Sorbents functionalized with ligands having amino silicone functional groups

Abstract

Described herein are adsorbents functionalized with ligands having amino silicone functional groups. Also described herein are methods of making adsorbents functionalized with ligands having amino silicone functional groups. Also described herein are methods of using adsorbents functionalized with ligands having amino silicone functional groups.

Description

[0001] Related Applications

[0002] This application claims priority to U.S. Provisional Application Serial No. 63 / 399,251, filed on August 19, 2022, and also claims priority to U.S. Provisional Application Serial No. 63 / 386,231, filed on December 6, 2022, the contents of both applications are hereby incorporated by reference in their entirety. Background Art

[0003] The field of the present disclosure relates generally to adsorbents functionalized with ligands having aminoorganosilicon functional groups, methods of making the same, and methods of using the same.

[0004] Solid adsorbents can be used for a variety of purposes. For example, they are particularly useful in carbon capture adsorbent systems, such as for CO 2 Point source, post combustion air capture and direct air capture.

[0005] Solid sorbents for carbon capture offer viable and superior performance to conventional liquid amine-based CO 2 Techno-economic alternatives to capture methods. For example, solid adsorbents tend to have better adsorption capacity, lower regeneration energy requirements, and reduced system complexity and environmental and safety risks compared to active liquid amines.

[0006] There are two types of adsorbent materials based on the underlying adsorption mechanism. The first type is physical adsorbents, which rely on non-covalent interactions (e.g., van der Waals interactions, dipole-dipole interactions, etc.) to adsorb gaseous species such as CO. 2 and H 2 O. Examples of physical adsorbents include activated carbon, zeolites, and metal organic frameworks (MOFs). The second type is chemical adsorbents, which adsorb CO through a reversible chemical reaction and by forming ammonium carbamate, carbamic acid, ammonium carbonate, and / or ammonium bicarbonate. 2 Examples of chemical adsorbents include amine-functionalized silica particles, amine-functionalized polymers and resins, amine-functionalized metal organic frameworks (MOFs), and amine-functionalized covalent organic frameworks (COFs).

[0007] Due to chemical bonding, chemical adsorbent materials are generally more resistant to interfering substances such as N than physical adsorbent materials. 2 , methane and CO have better CO 2 Adsorption selectivity. However, the effectiveness of chemical adsorbent systems can be limited by the compositional nature of the functionalized molecules that undergo the chemical adsorption and functionalization processes. Therefore, there is a need for functionalized adsorbents containing chemically and thermally stable molecular species that selectively absorb CO with high capacity and rapid kinetics. 2 . Summary of the invention

[0008] In one aspect, a functionalized adsorbent is provided, comprising an adsorbent and at least one functionalized ligand comprising an aminoorganosilicon group.

[0009] In another aspect, a method for preparing a functionalized adsorbent is provided. The method comprises: (I) forming a mixture comprising an adsorbent, at least one functionalized ligand comprising an aminoorganosilicon group, optionally at least one functionalized ligand not comprising an aminoorganosilicon group, optionally a solvent; and optionally a non-solvent; and (II) functionalizing the adsorbent.

[0010] In another aspect, a method of capturing at least one gas is provided. The method comprises: (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising an amino organosilicon group; and (II) capturing a quantity of the at least one gas with the functionalized adsorbent.

[0011] In another aspect, a method of collecting at least one gas is provided. The method comprises: (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising an amino organosilicon group; (II) capturing an amount of the at least one gas with the functionalized adsorbent; and (III) releasing the at least one gas from the functionalized adsorbent. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] These and other features, aspects and advantages of the present disclosure will be better understood when the following detailed description is read with reference to the accompanying drawings, in which like characters refer to like parts throughout the several views, and in which:

[0013] Figure 1 is a flow chart of an exemplary method according to the present disclosure;

[0014] Figure 2 is a flow chart of an exemplary method according to the present disclosure;

[0015] Figure 3 is a flow chart of an exemplary method according to the present disclosure;

[0016] Figure 4 It is shown that according to the present disclosure, at 4.5% (v / v) CO 2 Potential CO ions of MOF compounds functionalized with pure AEAM, pure spermine, or mixed amines (spermine and AEAM) measured at 60 °C and 30% RH. 2 capacity;

[0017] Figure 5It is shown that according to the present disclosure, at 400 ppmv CO 2 Potential CO 2 removal of MOF compounds functionalized with pure AEAM, pure spermine or mixed amines (spermine and AEAM) measured at 25 °C and 30% RH. 2 capacity;

[0018] Figure 6 It is shown that according to the present disclosure, at 4.5% (v / v) CO 2 Potential CO ions of MOF compounds functionalized with pure AEAM, pure spermine, or mixed amines (spermine and AEAM) measured at 60 °C and 30% RH. 2 productivity;

[0019] Figure 7 It is shown that according to the present disclosure, at 400 ppmv CO 2 Potential CO 2 removal of MOF compounds functionalized with pure AEAM, pure spermine or mixed amines (spermine and AEAM) measured at 25 °C and 30% RH. 2 productivity;

[0020] Figure 8 Depicted is the drying CO of MOF compounds functionalized with pure spermine or mixed amines (spermine and AEAM) according to the present disclosure. 2 Isotherms;

[0021] Fig. 9 It is shown that according to the present disclosure, at 4.5% (v / v) CO 2 Potential CO ions of MOF compounds functionalized with pure AEAM, pure spermidine, or mixed amines (spermidine and AEAM) measured at 60 °C and 30% RH. 2 capacity;

[0022] Fig.10 It is shown that according to the present disclosure, at 4.5% (v / v) CO 2 Figure 2 Potential CO kinetics of MOF compounds functionalized with pure AEAM, pure spermidine, or mixed amines (spermidine and AEAM) measured at 60 °C and 30% RH for 15 min. 2 productivity; and

[0023] Fig.11 It is shown that according to the present disclosure, at 4.5% (v / v) CO 2 The potential H ions of MOF compounds functionalized with pure AEAM, pure spermidine or mixed amines (spermidine and AEAM) measured at 60 °C and 30% RH. 2 O / CO 2 Compare.

[0024] Unless otherwise indicated, the drawings provided herein are intended to illustrate the features of the embodiments of the present disclosure. It is believed that these features are applicable to a wide variety of systems including one or more embodiments of the present disclosure. Therefore, the drawings are not intended to include all conventional features required for practicing the embodiments disclosed herein known to those of ordinary skill in the art. DETAILED DESCRIPTION

[0025] Embodiments described herein overcome at least some of the disadvantages of known adsorbents. Exemplary embodiments described herein include functionalized adsorbents. The functionalized adsorbents include: an adsorbent and at least one functionalized ligand comprising an aminoorganosilicon group. Compared to known adsorbents, exemplary embodiments described herein promote CO 2 Capacity and CO 2 The productivity is significantly improved. 2 O absorption, the exemplary embodiments described herein also promote CO 2 Significant improvement in absorption.

[0026] In some embodiments, the functionalized adsorbent includes a first type of functionalized ligand, wherein the first type of functionalized ligand includes at least one functionalized ligand comprising an aminoorganosilicon group. Generally, the at least one functionalized ligand comprising an aminoorganosilicon group can include any such suitable ligand that promotes the functionalized adsorbent described herein. The at least one functionalized ligand comprising an aminoorganosilicon group can include only one functionalized ligand comprising an aminoorganosilicon group, or include two or more functionalized ligands each comprising an aminoorganosilicon group.

[0027] Generally, the adsorbent can be any suitable adsorbent known in the art to promote the functionalized adsorbent described herein. In some embodiments, the adsorbent is selected from the group consisting of coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCP), covalent organic framework (COF) compounds, zeolitic imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open frameworks, network chemical compositions, silica particles, zeolites, silicon-aluminum-phosphates (SAPO), aluminum-phosphates (AlPO), polyaromatic frameworks (PAF), activated carbon, molecular organic solids, and combinations thereof.

[0028] As used herein, MOF compounds are compounds that include metal ions or clusters coordinated with organic ligands to form one-dimensional, two-dimensional or three-dimensional structures. The metal ions or clusters act as connectors and are bound by multi-directional organic ligands, which act as connectors in the network structure. MOF compounds have modular properties that allow synthetic tunability, which provide fine chemicals and structural control. Properties such as porosity, stability, particle morphology and conductivity can be customized for specific applications.

[0029] In many embodiments, the adsorbent is a MOF compound including a MOF metal or a metal-containing cluster and a MOF linker.

