] Dry CO isotherms measured at 25° C. using gravimetric DVS techniques for exemplary MOF-based sorbents functionalized with —OH-containing amines are shown in Figures 32 through 37. CO uptake is expressed as the mass ratio, i.e., grams of CO adsorbed per gram of sorbent (gCO / g sorbent), and the number ratio of CO per amine functional group, i.e., the average number of CO molecules per amine group, measured at 25° C. The results are summarized in Table 5.

[0453] [Table 8]

[0454] The incorporation of the -OH group has many unexpected consequences, which are summarized below.

[0455] First, the presence of -OH groups can enhance dry CO2 uptake at low CO2 pressures relative to the corresponding amines that do not have any -OH groups (Figures 31 to 37 and Table 5).

[0456] Second, the degree of enhancement can be adjusted by varying the reactants or by varying the degree of -OH incorporation. Increasing the incorporation of epoxide does not result in significant enhancement. Without being bound to any particular theory, this is believed to be due to the extra mass added from the ring-opening reaction and increased steric effects due to the increased size of the amine.

[0457] Third, the shape of the drying CO isotherm can be adjusted by varying the reactant, degree of incorporation, and -OH content. For example, sorbents functionalized with unmodified spermine exhibit a stepped isotherm that shows a rapid transition between CO partial pressures of 1 and 10 mBar (Figures 32-33). This step is less evident or even reduced for sorbents functionalized with spermine, which contains -OH groups.

[0458] Example D5: Dry CO2 adsorption of exemplary non-MOF based sorbents functionalized with -OH containing amines.

[0459] Dry CO2 isotherms for exemplary non-MOF-based sorbents functionalized with spermine and -OH-containing spermines measured at 25°C using gravimetric DVS method are shown in Figures 38-39, respectively.

[0460] In addition to the enhanced thermal stability shown in Figure 16, the presence of -OH groups in GE321-184B significantly enhances dry CO2 uptake at low CO2 pressures relative to the control (GE320-184A) that does not contain any -OH groups (Figures 38-39).

[0461] Example D6: Desorption residue of exemplary sorbent materials.

[0462] Dry CO uptake at 120°C and CO partial pressures of 100 and 400 mBar can be used to assess the desorption residues for each material. With the incorporation of -OH groups, the desorption residues at both 100 and 400 mBar CO pressures can be adjusted relative to two comparative examples that do not contain any -OH groups (Table 6).

[0463] [Table 9]

[0464] Example D7 Wet CO2 adsorption of exemplary sorbent materials measured using a flow-through test apparatus.

[0465] Table 7 lists some exemplary sorbent materials and their adsorption performance measured under DAC-relevant co-adsorption conditions (25° C., 50% RH, and 400 vppm CO 2 ) using a flow-through test apparatus.

[0466] [Table 10]

[0467] (Coating with amine-functionalized sorbents)

[0468] Example E1 General procedure for preparing coatings using amine-functionalized sorbents.

[0469] The functionalized sorbent material may be in any form, including, but not limited to, a powder, a composite mixed with a binder, a thin film or coating, a packed bed, and a column. In one embodiment, the functionalized sorbent is provided as a thin film or coating further comprising at least one binder. In another embodiment, the functionalized sorbent is provided as a thin film or coating further comprising at least one polymeric binder and at least one additive, including, but not limited to, clay particles, silica particles, and alumina particles. In another embodiment, the functionalized sorbent is provided as a thin film or coating prepared using an organic solvent, including, but not limited to, xylene, p-xylene, o-xylene, ketones, ethanol, and isopropyl alcohol. In another embodiment, the functionalized sorbent is provided as a thin film or coating prepared using water.

[0470] According to a typical procedure, thin film coatings containing a sorbent can be prepared by making a suspension composition containing a solvent, a functionalized sorbent, and a binder, optionally including additional additives as needed to improve suspension flowability and coating quality, applying the suspension to a substrate by a coating technique, drying the suspension to remove the solvent, and optionally curing under heat or ultraviolet light irradiation, etc.

[0471] The solvent may be aqueous or organic, or a mixture thereof in any suitable ratio.

