Sorbents functionalized with ligands containing aminosilicone functional groups.

Abstract

Sorbents functionalized with aminosilicone-functional ligands are disclosed. Methods for making the aminosilicone-functional ligand-functionalized sorbents are also disclosed. Methods for using the aminosilicone-functional ligand-functionalized sorbents are also disclosed.

Description

[Technical Field]

[0001] The technical field of this disclosure relates generally to sorbents functionalized with ligands having aminosilicone functionality, methods for making same, and methods for using same. [Background technology]

[0002] Solid sorbents are useful in a wide variety of applications. For example, they are particularly useful for use in carbon capture sorbent systems, such as point source post-combustion and direct air capture of CO2.

[0003] Solid sorbents used for carbon capture offer a promising and technically and economically superior alternative to traditional liquid amine-based CO capture processes. For example, solid sorbents tend to have better adsorption capacity, lower regeneration energy requirements, and reduced system complexity and environmental and safety risks compared to activated liquid amines.

[0004] Sorbent materials are classified into two types based on their adsorption mechanism. The first type, physical sorbents, rely on non-covalent interactions (e.g., van der Waals interactions, dipole-dipole interactions, etc.) to absorb gaseous species such as CO and HO. Examples of physical sorbents include activated carbon, zeolites, and metal-organic frameworks (MOFs). The second type, chemical sorbents, adsorb CO through a reversible chemical reaction and the formation of ammonium carbamate, carbamic acid, ammonium carbonate, and / or ammonium bicarbonate. Specific examples of chemical sorbents include amine-functionalized silica particles, amine-functionalized polymers and resins, amine-functionalized metal-organic frameworks (MOFs), and amine-functionalized covalent organic frameworks (COFs).

[0005] As a result of chemical bonding, chemisorbent materials generally exhibit superior CO adsorption selectivity relative to interfering species such as N, methane, and CO compared to physisorbent materials. However, the effectiveness of chemisorbent systems is limited by the compositional nature of the functionalizing molecules that perform the chemisorption and the functionalization process. Therefore, there is a need for functionalized sorbents containing chemically and thermally stable molecular species that selectively absorb CO with high capacity and fast kinetics. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent No. 8,138,117 Summary of the Invention

[0007] In one aspect, a functionalized sorbent is provided, which comprises a sorbent and one or more functionalizing ligands comprising an aminosilicone group.

[0008] In another aspect, a method for making a functionalized sorbent is provided, the method comprising: (I) forming a mixture comprising a sorbent, one or more functionalizing ligands comprising aminosilicone groups, optionally one or more functionalizing ligands not comprising aminosilicone groups, optionally a solvent, and optionally a non-solvent; and (II) functionalizing the sorbent.

[0009] In another aspect, a method for capturing one or more gases is provided, the method comprising the steps of (I) receiving a gas source containing one or more gases with a functionalized sorbent, the functionalized sorbent comprising a sorbent and one or more functionalizing ligands comprising aminosilicone groups, and (II) capturing a quantity of the one or more gases with the functionalized sorbent.

[0010] In another aspect, a method for recovering one or more gases is provided, the method comprising the steps of (I) receiving a gas source containing one or more gases with a functionalized sorbent, the functionalized sorbent comprising a sorbent and one or more functionalizing ligands comprising aminosilicone groups, (II) capturing a quantity of the one or more gases with the functionalized sorbent, and (III) releasing the one or more gases from the functionalized sorbent. [Brief explanation of the drawings]

[0011] These and other features, aspects, and advantages of the present disclosure will become better understood by reference to the following detailed description taken in conjunction with the accompanying drawings, in which like reference numerals represent like elements throughout. [Figure 1] 1 is a flowchart of an exemplary method according to the present disclosure. [Figure 2] 1 is a flowchart of an exemplary method according to the present disclosure. [Figure 3] 1 is a flowchart of an exemplary method according to the present disclosure. [Figure 4] Figure 1 shows the potential CO2 capacity of MOF compounds functionalized with pure AEAM, pure spermine, or hybrid amine (spermine and AEAM) measured at 4.5% (v / v) CO2 concentration, 60 °C, and 30% RH according to the present disclosure. [Figure 5] Figure 1 shows the potential CO2 capacity of MOF compounds functionalized with pure AEAM, pure spermine, or hybrid amine (spermine and AEAM) measured at 400 ppmvCO2 concentration, 25°C, and 30% RH according to the present disclosure. [Figure 6] Figure 1 shows the potential CO productivity of MOF compounds functionalized with pure AEAM, pure spermine, or hybrid amine (spermine and AEAM) measured at 4.5% (v / v) CO concentration, 60 °C, and 30% RH according to the present disclosure. [Figure 7] Figure 1 shows the potential CO productivity of MOF compounds functionalized with pure AEAM, pure spermine, or hybrid amine (spermine and AEAM) measured at 400 ppmvCO concentration, 25°C, and 30% RH according to the present disclosure. [Figure 8]Dry CO2 isotherms of MOF compounds functionalized with pure spermine or hybrid amines (spermine and AEAM). [Figure 9] Figure 1 shows the potential CO2 capacity of MOF compounds functionalized with pure AEAM, pure spermidine, or hybrid amine (spermidine and AEAM) measured at 4.5% (v / v) CO2 concentration, 60 °C, and 30% RH according to the present disclosure. [Figure 10] Figure 1 shows the potential CO productivity over 15 min of MOF compounds functionalized with pure AEAM, pure spermidine, or hybrid amine (spermidine and AEAM) measured at 4.5% (v / v) CO concentration, 60 °C, and 30% RH according to the present disclosure. [Figure 11] Figure 1 shows the potential HO / CO ratio of MOF compounds functionalized with pure AEAM, pure spermidine, or hybrid amine (spermidine and AEAM) measured at 4.5% (v / v) CO concentration, 60 °C, and 30% RH according to the present disclosure.