[0030] In some embodiments, the MOF metal can be any suitable MOF metal known in the art to promote the functionalized adsorbents 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, their ions, their hydrates, their salts, their halides, their fluorides, their chlorides, their bromides, their iodides, their nitrates, their acetates, their sulfates, their phosphates, their carbonates, their oxides, their formates, their carboxylates, and combinations thereof. In some embodiments, the MOF metal includes Mg.

[0031] In some embodiments, the MOF metal-containing cluster can be any suitable MOF metal-containing cluster known in the art to promote the functionalized adsorbent described herein. In some embodiments, the MOF metal-containing cluster includes a MOF metal node and a linker pillar, wherein the MOF metal and the linker are each defined as described herein. In other embodiments, the MOF metal-containing cluster includes a MOF metal-oxygen cluster.

[0032] In some embodiments, the MOF linker can be any suitable MOF linker known in the art to facilitate the functionalized adsorbents described herein. Generally, the geometry and connectivity of the linker contribute to the structure of the resulting MOF compound. Adjusting the linker geometry, length, ratio, and functional groups can adjust the size, shape, and internal surface properties of the MOF compound for targeted applications.

[0033] In at least some embodiments, the MOF linker is a linker selected from the group consisting of a polytopic linker, a dihedral linker, a trihedral linker, a tetrahedral linker, a pentahedral linker, a hexahedral linker, a heptahedral linker, an octahedral linker, a mixed linker, an asymmetric linker, a metal linker, an N-heterocyclic linker, and combinations thereof.

[0034] In at least some embodiments, the MOF linker is a linker selected from the group consisting of: a polyhedral linker, 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H 4 DOBPDC), 4,4′-dioxybiphenyl-3,3′-dicarboxylate (DOBPDC 4- )、4,4″-dioxo-[1,1′:4′,1″-terphenyl]-3,3″-dicarboxylate (dotpdc4- )、2,5-dioxybenzene-1,4-dicarboxylate (dobdc 4- )、4,6-dihydroxyisophthalic acid (m-dobdc 4- )、3,3′-dioxo-biphenyl-4,4′-dicarboxylate (p-carboxylate-dobpdc 4- ), 4,4′-[oxalylbis(imino)]bis(2-hydroxybenzoic acid)(H 4 ODA), 4,4′-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H 4 TDA), 4,4′-dihydroxyazobenzene-3,3′-dicarboxylic acid (H 4 OSA), their protonated, partially and completely deprotonated forms, and combinations thereof. As another example, in at least 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, tetrazoles, and combinations thereof.

[0035] As another example, in at least some embodiments, the MOF linker is a dicarboxylic acid linker 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, acetylene dicarboxylic 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, terephthalic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline quinoline-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, diimide dicarboxylic 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-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic 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, 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-chloroquine 1,4-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,8-naphthalene-2-carboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2′-biquinoline-4,4′-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenone dicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E400-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′-diaminodiphenyl ether imide dicarboxylic acid, 4,4′-diaminodiphenylmethane imide dicarboxylic acid, 4,4′-diaminodiphenyl sulfone imide dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 8-methoxy-2,3-naphthalene dicarboxylic acid, 8-nitro-2,3-naphthalene dicarboxylic acid, 8-sulfo-2,3-naphthalene dicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2′-3′-diphenyl-4,4″-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromic acid 2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, trihexadecanedicarboxylic 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′-dihydroxy Diphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorescein ring-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-phthalic acid, 2,6-pyridinedicarboxylic acid 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.

[0036] As another example, in at least some embodiments, the MOF linker is a tricarboxylic acid linker 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.

[0037] As another example, in at least some embodiments, the MOF linker is a tetracarboxylic acid linker selected from the group consisting of 1,1-dioxide-perylene[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7, 10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 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.

[0038] In this exemplary embodiment, the MOF linker is 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H 4 dobpdc) and / or 4,4′-dioxybiphenyl-3,3′-dicarboxylate (dobpdc 4- In some embodiments, dobpdc includes 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid, its monocarboxylate form, its dicarboxylate form, its monophenolate form, its diphenolate form, and combinations thereof.

[0039] In some embodiments, the MOF linker is one or more of the following linkers:

[0040]

[0041]

[0042]

[0043] and / or

[0044]

[0045] 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-303 family. In some embodiments, the MOF compound is Mg 2 (dobpdc).

[0046] In some embodiments, the functionalized adsorbent is a functionalized MOF compound of formula (I)

[0047]

[0048] in:

[0049] M is the MOF metal or metal-containing cluster;

[0050] L is a MOF linker;

[0051] F A is at least one functionalized ligand comprising an amino organosilicon group;

[0052] F B is at least one functionalized ligand that does not contain an amino organosilicon group;

[0053] x is a value in the range of 1 to 6;

[0054] y is a value in the range of 1 to 6;

[0055] a is a value greater than 0 and less than or equal to 2; and

[0056] b is a value in the range of 0 to 2.

[0057] In some embodiments, the functionalized adsorbent includes a second type of functionalized ligand, wherein the second type of functionalized ligand includes at least one functionalized ligand that does not contain an aminoorganosilicon group. In some embodiments, the functionalized adsorbent also includes at least one functionalized ligand that does not contain an aminoorganosilicon group. Generally, the at least one functionalized ligand that does not contain an aminoorganosilicon group can include any such suitable ligand that promotes the functionalized adsorbent described herein. The at least one functionalized ligand that does not contain an aminoorganosilicon group can include only one functionalized ligand that does not contain an aminoorganosilicon group, or include two or more functionalized ligands that each do not contain an aminoorganosilicon group.

[0058] In some embodiments, the at least one functionalized ligand that does not contain an amino silicone group is selected from the group consisting of: amine ligands, monoamine ligands, diamine ligands, triamine ligands, tetraamine ligands, pentamine ligands, hexamine ligands, polyamine ligands, alkylamine ligands, and amino alcohol ligands. 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-aminoethyl) -1,3-propylenediamine, bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane (spermidine), triethylenetetramine, N,N′-bis(2-aminoethyl)-1,3-propylenediamine, 1,2-bis(3-aminopropylamino)ethane, N,N′-bis(3-aminopropyl)-1,3-propylenediamine, N,N′-bis(3-aminopropyl)-1,4-diaminobutane (spermidine), tetraethylenepentamine and / or combinations thereof.

[0059] Typically, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group may be present in any suitable ratio known in the art to promote the functionalized adsorbent 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 functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 10:1 to about 1:10. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 9:1 to about 1:9. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 8:1 to about 1:8. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 7:1 to about 1:7. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 6:1 to about 1:6. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 5:1 to about 1:5. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 4:1 to about 1:4. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 3:1 to about 1:3. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 2: 1 to about 1: 2. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio of about 1: 1.

[0060] In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group is present in an amount less than the at least one functionalized ligand not comprising an aminoorganosilicon group.

[0061] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group 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.

[0062] In many embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group can be any suitable at least one functionalized ligand comprising an aminoorganosilicon group known in the art to promote the functionalized adsorbents described herein.

[0063] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group 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 an aminosilicone group comprises at least one primary amine or at least one secondary amine.

[0064] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentamines, hexamines, polyamines, and combinations thereof.

[0065] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group 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.

[0066] In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group comprises a symmetrical structure. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group comprises an asymmetrical structure.

[0067] In some embodiments, when the at least one functionalized ligand comprising an aminoorganosilicon group comprises a disiloxane group, the at least one functionalized ligand comprising an aminoorganosilicon group comprises the same amine on both sides of the disiloxane group. In some embodiments, when the at least one functionalized ligand comprising an aminoorganosilicon group comprises a disiloxane group, the at least one functionalized ligand comprising an aminoorganosilicon group comprises different amines on either side of the disiloxane group.