[0472] The binder may generally be a polymer or a precursor (eg, a mixture of monomers, etc.) that includes a polymer that crosslinks upon curing.

[0473] The additive must be compatible with the solvent and the functionalized sorbent to facilitate binding of the sorbent particles and also dispersion through the solvent.

[0474] Any suitable coating technique may be used, such as, but not limited to, spray coating, dip coating, flow coating, spin coating, drop coating, and the like.

[0475] Example E2 General procedure for water immersion testing.

[0476] To a 15 mL falcon tube was added 50 mg of sorbent along with 1 mL of DI water. The tube was sonicated for 5 minutes and then allowed to soak for 30 minutes. The tube was centrifuged, decanted, and then dried overnight in a vacuum oven at 120°C. The material was digested to 1 HNMR was used to determine loading after the elution test. The change in amine loading is defined as the resistance of the amine to water immersion.

[0477] Example E3: Exemplary coating of GE314 with organic solvents.

[0478] Thin film specimens of GE314 were prepared according to the following procedure. First, 0.05 g of Butvar B98 was dissolved in 2.5 g of ethanol as a binder. 0.05 g of clay particles was then added to the solution and stirred for 15 minutes. Next, 1 g of GE314 was added, and the suspension was vortexed for several minutes before being coated onto a 2" x 2" aluminum piece. The coated specimen was air-dried in a fume hood for 1 hour and then dried in a drying oven at 90°C for 1 hour.

[0479] Figure 40 shows the CO2 uptake and HO uptake over time for the GE314 thin film. Under the conditions tested, the CO2 adsorption reaction kinetics (1 / k) is 33.8 min. This fast reaction kinetics is partly due to the use of small MOF particles with a D50 of 0.24 μm.

[0480] [Example E4] Durability against water immersion.

[0481] Amine-functionalized sorbent materials generally suffer from amine loss when in contact with liquid water, and it is desirable to increase the durability of sorbents to liquid water for practical uses and applications.

[0482] In CO2 capture plants, sorbent materials can be in any form, including, but not limited to, powders, composites mixed with binder materials, thin films, coatings, packed beds, and columns. In some embodiments, the sorbent is present as a coating on a substrate or contact body. The sorbent coating can be formed by coating a substrate with a preformed suspension of the sorbent material in a solvent, optionally including binders and additives. Water-based suspension or coating procedures are preferred over solvent-based ones because they eliminate or reduce volatile organic compounds (VOCs), but this requires the sorbent material to be durable to liquid water. Furthermore, as shown in Figures 19 through 26, amine-functionalized sorbents can have Type IV water isotherms, indicating the potential for water condensation under high relative humidity. Increasing the sorbent material's durability to liquid water can, in principle, reduce potential degradation, amine loss, or leaching due to condensed water when the sorbent is exposed to a highly humid environment.

[0483] The durability of sorbent materials to liquid water is evaluated according to the general procedure of a water immersion test. Table 8 shows the results of water immersion experiments for several exemplary sorbent materials. The degree of amine loss due to water immersion can be adjusted by varying the reactant, degree of incorporation, and -OH content. For example, modification of spermine with TFEO significantly reduced the amine loss after water immersion to 8.9% (GE319-PSM) compared to 40.2% for the unmodified spermine-functionalized sorbent.

[0484] [Table 11]

[0485] Another useful method for assessing water solubility is to use the logP value, the logarithm (base 10) of the partition coefficient (P), defined as the ratio of a substance's concentration in the organic (oil) phase to that in the aqueous phase. LogP is widely used in the pharmaceutical industry to help identify drug candidates suitable for oral administration. LogP values ​​can be measured empirically or calculated using a number of software packages, such as ALOGPS 2.1, which was used in this disclosure. Table 9 shows the LogP values ​​for some exemplary functionalized sorbents versus amine changes upon immersion in water. Amine-functionalized sorbents with more positive LogP values ​​tend to exhibit less amine loss.

[0486] [Table 12]

[0487] Example E5: Exemplary coating of amine-functionalized sorbents with aqueous compositions.