[0068] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group is an amino-substituted siloxane of formula (II), formula (III), formula (IV), formula (V), formula (VI), or formula (VII):

[0069]

[0070]

[0071]

[0072] in:

[0073] R 1 , R 2 , R 3 , R 4 , R 9 , 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 C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0074] R 5 , R 6 , R 11 , R 15 and R 17 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 alkyl,

[0075] R 7 , R 8 , R 12 and R 16 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 an alkyl group, and a substituent of formula (VIII)

[0076]

[0077] in:

[0078] The wavy bond represents the bonding position with formula (II) or formula (III) or formula (IV) or formula (V) or formula (VI) or formula (VII);

[0079] 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 C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C 1 -C 6 Straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0080] R 25 and R 26 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl and substituted or unsubstituted C 4 -C6 Cycloalkyl, or when taken together, R 25 and R 26 forming a monocyclic ring selected from the group consisting of heterocycloalkyl and heteroaryl;

[0081] R 27 , R 28 and R 29 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, ether, -OCH 2 CH 2 -、-OCH 2 CH 2 CH 2 -、-OCH 2 CH 2 CH 2 CH 2 -、-NHCH 2 CH 2 -、-NHCH 2 CH 2 CH 2 - and -NHCH 2 CH 2 CH 2 CH 2 -;

[0082] R 30 Selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 4 -C 6 Cycloalkyl, heterocycloalkyl, and heteroaryl;

[0083] j is an integer ranging from 0 to 20;

[0084] k is an integer ranging from 0 to 20;

[0085] m is an integer in the range of 0 to 20; and

[0086] n is an integer ranging from 0 to 20.

[0087] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group is selected from the group consisting of:

[0088]

[0089]

[0090]

[0091]

[0092] as well as

[0093]

[0094] Generally, the adsorbent can be in any suitable form known in the art to facilitate the functionalized adsorbent described herein. In some embodiments, the adsorbent is in a form selected from the group consisting of powders, pellets, composites, composites mixed with a binder, membranes, coatings, packed beds, columns, monoliths, and combinations thereof.

[0095] Exemplary embodiments described herein include an adsorbent system. Generally, the adsorbent system can be any suitable adsorbent system known in the art that promotes the functionalized adsorbent described herein. In some embodiments, the adsorbent system includes a functionalized adsorbent and an optional binder. In some embodiments, the adsorbent system is disposed on a polymer membrane.

[0096] In some embodiments, the adsorbent system comprises at least one contactor. In some embodiments, the adsorbent system comprises more than one contactor. In some embodiments, the adsorbent system comprises a contactor configured for an adsorption cycle and a contactor configured for a desorption cycle. The contactor can be any suitable contactor known in the art to promote the functionalized adsorbent described herein. In some embodiments, the adsorbent is integrated into at least one channel of the contactor. In some embodiments, the contactor is made of the adsorbent itself. In some embodiments, the contactor is coated with an adsorbent system. In some embodiments, the contactor comprises more than one adsorbent coating, wherein at least one adsorbent coating is an adsorbent system.

[0097] In some embodiments, the adsorbent system includes a skeleton. The skeleton can be any suitable skeleton known in the art that promotes the functionalized adsorbent described herein. The skeleton can be included in a contactor or between two contactors. The skeleton can be composed of one component or more than one component. In some embodiments, the skeleton is an air skeleton. In some embodiments, the configuration of the skeleton is selected from the group consisting of a polygonal configuration, a rectangular configuration, a square configuration, a circular configuration, an asymmetric configuration, and a combination thereof. In some embodiments, the adsorbent system is mounted on the skeleton.

[0098] In some embodiments, the adsorbent system includes at least one concentrator. The concentrator can be any suitable concentrator known in the art to facilitate the functionalized adsorbent described herein. The concentrator can be a passive concentrator or an active concentrator.

[0099] In some embodiments, the adsorbent system includes at least one component configured to drive fluid flow. The component configured to drive fluid flow can be any suitable component configured to drive fluid flow known in the art to promote the functionalized adsorbent described herein. In some embodiments, the component configured to drive fluid flow is selected from the group consisting of a pump, a fan, and a combination thereof.

[0100] In some embodiments, the adsorbent system includes at least one component configured to change temperature. The component configured to change temperature can be any suitable component configured to change temperature known in the art to facilitate the functionalized adsorbent described herein. In some embodiments, the component configured to change temperature is selected from the group consisting of a heater, a cooler, and a combination thereof.

[0101] In some embodiments, the adsorbent system includes at least one component configured to transport a fluid. The component configured to transport a fluid can be any suitable component configured to transport a fluid known in the art that facilitates the functionalized adsorbent 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.

[0102] In general, the functionalized adsorbents may be used for any suitable purpose known in the art that facilitates the use of the functionalized adsorbents described herein. In some embodiments, the functionalized adsorbents are used in adsorbent systems. In some embodiments, the functionalized adsorbents are used in carbon capture adsorbent systems. In some embodiments, the functionalized adsorbents are used in moisture adsorbent systems. In some embodiments, the functionalized adsorbents are used in carbon capture adsorbent systems in the presence of water. In some embodiments, the functionalized adsorbents are used to capture gases. In some embodiments, the functionalized adsorbents are used to capture CO after combustion.2 and / or direct air capture CO 2 .

[0103] Exemplary embodiments described herein include methods of making adsorbent systems. Generally, the functionalized adsorbents can be prepared according to any suitable synthesis method known in the art that facilitates the functionalized adsorbents described herein.

[0104] In many embodiments, the method of preparing an adsorbent system comprises functionalizing the adsorbent with at least one functionalized ligand comprising an aminoorganosilicon group. In some embodiments, the method of preparing an adsorbent system comprises functionalizing the adsorbent with at least two functionalized ligands each comprising an aminoorganosilicon group, wherein the aminoorganosilicon groups are different from each other. In some embodiments, the method of preparing an adsorbent system further comprises functionalizing the adsorbent with at least one functionalized ligand that does not comprise an aminoorganosilicon group. In some embodiments, the method of preparing an adsorbent system comprises controlling the ratio between at least one functionalized ligand comprising an aminoorganosilicon group and at least one functionalized ligand that does not comprise an aminoorganosilicon group.

[0105] In some embodiments, the method of preparing the adsorbent system further comprises annealing the functionalized adsorbent. Annealing the adsorbent system may remove excess ligands. In some embodiments, annealing the functionalized adsorbent comprises annealing the functionalized adsorbent at an elevated temperature. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 50°C to about 400°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 100°C to about 300°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 150°C to about 250°C.

[0106] Figure 1 is an exemplary process flow diagram 110. In this exemplary embodiment, process flow diagram 110 depicts exemplary steps of process embodiments described herein and is not intended to limit these process embodiments. In this exemplary embodiment, the process includes forming 112 a mixture comprising: an adsorbent; at least one functionalized ligand comprising an aminoorganosilicon group; optionally at least one functionalized ligand not comprising an aminoorganosilicon group; optionally a solvent, and optionally a non-solvent. The process also includes functionalizing 114 the adsorbent.

[0107] In some embodiments, a method of preparing a functionalized adsorbent includes (I) forming 112 a mixture comprising an adsorbent, at least one functionalized ligand comprising an aminosilicone group, optionally at least one functionalized ligand not comprising an aminosilicone group, optionally a solvent, and optionally a non-solvent; and (II) functionalizing 114 the adsorbent.

[0108] In some embodiments, functionalizing 114 the adsorbent includes stirring the mixture.

[0109] In some embodiments, functionalizing 114 the adsorbent includes functionalizing 114 the adsorbent in the presence of an inert gas.

[0110] In some embodiments, functionalizing 114 the adsorbent includes functionalizing 114 the adsorbent at a temperature in a range of about 0° C. to about 100° C. In some embodiments, functionalizing 114 the adsorbent includes functionalizing 114 the adsorbent at a temperature in a range of about 20° C. to about 80° C. In some embodiments, functionalizing 114 the adsorbent includes functionalizing 114 the adsorbent at a temperature in a range of about 20° C. to about 60° C.

[0111] In some embodiments, functionalizing 114 the adsorbent includes functionalizing 114 the adsorbent for a time in a range of about 1 minute to about 7 days. In some embodiments, functionalizing 114 the adsorbent includes functionalizing 114 the adsorbent for a time in a range of about 1 hour to about 3 days.

[0112] In some embodiments, the adsorbent is desolvated prior to functionalization 114. In some embodiments, the adsorbent is dry prior to functionalization.

[0113] In some embodiments, the adsorbent is annealed after functionalization 114. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at an elevated temperature. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 50°C to about 400°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 100°C to about 300°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 150°C to about 250°C.

[0114] In some embodiments, the adsorbent is prepared according to the method disclosed in US Provisional Patent Application No. 63 / 399,251. In some embodiments, at least one functionalized ligand comprising an aminosilicone group is prepared according to the method disclosed in US Provisional Patent Application No. 63 / 386,231.

[0115] 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.

[0116] Typically, a non-solvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, a non-solvent is a liquid-based component contained in the reaction mixture. In some embodiments, a non-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, a non-solvent is selected from the group consisting of an organic solvent, an aqueous solvent, and a combination thereof.

[0117] In some embodiments, the non-solvent facilitates functionalization. In some embodiments, the selectivity of functionalization is controlled by relative solubility. For example, one or more adsorbents or amines may have different solubility in a liquid-based reaction mixture compared to another adsorbent or amine or functionalized adsorbent. Thus, relative solubility introduces limiting reactions and / or reagents.

[0118] In many embodiments, the method may also include any other suitable processing steps known in the art that promote the success of the methods described herein. Such processing steps may include, but are not limited to, only washing, drying, filtering, purifying, separating, centrifuging, and any combination thereof. In some embodiments, the method also includes washing the functionalized adsorbent. In some embodiments, the method also includes purifying the functionalized adsorbent. In some embodiments, purification includes using distillation, vacuum distillation, and / or heating.

[0119] Exemplary embodiments described herein include methods of capturing at least one gas.

[0120] Figure 2 is an exemplary method flow chart 210. In this exemplary embodiment, the method flow chart 210 depicts exemplary method steps of the method embodiments described herein and is not intended to limit these method embodiments. The method includes receiving 212 a gas source comprising at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises: an adsorbent; and at least one functionalized ligand comprising an aminoorganosilicon group. In some embodiments, the functionalized adsorbent includes at least two functionalized ligands each comprising an aminoorganosilicon group, wherein the aminoorganosilicon groups are different from each other. In some embodiments, the functionalized adsorbent also includes at least one functionalized ligand that does not include an aminoorganosilicon group. The method also includes capturing 214 a certain amount of at least one gas with the functionalized adsorbent.

[0121] In some embodiments, the method includes: (I) receiving 212 a gas source comprising at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising an aminosilicone group; and (II) capturing 214 a quantity of the at least one gas with the functionalized adsorbent.

[0122] Generally, the gas source can be any suitable gas source known in the art to promote the methods described herein. In some embodiments, the gas source is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, and combinations thereof.

[0123] Typically, the at least one gas can be any suitable gas known in the art to promote the methods described herein. In 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 gas, and combinations thereof.

[0124] In some embodiments, the 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, the 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, the 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).

[0125] 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 300 ppmv to about 5000 ppmv.

[0126] In some embodiments, the at least one gas comprises water vapor. In some embodiments, the at least one gas comprises water vapor in an amount in the range of about 0.001% (v / v) to about 25% (v / v). In some embodiments, the at least one gas comprises water vapor in an amount in the range of about 0.01% (v / v) to about 20% (v / v). In some embodiments, the at least one gas comprises water vapor in an amount in the range of about 0.5% (v / v) to about 15% (v / v). In some embodiments, the at least one gas comprises water vapor in an amount in the range of about 0.5% (v / v) to about 4% (v / v). In some embodiments, the at least one gas comprises water vapor in an amount in the range of about 4% (v / v) to about 15% (v / v).

[0127] In some embodiments, the 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 water vapor is present. In some embodiments, the 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 water vapor is present. In some embodiments, the 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 water vapor is present. In some embodiments, the at least one gas is present in the source gas in an amount greater than about 10% (v / v) and water vapor is present. 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).

[0128] In some embodiments, capturing 214 an amount of the at least one gas with a functionalized adsorbent includes adsorbing an amount of the at least one gas with a functionalized adsorbent. In some embodiments, capturing 214 an amount of the at least one gas with a functionalized adsorbent includes adsorbing an amount of the at least one gas with a functionalized adsorbent in the presence of water vapor.

[0129] In some embodiments, the amount of at least one gas captured 214 with the functionalized adsorbent is in the range of 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 at least one gas captured 214 with the functionalized adsorbent is in the range of 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 at least one gas captured 214 with the functionalized adsorbent is in the range of 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 at least one gas captured 214 with the functionalized adsorbent is in the range of 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 captured 214 with the functionalized sorbent is in a range from about 40% (v / v) to about 60% (v / v) of the at least one gas present in the source gas.

[0130] In some embodiments, the amount of at least one gas captured 214 with a functionalized adsorbent is in the range of 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 at least one gas captured 214 with a functionalized adsorbent is in the range of 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 at least one gas captured 214 with a functionalized adsorbent is in the range of 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 at least one gas captured 214 with a functionalized adsorbent is in the range of 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 at least one gas captured 214 with a functionalized adsorbent is in the range of about 1% (v / v) to about 5% (v / v) of the at least one gas present in the source gas.

[0131] In some embodiments, the amount of at least one gas captured 214 with the functionalized adsorbent is in the range of 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 at least one gas captured 214 with the functionalized adsorbent is in the range of 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 at least one gas captured 214 with the functionalized adsorbent is in the range of 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 at least one gas captured 214 with the functionalized adsorbent is in the range of about 95% (v / v) to about 100% (v / v) of the at least one gas present in the source gas.

[0132] In some embodiments, the source gas is modified to change the amount of water vapor. In some embodiments, changing the amount of water vapor includes increasing the amount of water vapor. In some embodiments, changing the amount of water vapor includes reducing the amount of water vapor. In some embodiments, increasing the amount of water vapor includes adding or injecting water vapor into the source gas. In some embodiments, reducing the amount of water vapor includes removing water vapor from the source gas by evaporation, condensation and / or pre-adsorption. In some embodiments, changing the amount of water vapor includes exhaust gas recirculation (EGR) and / or mixing.

[0133] In many embodiments, the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof is at a temperature. Each temperature may be varied to facilitate the methods described herein. Each temperature may have a uniform temperature profile, a gradient temperature profile, a discrete temperature profile, or a combination thereof.

[0134] In some embodiments, the method includes an adsorption cycle. In some embodiments, the method includes a desorption cycle. In some embodiments, during the gas adsorption cycle, at least one of the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof is at a temperature in the range of about 0°C to about 150°C. In some embodiments, during the gas desorption cycle, at least one of the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof is at a temperature in the range of about 60°C to about 250°C.

[0135] In some embodiments, the method includes controlling the temperature.The temperature of the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof can be controlled.

[0136] Exemplary embodiments described herein include methods of collecting at least one gas from a gas source.

[0137] Figure 3310 is an exemplary method flow chart. In this exemplary embodiment, the method flow chart 310 depicts exemplary method steps of the method embodiments described herein and is not intended to limit these method embodiments. The method includes receiving 212 a gas source containing at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent includes: an adsorbent; and at least one functionalized ligand containing an aminoorganosilicon group. In some embodiments, the functionalized adsorbent includes at least two functionalized ligands each containing an aminoorganosilicon group, wherein the aminoorganosilicon groups are different from each other. In some embodiments, the functionalized adsorbent also includes at least one functionalized ligand that does not contain an aminoorganosilicon group. The method also includes capturing 314 a certain amount of at least one gas with the functionalized adsorbent. The method also includes releasing 316 at least one gas from the functionalized adsorbent.

[0138] In some embodiments, the method includes: (I) receiving 312 a gas source comprising at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent includes an adsorbent and at least one functionalized ligand comprising an aminosilicone group; (II) capturing 314 an amount of the at least one gas with the functionalized adsorbent; and (III) releasing 316 the at least one gas from the functionalized adsorbent.

[0139] In some embodiments, releasing 316 the at least one gas from the functionalized adsorbent includes purging the at least one gas from the functionalized adsorbent with a purge gas. In some embodiments, releasing 316 the at least one gas from the functionalized adsorbent includes receiving a change in temperature or pressure at the functionalized adsorbent.

[0140] In some embodiments, at least one gas is released 316 from the functionalized adsorbent into a receiving gas. In some embodiments, the receiving gas is selected from the group consisting of air, N 2 , steam, and combinations thereof. In some embodiments, after receiving the at least one gas, the receiving gas is removed from the presence of the functionalized adsorbent. In some embodiments, the receiving gas has a higher concentration of at least one gas than the source gas.

[0141] Other aspects of the disclosure are provided by the subject matter of the following clauses:

[0142] 1. A functionalized adsorbent, comprising:

[0143] Adsorbents; and

[0144] At least one functionalized ligand comprising an aminosilicone group.

[0145] 2. A method for preparing a functionalized adsorbent, the method comprising:

[0146] (I) forming a mixture, the mixture comprising:

[0147] Adsorbent;

[0148] at least one functionalized ligand comprising an aminoorganosilicon group;

[0149] optionally at least one functionalized ligand not comprising an aminosilicone group;

[0150] optionally a solvent; and

[0151] optionally a non-solvent; and

[0152] (II) functionalizing the adsorbent.