[0488] Thin film specimens of amine-functionalized sorbents without -OH groups were prepared using the following aqueous formulation procedure and aqueous epoxy binder. First, 0.2 g of Westcoat EC epoxy binder solution (46% solids) was added to 2.5 g of water. The mixture was vortexed for 2 minutes, after which 0.5 g of sorbent was added. The suspension was sonicated in a vortex mixer for 10 minutes before coating onto 1" x 1" aluminum coupons. The coated coupons were allowed to air-dry on the bench for 24 hours to self-cure, followed by drying in a 90°C oven for 1 hour. The amine content in the thin films was determined using 1H NMR as previously described. The amount of amine present in the final coatings and the corresponding change as a result of the aqueous formulation process are summarized in Table 10. While unmodified amines such as spermine exhibited a 24.5% reduction in amine loading, both PLM- and PSM-modified amines containing -OH groups exhibited little change in amine loading.

[0489] [Table 13]

[0490] [Example E6] Desorption temperature.

[0491] The CO2 desorption characteristics were tested by monitoring the CO2 desorption signal while gradually increasing the test bed temperature (Figures 41 to 46). For each experiment, the sorbent was subjected to adsorption under DAC-relevant conditions, i.e., 25 °C, 400 vppm CO2, and 50% RH, until complete equilibrium was reached. As shown in Figure 41, the pure spermine-functionalized MOF-based sorbent (GE5-A369) exhibits multiple desorption peaks corresponding to desorption temperatures up to 100 °C. The -OH-containing spermine-functionalized MOF-based sorbents modified with either 1,2-epoxybutane (GE296-A366A) (Figure 42) or 1,2-epoxyoctane (GE301-A370A) (Figure 43) were completely desorbed at a reduced temperature of 80 °C. A similar decrease in desorption temperature relative to the bare amine (Figure 44) was observed for the MOF-based sorbent functionalized with the -OH-containing amine 2-3-2 in both powder (Figure 45) and thin film form (Figure 46).

[0492] (summary)

[0493] Important advantages are described herein when sorbents are functionalized with at least one functionalizing ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof. Additionally, the incorporation of -OH groups, whether PLM or PSM, leads to many unexpected results, as disclosed herein. The materials and methods of this disclosure are broadly applicable to a wide range of sorbents and functionalizing ligands.

[0494] (definition)

[0495] As used herein, references to an "exemplary embodiment" or "one embodiment" or "some embodiments" of the present disclosure should not be interpreted as excluding the existence of additional embodiments that also incorporate the recited features.

[0496] When presenting elements of various embodiments disclosed herein, the singular indefinite article, the definite article, "the," "said," and the like are intended to mean that there are one or more of the elements in question. Also, the terms "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0497] Unless otherwise indicated, approximating terms such as "generally," "substantially," and "about" used herein apply only to an approximate, rather than an absolute or complete, degree, as would be recognized by one of ordinary skill in the art. Thus, a value modified by one or more terms such as "about," "approximately," and "substantially" is not limited to the exact value specified. In at least some instances, approximating terms may correspond to the precision of an instrument measuring the value. Additionally, unless otherwise indicated, terms such as "first" and "second" are used herein merely as labels and do not impose any order, arrangement, or hierarchical requirements on the items to which they refer. Furthermore, a reference to, for example, a "second" item does not require or exclude the presence of, for example, "first" or subsequent numbered items or "third" or subsequent numbered items.

[0498] Unless otherwise indicated, approximating terms such as "generally," "substantially," and "about" used herein apply only to an approximate, rather than an absolute or complete, degree, as would be recognized by one of ordinary skill in the art. Thus, a value modified by one or more terms such as "about," "approximately," and "substantially" is not limited to the exact value specified. In at least some instances, approximating terms may correspond to the precision of an instrument measuring the value. Additionally, unless otherwise indicated, terms such as "first" and "second" are used herein merely as labels and do not impose any order, arrangement, or hierarchical requirements on the items to which they refer. Furthermore, a reference to, for example, a "second" item does not require or exclude the presence of, for example, "first" or subsequent numbered items or "third" or subsequent numbered items.