[0153] 3. A method for capturing at least one gas, the method comprising:

[0154] (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises:

[0155] Adsorbents; and

[0156] at least one functionalized ligand comprising an aminosilicone group; and

[0157] (II) capturing a quantity of the at least one gas with the functionalized adsorbent.

[0158] 4. A method of collecting at least one gas, the method comprising:

[0159] (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises:

[0160] Adsorbents; and

[0161] at least one functionalized ligand comprising an aminoorganosilicon group;

[0162] (II) capturing a quantity of the at least one gas with the functionalized adsorbent; and

[0163] (III) releasing the at least one gas from the functionalized adsorbent.

[0164] 5. The functionalized adsorbent according to any preceding clause, further comprising at least one functionalized ligand not comprising an aminosilicone group.

[0165] 6. The functionalized adsorbent according to any preceding clause, wherein the at least one functionalized ligand comprising aminoorganosilicon groups and the at least one functionalized ligand not comprising aminoorganosilicon groups are present in a ratio ranging from about 10:1 to about 1:10.

[0166] 7. A functionalized adsorbent according to any of the preceding clauses, wherein the adsorbent is selected from the group consisting of coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCP), covalent organic framework (COF) compounds, zeolitic imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open frameworks, network chemical components, silica particles, zeolites, silicon-aluminum-phosphates (SAPO), aluminum-phosphates (AlPO), polyaromatic frameworks (PAF), activated carbon, molecular organic solids and combinations thereof.

[0167] 8. A functionalized adsorbent according to any preceding clause, wherein the functionalized adsorbent is a functionalized MOF compound of formula (I)

[0168]

[0169] in:

[0170] M is the MOF metal or metal-containing cluster;

[0171] L is a MOF linker;

[0172] F A is the at least one functionalized ligand comprising an amino organosilicon group;

[0173] F B is at least one functionalized ligand that does not contain an amino organosilicon group;

[0174] x is a value in the range of 1 to 6;

[0175] y is a value in the range of 1 to 6;

[0176] a is a value greater than 0 and less than or equal to 2; and

[0177] b is a value in the range of 0 to 2.

[0178] 9. A functionalized adsorbent according to any preceding clause, wherein the MOF metal or metal-containing cluster comprises a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, their ions, their hydrates, their salts, their halides, their fluorides, their chlorides, their bromides, their iodides, their nitrates, their acetates, their sulfates, their phosphates, their carbonates, their oxides, their formates, their carboxylates and combinations thereof.

[0179] 10. The functionalized adsorbent according to any preceding clause, wherein the MOF linker comprises a linker selected from the group consisting of: a polyhedral linker, 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H 4 DOBPDC), 4,4′-dioxybiphenyl-3,3′-dicarboxylate (DOBPDC 4- )、4,4″-dioxo-[1,1′:4′,1″-terphenyl]-3,3″-dicarboxylate (dotpdc 4- )、2,5-dioxybenzene-1,4-dicarboxylate (dobdc 4- )、4,6-dihydroxyisophthalic acid (m-dobdc 4- )、3,3′-dioxo-biphenyl-4,4′-dicarboxylate (p-carboxylate-dobpdc 4- ), 4,4′-[oxalylbis(imino)]bis(2-hydroxybenzoic acid)(H 4 ODA), 4,4′-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H 4 TDA), 4,4′-dihydroxyazobenzene-3,3′-dicarboxylic acid (H 4OSA), dicarboxylates, terephthalic acid, tricarboxylates, 1,3,5-benzenetricarboxylic acid, nitrogen azoles, tetrazoles, 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, terephthalic acid, imidazole-2,4-dicarboxylic acid, 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, diimide dicarboxylic 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-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic 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, 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-chloroquine 1,4-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-benzoylphenyl-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic 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′-diaminodiphenyl ether imide dicarboxylic acid, 4,4′-diaminodiphenylmethane imide dicarboxylic acid, 4,4′-diaminodiphenyl sulfone imide dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 8-methoxy-2,3-naphthalene dicarboxylic acid, 8-nitro-2,3-naphthalene dicarboxylic acid, 8-sulfo-2,3-naphthalene dicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2′-3′-diphenyl-p-terphenyl-4,4″-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinoline dicarboxylic acid, 4,5-imidazole dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, trihexane dicarboxylic acid, tetradecanedicarboxylic acid formic 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, eicosene dicarboxylic 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-2,3-dicarboxylic acid, 2,9-dichlorofluorescein ring-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2′,5′-dicarboxylic acid, 1,3-benzenedicarboxylic acid,

[0180] 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, 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, 1,1-dioxide-perylene[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, 1,2,4,5-benzene tetracarboxylic acid, 1,2,11,12-dodecane tetracarboxylic acid, 1,2,5,6-hexane tetracarboxylic 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, polyhedral linkers, dihedral linkers, trihedral linkers, tetrahedral linkers, pentahedral linkers, hexahedral linkers, heptahedral linkers, octahedral linkers, mixed linkers, asymmetric linkers, metal linkers, N-heterocyclic linkers, their protonated, partially or completely deprotonated forms, and combinations thereof.

[0181] 11. The functionalized adsorbent according to any preceding clause, wherein the at least one functionalized ligand comprising an aminosilicone group comprises at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof.

[0182] 12. The functionalized adsorbent according to any preceding clause, wherein the at least one functionalized ligand comprising aminosilicone groups comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentamines, hexamines, polyamines, and combinations thereof.

[0183] 13. A functionalized adsorbent according to any preceding clause, wherein the at least one functionalized ligand comprising an aminosilicone group 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] 14. The functionalized adsorbent according to any preceding clause, wherein the at least one functionalized ligand comprising an aminoorganosilicon group comprises a symmetrical structure.

[0185] 15. The functionalized adsorbent according to any preceding clause, wherein the at least one functionalized ligand comprising an aminosilicone group comprises an asymmetric structure.

[0186] 16. A functionalized adsorbent according to any preceding clause, wherein the at least one functionalized ligand comprising an aminosilicone group is an amino-substituted siloxane of formula (II), formula (III), formula (IV), formula (V), formula (VI) or formula (VII)

[0187]

[0188]

[0189]

[0190] in:

[0191] R 1 , R 2 , R 3 , R 4 , R 9 , 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 C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0192] R 5 , R 6 , R 11 , R 15 and R 17 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 alkyl,

[0193] R 7 , R 8 , R 12 and R 16 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 an alkyl group, and a substituent of formula (VIII)

[0194]

[0195] in:

[0196] The wavy bond represents the bonding position with formula (II) or formula (III) or formula (IV) or formula (V) or formula (VI) or formula (VII);

[0197] 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 C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C 1 -C 6 Straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0198] R 25 and R 26 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl and substituted or unsubstituted C 4 -C 6 Cycloalkyl, or when taken together, R 25 and R 26 forming a monocyclic ring selected from the group consisting of heterocycloalkyl and heteroaryl;

[0199] R 27 , R 28 and R 29 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, ether, -OCH 2 CH 2 -、-OCH 2 CH 2 CH 2 -、-OCH 2 CH 2 CH 2 CH 2 -、-NHCH 2 CH 2 -、-NHCH 2 CH2 CH 2 - and -NHCH 2 CH 2 CH 2 CH 2 -;

[0200] R 30 Selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 4 -C 6 Cycloalkyl, heterocycloalkyl, and heteroaryl;

[0201] j is an integer ranging from 0 to 20;

[0202] k is an integer ranging from 0 to 20;

[0203] m is an integer in the range of 0 to 20; and

[0204] n is an integer ranging from 0 to 20.

[0205] 17. The functionalized adsorbent according to any preceding clause, wherein the at least one functionalized ligand comprising an aminosilicone group is selected from the group consisting of:

[0206]

[0207]

[0208]

[0209]

[0210] as well as

[0211]

[0212] 18. An adsorbent system comprising a functionalized adsorbent according to any preceding clause.

[0213] 19. The method according to any preceding clause, wherein functionalizing the adsorbent comprises stirring the mixture.

[0214] 20. The method according to any preceding clause, wherein functionalizing the adsorbent comprises functionalizing the adsorbent in the presence of an inert gas.

[0215] 21. The method according to any preceding clause, wherein functionalizing the adsorbent comprises functionalizing the adsorbent at a temperature in the range of about 0°C to about 100°C.

[0216] 22. The method according to any preceding clause, wherein functionalizing the adsorbent comprises functionalizing the adsorbent for a time in a range from about 1 minute to about 7 days.

[0217] 23. A method according to any preceding clause, wherein the adsorbent is desolvated prior to functionalization.

[0218] 24. A method according to any preceding clause, wherein the adsorbent is dried prior to functionalization.

[0219] 25. A method according to any preceding clause, wherein the adsorbent is annealed at an elevated temperature after functionalization.

[0220] 26. The method according to any preceding clause, wherein the solvent is selected from the group consisting of organic solvents, aqueous solvents, and combinations thereof.

[0221] 27. A method according to any preceding clause, 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 gas and combinations thereof.

[0222] 28. A method according to any preceding clause, 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 gas and combinations thereof.

[0223] 29. A method of collecting at least one gas from a gas source, the method comprising:

[0224] The method according to any preceding clause captures the at least one gas, and (III) releases the at least one gas from the functionalized adsorbent.

[0225] 30. A method according to any preceding clause, wherein the at least one gas is in the presence of water.

[0226] 31. The method of any preceding clause, further comprising capturing an amount of water with the functionalized adsorbent.

[0227] 32. The method according to any preceding clause, further comprising releasing water from the functionalized adsorbent.

[0228] References to “some embodiments” in the above description are not intended to be interpreted as excluding the existence of additional embodiments that also incorporate the recited features.

[0229] Example

[0230] Without further detailed description, it is believed that those skilled in the art can make the most of the present invention using the foregoing description. Therefore, the following examples are to be construed as illustrative only and not to limit the present disclosure in any way. The starting materials for the following examples may not necessarily be prepared by a specific preparation run, the procedures of which are described in other embodiments. It should also be understood that any numerical range described herein includes all values ​​from the lower limit to the upper limit. For example, if the range is stated as 10 to 50, it is intended to explicitly list values ​​such as 12 to 30, 20 to 40, or 30 to 50 in this specification. These are only examples of specific intent, and all possible combinations of numerical values ​​between and including the lowest and highest values ​​listed are considered to be explicitly stated in the present application.

[0231] Example 1. Synthesis of MOF compound 1 .

[0232] A 20 mL scintillation vial was charged with 2 equivalents of 1,3-bis(aminoethylaminomethyl)tetramethyldisiloxane (AEAM, 0.556 g, 2 mmol, 2 equivalents) and dissolved in 5 mL of toluene. Then, 0.320 g (1 mmol) of Mg was desolvated overnight in a vacuum oven at 120 °C. 2 (dobpdc) was added to the vial. The slurry was then placed on a hot plate and stirred at 300-400 rpm for 3 days at 60°C. The material was cooled to room temperature and transferred to a conical tube. The material was spun at 4000 rpm for 2 minutes, then the solvent was poured out and resuspended in another 10 mL of toluene for 4-6 hours. It was centrifuged, poured out and dried in a vacuum oven at 120°C overnight to obtain 0.4881 g of MOF compound 1 (yield 84%, Mg 2 (dobpdc)(AEAM) 0.94 ).

[0233] Incubate with 20 μL of 35% DCl 2 O solution, 200 μL of D 2After digestion with 600 μL of DMSO-d6, the final material was 1 H NMR analysis. 1 H NMR (DMSO-d 6, D 2 O)δ7.87(dd,2H),7.70(dd,2H),7.00(dd,2H),3.22-3.16(m,7.52H),2.38(s,3.76H),0.17(s,11.28H).

[0234] Example 2. Synthesis of MOF compound 2 .

[0235] Spermine (1.406 g, 0.0069 mol, 1.2 equivalents) was placed in a 250 mL three-necked round-bottom flask and dissolved in 60 mL of toluene. 2 The mixture was bubbled for 30 minutes. Then, 1.846 g (0.0058 mol, 1 equivalent) of Mg was desolvated overnight in a vacuum oven at 120°C. 2 (dobpdc) was added to the container. At 60°C, under N 2 The slurry was stirred at 300 rpm for 3 days. The material was cooled to room temperature and collected by vacuum filtration. The filter cake was dissolved in another 100 mL of toluene, stirred at room temperature for 2 hours and filtered. The material was placed in a glass container and dried in a vacuum oven at 120°C overnight to obtain 2.738 g of MOF compound 2 (yield 90.3%, Mg2(dobpdc)(spermine) 1.01 ).

[0236] Incubate with 20 μL of 35% DCl 2 O solution, 200 μL of D 2 After digestion with 600 μL of DMSO-d6, the final material was 1 H NMR analysis. 1 H NMR (DMSO-d 6, D 2 O)δ7.86(dd,2H),7.69(dd,2H),6.99(dd,2H),2.98-2.88(m,12H),1.93(m,4H),1.65(bs,4H)

[0237] Example 3. Synthesis of MOF compound 3 .

[0238] Spermine (13.25 g, 0.065 mol, 3 equivalents) was placed in a 1 liter (L) three-necked round-bottom flask and dissolved in 220 mL of toluene. The mixture was then heated to 40°C with N2 gas dispersion tube. 2The mixture was bubbled for 30 minutes. Then, Mg (7.0 g, 0.022 mol, 1 eq.) which was desolvated overnight in a vacuum oven at 120°C was added. 2 (dobpdc) to the container. Then use N 2 The slurry was bubbled for another 30 min and heated under N 2 The mixture was stirred at 60°C at 300-400 rpm for 3 days. The material was cooled to room temperature and collected by vacuum filtration. The filter cake was dissolved in another 300 mL of toluene, stirred at room temperature for 4-6 hours and filtered. This step was repeated again. The material was placed in a glass container and dried in a vacuum oven at 120°C overnight to obtain 8.25 g of MOF compound 3 (yield 67.1%, Mg 2 (dobpdc)(spermine) 1.2 ).

[0239] Incubate with 20 μL of 35% DCl 2 O solution, 200 μL of D 2 After digestion with 600 μL of DMSO-d6, the final material was 1 H NMR analysis. 1 H NMR (DMSO-d 6, D 2 O)δ7.85(dd,2H),7.66(dd,2H),6.98(dd,2H),2.98-2.86(m,14.4H),1.93(m,4.8H),1.65(bs,4.8H).

[0240] Example 4. Synthesis of MOF compound 4 .

[0241] 1 equivalent of spermidine (0.0526 g, 0.36 mmol) was placed in a 20 mL scintillation vial and dissolved in 5 mL of toluene. Then, 0.160 g (0.36 mmol) of MgSO4 was desolvated overnight in a vacuum oven at 120°C. 2 (dobpdc)(IPA) 2 Add to a vial. The slurry was then placed on a hot plate and stirred at 300-400 rpm at 60°C overnight. The material was cooled to room temperature and transferred to a conical tube. The material was spun at 4000 rpm for 2 minutes, the solvent was poured out, and resuspended in another 10 mL of toluene for 4-6 hours. It was centrifuged, poured out, and dried in a vacuum oven at 120°C overnight to obtain 0.139 g of MOF compound 4 (yield 80.1%, Mg 2 (dobpdc (spermidine) 1.08 ).

[0242] Incubate with 20 μL of 35% DCl2 O solution, 200 μL of D 2 After digestion with 600 μL of DMSO-d6, the final material was 1 H NMR analysis. 1 H NMR (DMSO-d 6, D 2 O)δ7.85(dd,2H),7.68(dd,2H),6.98(dd,2H),2.97-2.78(m,8.64H),1.92(m,2.16H),1.61(m,4.32H).

[0243] Example 5. Variation of the functionalized ligands containing aminoorganosilicon groups and those not containing aminoorganosilicon groups. Methods for quantifying the amount of ligand .

[0244] The metal organic framework (MOF) is synthesized by an aqueous preparation method and washed three times with water and three times with a solvent (e.g., isopropanol). The material is then dried by vacuum filtration to obtain about 70%-75% solvated material. The exact molar amount of the MOF can be determined by determining how much residual solvent is present in the MOF. One possible method for this determination is by 1 HNMR analysis of solvent peaks, such as Mg 2 (dobpdc) 1 (alcohol) x .

[0245] Incubate with 20 μL of 35% DCl 2 O solution, 200 μL of D 2 O and 600 μL DMSO-d6 digestion, Mg 2 (dobpdc) 1 (IPA) 1.92 conduct 1 H NMR analysis. 1 H NMR (DMSO-d 6, D 2 O)δ7.86(dd,2H),7.69(dd,2H),6.99(dd,2H),3.75(m,1H),1.00(d,6H).

[0246] By adding at least one functionalized ligand not containing aminoorganosilicon groups, such as spermine, as a limiting reagent of x equivalents, and at least one functionalized ligand containing aminoorganosilicon groups, such as AEAM, as an excess reagent, a (MOF metal) can be formed. x (MOF connector) y (at least one functionalized ligand not comprising an aminosilicone group) z (at least one functionalized ligand comprising an aminosilicone group) 1-zComposition of materials.