[0499] As used herein, the term "isomer" refers to molecules having the same molecular formula but different atomic configurations in space. Isomers include structural isomers and stereoisomers. Stereoisomers include (R)-enantiomers and (S)-enantiomers, and cis / trans diastereomers. Each compound disclosed in this disclosure discloses all individual isomers and all mixtures of multiple isomers, whether or not a specific isomer is indicated.

[0500] As used herein, the term "alkyl," whether used alone or in compound words such as "haloalkyl," includes straight-chain or branched alkyls such as methyl, ethyl, n-propyl, and i-propyl, or the various butyl, pentyl, or hexyl isomers. Alkyl defined by the number of carbon atoms, for example, C alkyl, is understood to have this number of carbon atoms, but is not otherwise limited.

[0501] As used herein, the term "heteroalkyl" refers to an alkyl chain in which at least one of the atoms forming the backbone of the chain is other than carbon.

[0502] As used herein, "aminoalkyl" includes an N group substituted with a straight chain or branched alkyl.

[0503] As used herein, the terms "halogen" or "halide," used alone or in compound words such as "haloalkyl," include fluorine, chlorine, bromine, or iodine. Additionally, when used in compound words such as "haloalkyl," these alkyls may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of "haloalkyl" include F3C, ClCH2, CF3CH2, and CF3CCl2, and the like. Terms such as "haloalkoxy" are defined in an analogous manner to the term "haloalkyl." Examples of "haloalkoxy" include CFO, CCl3CHO, F2CHCH2CHO, and CF3CHO, and the like.

[0504] As used herein, the term "heterocyclic ring" refers to a ring in which at least one of the atoms forming the backbone of the ring is other than carbon. Unless otherwise specified, a heterocyclic ring may be saturated, partially saturated, or fully saturated. When a fully unsaturated heterocyclic ring satisfies Hückel's rule, the ring is also referred to as a "heteroaryl" ring or an aromatic heterocyclic ring. A "saturated heterocyclic ring" refers to a heterocyclic ring that contains only single bonds between ring members.

[0505] As used herein, the term "aminosilicone group" includes functional groups that contain both amine groups and siloxane groups containing Si-O-Si bonds (also called disiloxane groups).

[0506] Ring-shaped cyclic units are divided into two categories: alicyclic units and aromatic units. A cyclic unit refers to any chemical species in which at least three atoms are bonded together to form a closed ring structure. Some cyclic units are considered alicyclic because they are simultaneously aliphatic and cyclic. Aromatic units are also cyclic compounds with closed ring structures. However, the main difference between alicyclic and aromatic units is that aromatic units are formed by the sp π electrons incorporated into a planar conjugated ring system via delocalized π electrons. 2 It is composed of atoms with hybrid orbitals, while alicyclic units do not contain delocalized π electrons around the ring, sp, sp 2 , or sp 3 Furthermore, aromatic units or compounds generally follow Hückel's rule, which states that the total number of π electrons belonging to a ring-shaped cyclic unit or molecule is equated to the formula "4N+2", where N can be any positive integer.

[0507] As used herein, the term "polyamine" refers to a compound having at least two amine groups. Thus, polyamines include diamines, triamines, tetraamines, pentaamines, hexaamines, and combinations thereof.

[0508] As used herein, the term "hydroxyl unit" refers to an -OH group, which may be a primary -OH group, where the -OH group is attached to a primary carbon atom to form a primary alcohol, a secondary -OH group, where the -OH group is attached to a secondary carbon atom to form a secondary alcohol, or a tertiary -OH group, where the -OH group is attached to a tertiary carbon atom to form a tertiary alcohol.

[0509] As used herein, "carbonyl unit" refers to a C=O group. The C=O group is not limited by surrounding bonds or functional groups and may form part of other functional groups. For example, the C=O group may be part of an amide group, an aldehyde group, a ketone group, a thiocarboxylic acid group, or a carboxylic acid group.

[0510] 1H NMR spectra are reported as ppm downfield from tetramethylsilane, where "s" means singlet, "d" means doublet, "dd" means double doublet, "ddd" means double double doublet, "t" means triplet, "m" means multiplet, and "br s" means broad singlet.