[0247] Example 6. Synthesis of MOF compound 5 .

[0248] Spermine (3.14 g, 0.016 mol, 0.5 eq.), 1,3-bis(aminoethylaminomethyl)tetramethyldisiloxane (AEAM, 6.48 g, 0.023 mol, 0.75 eq.), and 310 mL of toluene were added to a 1-L three-necked round-bottom flask and heated to 40 ℃ with N2 gas dispersion tube. 2 The mixture was bubbled for 30 minutes. Then, 10 g (0.031 mol, 1 equivalent) of Mg was desolvated overnight in a vacuum oven at 120°C. 2 (dobpdc) to the container. Then use N 2 The slurry was bubbled for another 30 min and heated under N 2 The mixture was stirred at 60°C at 300-400 rpm for 3 days. The material was cooled to room temperature and collected by vacuum filtration. The filter cake was dissolved in another 300 mL of toluene, stirred at room temperature for 4-6 hours and filtered. The material was placed in a glass container and dried in a vacuum oven at 120°C overnight to obtain 12.8 g of MOF compound 5 (yield 75%, Mg 2 (dobpdc)(spermine) 0.65 (AEAM) 0.35 ).

[0249] Incubate with 20 μL of 35% DCl 2 O solution, 200 μL of D 2 After digestion with 600 μL of DMSO-d6, the final material was 1 H NMR analysis. 1 H NMR (DMSO-d 6 ,D 2 O)δ7.85(dd,2H),7.68(dd,2H),7.01(dd,2H),3.22-3.16(m,2.8H),2.98-2. 86(m,7.8H),2.38(s,1.4H),1.93(m,2.6H),1.65(bs,2.6H),0.16(s,4.2H).

[0250] Example 7. Synthesis of MOF compound 6 .

[0251] Spermidine (0.0363 g, 0.25 mmol, 0.5 eq.) and 1,3-bis(aminoethylaminomethyl)tetramethyldisiloxane (AEAM, 0.1044 g, 0.375 mmol, 0.75 eq.) were charged into a 20 mL scintillation vial and dissolved in 5 mL toluene. Then, 0.160 g (0.5 mmol) of MgSO4 was desolvated overnight in a vacuum oven at 120 °C. 2 (dobpdc) was added to the vial. The slurry was then placed on a hot plate and stirred at 300-400 rpm at 60°C for 3 days. The material was cooled to room temperature and transferred to a conical tube. The material was spun at 4000 rpm for 2 minutes, the solvent was poured out, and resuspended in another 10 mL of toluene for 4-6 hours. It was centrifuged, poured out, and dried in a vacuum oven at 120°C overnight to obtain 0.166 g of GE140 (yield 64%, Mg 2 (dobpdc)(spermidine) 0.68 (AEAM) 0.37 ).

[0252] Incubate with 20 μL of 35% DCl 2 O solution, 200 μL of D 2 O and 600 μL DMSO-d 6 After digestion, the final material was 1 H NMR analysis. 1 H NMR (DMSO-d 6 ,D 2 O)δ7.86(dd,2H),7.69(dd,2H),6.99(dd,2H),3.22-3.16(m,2.96H),2.97-2.7 8(m,5.44H),2.38(s,1.48H)1.92(m,1.36H),1.61(m,2.72H),0.17(s,4.44H).

[0253] Example 8. Comparative performance .

[0254] MOF adsorbents functionalized with pure AEAM (such as MOF compound 1), pure spermine (such as MOF compound 3), and mixed amines (such as MOF compound 5) were subjected to 4.5% (v / v) CO 2 and 400ppmv CO 2 The equilibrium CO measured under 2 Capacity(g CO2 / g 吸附剂 ) are shown as a function of spermine loading in Figure 4 and Figure 54.5% (v / v) corresponds to post-combustion capture (PCC) conditions, such as natural gas combined cycle post-combustion capture conditions, and 400 ppmv CO 2 Corresponds to direct air capture (DAC) conditions. These figures illustrate that for a 4.5% (v / v) CO 2 PCC conditions, maximum CO 2 The capacity increases with the increase of spermine percentage ( Figure 4 ). In the presence of 400ppmv CO 2 Under DAC conditions, the mixed amine-based adsorbent exhibited higher capacity ( Figure 5 ). In addition, by normalizing CO at a given cycle time 2 The unit of absorption calculation is g CO2 / (g 吸附剂 * hour) of CO 2 The productivity showed a strong dependence on the choice of ligand. For PCC conditions ( Figure 6 ) and DAC conditions ( Figure 7 ) both, the mixed amine adsorbent MOF compound 5 has a significantly improved productivity compared to the adsorbents with either amine component.

[0255] In addition, the mixed amine adsorbent MOF compound 5 significantly reduced the CO 2 absorb( Figure 8 ), indicating easier regeneration compared to pure spermine adsorbents such as MOF compound 3.

[0256] Similar performance improvements were obtained for spermidine-based adsorbent materials. Adsorbent materials functionalized with pure AEAM (such as MOF compound 1), pure spermidine (such as MOF compound 4), and mixed amines (such as MOF compound 6) were subjected to 4.5% (v / v) CO 2 The equilibrium CO concentration measured at 2 The capacity and productivity are shown as a function of spermidine loading. Fig. 9 and Fig.10 4.5% (v / v) corresponds to post-combustion capture conditions (PCC conditions), and 400 ppmv CO 2 Corresponding to direct air capture conditions (DAC conditions). These figures illustrate that for a 4.5% (v / v) CO 2 PCC conditions for concentration, maximum CO 2The capacity increased with increasing percentage of spermidine. However, the mixed amine adsorbent MOF compound 6 had the greatest productivity when compared to adsorbents with either amine component. In addition, the two adsorbent materials containing AEAM (such as MOF compound 1 with pure AEAM and MOF compound 6 with mixed amines) showed significantly reduced H compared to pure spermidine adsorbents (such as MOF compound 4). 2 O / CO 2 Compare( Fig.11 ).

[0257] Described herein are the significant advantages of functionalizing an adsorbent with at least one functionalized ligand comprising aminoorganosilicon groups, and optionally further functionalizing the adsorbent with at least one functionalized ligand not comprising aminoorganosilicon groups. The materials and methods of the present disclosure are broadly applicable to a wide variety of adsorbents and functionalized ligands.

[0258] Unless otherwise indicated, approximate language as used herein, such as "substantially", "substantially" and "about" indicate that as will be recognized by those of ordinary skill in the art, the terms so modified may apply only to approximate degrees, rather than absolute or perfect degrees. Therefore, the values ​​modified by one or more terms (such as "about", "approximately" and "substantially") are not limited to the specified precise values. In at least some cases, approximate language may correspond to the precision of the instrument used to measure the value. In addition, unless otherwise indicated, the terms "first", "second", etc. are used only as tags in this article, and are not intended to impose order, position or hierarchical requirements on the items to which these terms are related. In addition, for example, a reference to a "second" item does not require or exclude the existence of, for example, a "first" or lower numbered item or a "third" or higher numbered item.

[0259] Although specific features of various embodiments of the present invention may be shown in some drawings and not in other drawings, this is for convenience only. In addition, references to "some embodiments" in the above description are not intended to be interpreted as excluding the existence of additional embodiments that also include the described features. In accordance with the principles of the present invention, any feature of a drawing may be referenced and / or claimed in conjunction with any feature of any other drawing.

[0260] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any device or system and performing any combined method. The patentable scope of the invention is defined by the claims, and may include other examples that occur to one skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements that are not substantially different from the literal language of the claims.

[0261] It will be readily appreciated by those skilled in the art that some of the substituents disclosed herein depend on the presence of other substituents and are therefore optional. 9 When it is a direct key, R 1 and R 2 is an optional substituent not present in the compound. Similarly, in Formula II, when n is 0, in R 9 With R 10 There is a direct bond between them, and R 3 , R 4 and R 11 is an optional substituent that is not present in the compound. The optional nature of a substituent in one embodiment does not limit the presence of a substituent in another embodiment.

[0262] As used herein, the term "alkyl", whether used alone or in compound words such as "haloalkyl", includes straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl and isopropyl, or the different butyl, pentyl or hexyl isomers. Alkyl groups defined by multiple carbon atoms, such as C 6 Alkyl groups are understood to have that many carbon atoms, but are not otherwise limited.