[0511] Although some drawings may show specific features of various embodiments of the invention in others, this is for convenience only, and in accordance with the principles of the invention, any feature of a drawing may be referenced and / or claimed in combination with any feature of any other drawing.

[0512] While the invention has been described in terms of various specific embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the claims.

[0513] This written description uses examples to disclose the invention, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are considered to be within the scope of the claims if they have structural elements that do not differ from the literal wording of the claims, or if they include equivalent structural elements that have insubstantial differences from the literal wording of the claims.

[0514] Those skilled in the art will readily recognize that some substituents in the present disclosure are dependent on the presence of other substituents and are therefore optional. For example, in Formula AI, when R is a direct bond, R and R are optional substituents that are not present in the compound. Similarly, in Formula AI, when n is 0, R and R are optional substituents that are not present in the compound. 10 There is a direct bond between R3, R4, and R 11 is an optional substituent that is not present in the compound. The optionality of a substituent in one embodiment is non-restrictive with respect to the presence of the substituent in another embodiment.

[0515] Further aspects of the invention are set out by the subject matter of the following clauses.

[0516] Clause 1) A functionalized sorbent comprising a sorbent and at least one functionalizing ligand, wherein the functionalizing ligand comprises a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0517] Clause 2) The functionalized sorbent of clause 1, wherein the at least one oxygen-containing unit is selected from the group consisting of a primary hydroxyl unit, a secondary hydroxyl unit, a tertiary hydroxyl unit, and combinations thereof.

[0518] Clause 3) The functionalized sorbent of any one of the preceding clauses, wherein the polyamine comprises at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof.

[0519] Clause 4) The functionalized sorbent of any one of the preceding clauses, wherein the polyamine comprises at least one amine selected from the group consisting of diamines, triamines, tetraamines, pentaamines, hexaamines, heptamines, octaamines, and combinations thereof.

[0520] Clause 5) The functionalized sorbent of any one of the preceding clauses, wherein the sorbent comprises a metal-organic framework (MOF).

[0521] Clause 6) The functionalized sorbent of any one of the preceding clauses, wherein the sorbent comprises a mesoporous oxide support.

[0522] Clause 7) The functionalized sorbent of any one of the preceding clauses, comprising at least one functionalizing ligand that does not comprise a polyamine containing at least one oxygen-containing unit.

[0523] Clause 8) The functionalized sorbent of any one of the preceding clauses, wherein the sorbent has an aspect ratio of ≧0.2.

[0524] Clause 9) The functionalized sorbent of any one of the preceding clauses, wherein the sorbent has an average particle length of ≦3 μm.

[0525] Clause 10) The functionalized sorbent of any one of the preceding clauses, having a Type II, Type III, or Type IV isotherm with pure water.

[0526] Clause 11) The functionalized sorbent of any one of the preceding clauses, wherein at least one functionalizing ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, has a LogP of -1.0 or greater.

[0527] Clause 12) The functionalized sorbent of any one of the preceding clauses, wherein the sorbent is in a form selected from the group consisting of a powder, a pellet, a composite, a composite mixed with a binder, a thin film, a coating, an aqueous coating, a packed bed, a column, a monolith, and combinations thereof.

[0528] Clause 13) A sorption system comprising a functionalized sorbent according to any one of the preceding clauses.

[0529] Clause 14) A method of making a functionalized sorbent, the method comprising the steps of: (I) forming a mixture comprising a sorbent, at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, optionally at least one functionalizing ligand not comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof, optionally a solvent, and optionally a non-solvent; and (II) functionalizing the sorbent.

[0530] Clause 15) The method of any one of the preceding clauses, wherein the solvent comprises an aqueous solvent.

[0531] Clause 16) A method for modifying a functionalized sorbent, the method comprising the steps of: (I) forming a mixture comprising a sorbent functionalized with at least one functionalizing ligand that does not include a polyamine that includes at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; and a reactant; and (II) reacting the reactant with the sorbent functionalized with at least one functionalizing ligand that does not include a polyamine that includes at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof to produce a sorbent functionalized with at least one functionalizing ligand that includes a polyamine that includes at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0532] Clause 17) The method of any one of the preceding clauses, wherein the reactant contains at least one functional group selected from the group consisting of an epoxide group, an epoxide group containing a fluorine atom, a three-membered ring epoxide group, a monoepoxide group, a diepoxide group, an oxetane group, a four-membered ring oxetane group, and combinations thereof.