[0263] 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.

[0264] As used herein, "aminoalkyl" includes N groups substituted with straight or branched chain alkyl groups.

[0265] As used herein, the term "halogen" or "halide", whether used alone or in a compound word such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. In addition, when used in a compound word such as "haloalkyl", the alkyl group may be partially or fully substituted with the same or different halogen atoms. Examples of "haloalkyl" include F 3 C、ClCH 2 CF 3 CH 2 and CF 3 CCl 2 The term "haloalkoxy" and the like are defined similarly to the term "haloalkyl". Examples of "haloalkoxy" include CF 3 O、CCl 3 CH 2 O.F 2 CHCH 2 CH 2 O and CF 3 CH 2 O.

[0266] As used herein, the term "heterocycle" means a ring in which at least one of the atoms forming the ring backbone is not carbon. Unless otherwise specified, a heterocycle may be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocycle satisfies Hückel's rule, the ring is also referred to as a "heteroaryl" or aromatic heterocycle. A "saturated heterocycle" refers to a heterocycle containing only single bonds between ring members.

[0267] As used herein, the term "aminosilicone group" includes functional groups containing both an amine group and a siloxane group (also known as a disiloxane group), wherein the siloxane group includes a Si-O-Si linkage.

[0268] 1 H NMR spectra are reported in ppm downfield from tetramethylsilane; “s” indicates a singlet, “d” indicates a doublet, “dd” indicates a doublet of a doublet, “ddd” indicates a doublet of a doublet of a doublet, “t” indicates a triplet, “m” indicates a multiplet, and “brs” indicates a broad singlet.

Claims

1. A functionalized adsorbent, comprising: Adsorbents; and At least one functionalized ligand comprising an aminosilicone group.

2. The functionalized adsorbent according to claim 1, further comprising at least one functionalized ligand that does not contain an aminosilicone group.

3. The functionalized adsorbent of claim 2, wherein the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 10:1 to about 1:

10.

4. The functionalized adsorbent of claim 1, wherein the adsorbent is selected from the group consisting of coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCP), covalent organic framework (COF) compounds, zeolitic imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open frameworks, network chemical compositions, silica particles, zeolites, silicon-aluminum-phosphates (SAPO), aluminum-phosphates (AlPO), polyaromatic frameworks (PAF), activated carbons, molecular organic solids, and combinations thereof.

5. The functionalized adsorbent according to claim 1, wherein the functionalized adsorbent is a functionalized MOF compound of formula (I): in: M is the MOF metal or metal-containing cluster; L is a MOF linker; F A is the at least one functionalized ligand comprising an amino organosilicon group; F B is at least one functionalized ligand that does not contain an amino organosilicon group; x is a value in the range of 1 to 6; y is a value in the range of 1 to 6; a is a value greater than 0 and less than or equal to 2; and b is a value in the range of 0 to 2.

6. The functionalized adsorbent according to claim 5, wherein the MOF metal or metal-containing cluster comprises a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, their ions, their hydrates, their salts, their halides, their fluorides, their chlorides, their bromides, their iodides, their nitrates, their acetates, their sulfates, their phosphates, their carbonates, their oxides, their formates, their carboxylates, and combinations thereof.

7. The functionalized adsorbent according to claim 5, wherein the MOF linker comprises a linker selected from the group consisting of: a polyhedral linker, 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H 4 DOBPDC), 4,4′-dioxybiphenyl-3,3′-dicarboxylate (DOBPDC 4- )、4,4″-dioxo-[1,1′:4′,1″-terphenyl]-3,3″-dicarboxylate (dotpdc 4- )、2,5-dioxybenzene-1,4-dicarboxylate (dobdc 4- )、4,6-dihydroxyisophthalic acid (m-dobdc 4- )、3,3′-dioxo-biphenyl-4,4′-dicarboxylate (p-carboxylate-dobpdc 4- ), 4,4′-[oxalylbis(imino)]bis(2-hydroxybenzoic acid)(H 4 ODA), 4,4′-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid)(H 4 TDA), 4,4′-dihydroxyazobenzene-3,3′-dicarboxylic acid (H 4 OSA), dicarboxylates, terephthalic acid, tricarboxylates, 1,3,5-benzenetricarboxylic acid, nitrogen azoles, tetrazoles, 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, terephthalic acid, imidazole-2,4-dicarboxylic acid, 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, diimide dicarboxylic 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-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic 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, 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-chloroquine 1,4-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-benzoylphenyl-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic 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′-diaminodiphenyl ether imide dicarboxylic acid, 4,4′-diaminodiphenylmethane imide dicarboxylic acid, 4,4′-diaminodiphenyl sulfone imide dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 8-methoxy-2,3-naphthalene dicarboxylic acid, 8-nitro-2,3-naphthalene dicarboxylic acid, 8-sulfo-2,3-naphthalene dicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2′-3′-diphenyl-p-terphenyl-4,4″-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinoline dicarboxylic acid, 4,5-imidazole dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, trihexadecanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptane dicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid formic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosene dicarboxylic 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-2,3-dicarboxylic acid, 2,9-dichlorofluorescein ring-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, 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, aurinetricarboxylic acid, 1,1-dioxide-perylene[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 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, polyhedral linkers, dihedral linkers, trihedral linkers, tetrahedral linkers, pentahedral linkers, hexahedral linkers, heptahedral linkers, octahedral linkers, mixed linkers, asymmetric linkers, metal linkers, N-heterocyclic linkers, their protonated, partially or completely deprotonated forms, and combinations thereof.

8. The functionalized adsorbent of claim 1, wherein the at least one functionalized ligand comprising an aminosilicone group comprises at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof.

9. The functionalized adsorbent of claim 1, wherein the at least one functionalized ligand comprising an aminosilicone group comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentamines, hexamines, polyamines, and combinations thereof.

10. The functionalized adsorbent of claim 1, wherein the at least one functionalized ligand comprising an aminosilicone group 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.

11. The functionalized adsorbent of claim 1, wherein the at least one functionalized ligand comprising an aminoorganosilicon group comprises a symmetrical structure.

12. The functionalized adsorbent of claim 1, wherein the at least one functionalized ligand comprising an aminoorganosilicon group comprises an asymmetric structure.

13. The functionalized adsorbent according to claim 1, wherein the at least one functionalized ligand comprising an aminosilicone group is an amino-substituted siloxane of formula (II), formula (III), formula (IV), formula (V), formula (VI), or formula (VII): in: R 1 , R 2 , R 3 , R 4 , R 9 , 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 C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; R 5 , R 6 , R 11 , R 15 and R 17 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 alkyl, R 7 , R 8 , R 12 and R 16 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 an alkyl group, and a substituent of formula (VIII) in: The wavy bond represents the bonding position with formula (II) or formula (III) or formula (IV) or formula (V) or formula (VI) or formula (VII); 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 C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C 1 -C 6 Straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R 25 and R 26 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl and substituted or unsubstituted C 4 -C 6 Cycloalkyl, or when taken together, R 25 and R 26 forming 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, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, ether, -OCH 2 CH 2 -、 -OCH 2 CH 2 CH 2 -,-OCH 2 CH 2 CH 2 CH 2 -,-NHCH 2 CH 2 -,-NHCH 2 CH 2 CH 2 -and-NHCH 2 CH 2 CH 2 CH 2 -; R 30 Selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 4 -C 6 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 in the range of 0 to 20; and n is an integer ranging from 0 to 20.

14. The functionalized adsorbent according to claim 1, wherein the at least one functionalized ligand comprising an aminosilicone group is selected from the group consisting of: as well as 15. An adsorbent system comprising the functionalized adsorbent according to claim 1.

16. A method for preparing a functionalized adsorbent, the method comprising: include: (I) forming a mixture, the mixture comprising: Adsorbent; at least one functionalized ligand comprising an aminoorganosilicon group; optionally at least one functionalized ligand not comprising an aminosilicone group; optionally a solvent; and and optionally a non-solvent; and (II) functionalizing the adsorbent.

17. A method for capturing at least one gas, the method comprising: include: (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises: Adsorbent; and at least one functionalized ligand comprising an aminosilicone group; and (II) capturing a quantity of the at least one gas with the functionalized adsorbent.

18. The method of claim 17, 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 gas, and combinations thereof.

19. The method of claim 17, 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 gas, and combinations thereof.

20. A method of collecting at least one gas from a gas source, the method include: The method of claim 17, capturing the at least one gas, and (III) releasing the at least one gas from the functionalized adsorbent.

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