[0533] Clause 18) A method for recovering at least one gas, the method comprising: (I) receiving a gas source comprising at least one gas in a functionalized sorbent comprising a sorbent and at least one functionalizing ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof; and (II) recovering a quantity of the at least one gas with the functionalized sorbent.

[0534] Clause 19) The method of any one of the preceding clauses, wherein the gas source is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0535] Clause 20) The method of any one of the preceding clauses, wherein the at least one gas is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0536] Clause 21) A method for collecting at least one gas from a gas source, comprising: Recovering at least one gas according to the method of any one of the preceding clauses; (III) releasing at least one gas from the functionalized sorbent; A method including:

Claims

1. a sorbent; at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof; A functionalized sorbent comprising:

2. (a) the at least one oxygen-containing unit is selected from the group consisting of primary hydroxyl units, secondary hydroxyl units, tertiary hydroxyl units, and combinations thereof; and / or (b) the polyamine comprises at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof; The functionalized sorbent of claim 1 .

3. 2. The functionalized sorbent of any one of the above claims, wherein the polyamine comprises at least one amine selected from the group consisting of diamines, triamines, tetraamines, pentaamines, hexaamines, heptaamines, octaamines, and combinations thereof.

4. 10. The functionalized sorbent of any one of the above claims, wherein the sorbent comprises a metal organic framework (MOF).

5. 10. The functionalized sorbent of any one of the preceding claims, wherein the sorbent comprises a mesoporous oxide support.

6. 2. A functionalized sorbent according to any one of the preceding claims, comprising at least one functionalizing ligand that does not comprise a polyamine comprising at least one oxygen-containing unit.

7. (a) the sorbent has an aspect ratio of ≥ 0.2; and / or (b) the sorbent has an average particle length of ≦3 μm; A functionalized sorbent according to any one of the preceding claims.

8. (a) the functionalized sorbent has a Type II, Type III, or Type IV isotherm with pure water; and / or (b) the at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof has a Log P of −1.0 or greater; and / or (c) the sorbent is in a form selected from the group consisting of a powder, a pellet, a composite, a composite mixed with a binder, a thin film, a coating, a packed bed, a column, a monolith, and combinations thereof; A functionalized sorbent according to any one of the preceding claims.

9. A sorption system comprising the functionalized sorbent of any one of claims 1 to 8.

10. 1. A method of making a functionalized sorbent, comprising: (I) a sorbent; at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof; at least one functionalized ligand comprising no polyamine, optionally comprising at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof; Optionally, a solvent; Optionally, a non-solvent forming a mixture comprising: (II) functionalizing the sorbent; A method comprising:

11. 1. A method for modifying a functionalized sorbent, comprising: (I) a sorbent functionalized with at least one functionalizing ligand comprising no polyamine, wherein the functionalizing ligand comprises at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof; Reactant and forming a mixture comprising: (II) reacting the reactant with the sorbent functionalized with at least one functionalizing ligand that does not comprise a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof, to produce a sorbent functionalized with at least one functionalizing ligand that comprises a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; A method comprising:

12. 12. The method of claim 11, wherein the reactant comprises at least one functional group selected from the group consisting of an epoxide group, an epoxide group comprising a fluorine atom, a three-membered ring epoxide group, a monoepoxide group, a diepoxide group, an oxetane group, a four-membered ring oxetane group, and combinations thereof.

13. 1. A method for recovering at least one gas, comprising: (I) receiving a gas source comprising said at least one gas at the functionalized sorbent of any one of claims 1 through 8; (II) recovering a quantity of the at least one gas with the functionalized sorbent; A method comprising:

14. (a) the gas source is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof; and / or (b) the at least one gas is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof; The method of claim 13.

15. 1. A method for collecting at least one gas from a gas source, comprising: recovering the at least one gas according to the method of claim 14(a); (III) releasing the at least one gas from the functionalized sorbent; A method comprising:

Images