[0012] Unless otherwise indicated, the drawings accompanying this application illustrate features of embodiments of the disclosed technology. These features are contemplated as being applicable to a wide variety of systems incorporating one or more embodiments of the disclosed technology. As such, the drawings may not include all of the conventional features known to those skilled in the art to be required to practice the embodiments disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0013] The embodiments described herein overcome at least some of the shortcomings of known sorbents. Exemplary embodiments described herein include functionalized sorbents. The functionalized sorbents include a sorbent and one or more functionalizing ligands comprising aminosilicone groups. The exemplary embodiments described herein facilitate significantly improved CO capacity and CO productivity compared to known sorbents. The exemplary embodiments described herein facilitate significantly improved CO absorption relative to HO absorption.

[0014] In some embodiments, the functionalized sorbent comprises a first type of functionalizing ligand, and the first type of functionalizing ligand comprises one or more functionalizing ligands comprising an aminosilicone group. Generally, the one or more functionalizing ligands comprising an aminosilicone group include any suitable ligand conducive to the functionalized sorbents described herein. The one or more functionalizing ligands comprising an aminosilicone group may include a single functionalizing ligand comprising an aminosilicone group, or two or more functionalizing ligands each comprising an aminosilicone group.

[0015] In general, the sorbent can be any suitable sorbent known in the art that contributes to the functionalized sorbents described herein. In some embodiments, the sorbent is selected from the group consisting of coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCPs), covalent organic framework (COF) compounds, zeolitic imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open frameworks, network chemistries, silica particles, zeolites, silicoaluminophosphates (SAPOs), aluminophosphates (AlPOs), polyaromatic frameworks (PAFs), activated carbons, molecular organic solids, and combinations thereof.

[0016] As used herein, MOF compounds are a class of compounds in which organic ligands are coordinated to metal ions or clusters to form one-, two-, or three-dimensional structures. The metal ions or clusters act as joints and are connected by multidirectional organic ligands, which act as linkers in the network. MOF compounds possess modularity that can be tuned during synthesis, resulting in precise chemical and structural control. Properties such as porosity, stability, particle morphology, and electrical conductivity can be tailored to specific applications.

[0017] In many embodiments, the sorbent is a MOF compound comprising a MOF metal or metal-containing cluster and a MOF linker.

[0018] In some embodiments, the MOF metal can be any suitable MOF metal known in the art that contributes to the functionalized sorbents described herein. In other embodiments, the MOF metal is a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof. In some embodiments, the MOF metal comprises Mg.

[0019] In some embodiments, the MOF metal-containing cluster can be any suitable MOF metal-containing cluster known in the art that is conducive to the functionalized sorbents described herein. In some embodiments, the MOF metal-containing cluster comprises a MOF metal node and a linker strut, where the MOF metal and linker are each as defined herein. In other embodiments, the MOF metal-containing cluster comprises a MOF metal-oxycluster.

[0020] In some embodiments, the MOF linker can be any suitable MOF linker known in the art that contributes to the functionalized sorbents described herein. In general, the shape and connectivity of the linker contribute to the structure of the resulting MOF compound. By adjusting the linker shape, length, and functional groups, the size, shape, and internal surface properties of the MOF compound can be tailored to the target application.

[0021] In at least some embodiments, the MOF linker is a linker selected from the group consisting of a polytopic linker, a ditopic linker, a tritopic linker, a tetratopic linker, a pentatopic linker, a hexatopic linker, a heptatopic linker, an octatopic linker, a mixed linker, an asymmetric linker, a metallolinker, an N-heterocyclic linker, and combinations thereof.

[0022] In at least some embodiments, the MOF linker is a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4”-dioxide-[1,1':4',1”-terphenyl]-3,3”-dicarboxylate (dotpdc 4- ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-DOBDC 4- ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4- ), 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), their protonated forms, partially or fully 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 a dicarboxylate (e.g., terephthalic acid), a tricarboxylate (e.g., 1,3,5-benzenetricarboxylic acid), an azolate, a tetrazolate, and combinations thereof.

[0023] As another example, in at least some embodiments, the MOF linker may be selected from the group consisting of 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, and the like. carboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimidedicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis-(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl-8,8'-dicarboxylic acid carboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7,-hexachloro-5-norbornene-2,3-Dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cisdicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenonedicarboxylic acid, Pluriol E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diaminodiphenyletherdiimidedicarboxylic acid, 4,4'-diaminodiphenylmethanediimidedicarboxylic acid, 4,4'-diaminodiphenylsulfondiimidedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2'-3'-diphenyl-p-terphenyl-4,4"-dicarboxylic acid, diphenylether-4,4'-dicarboxil carboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,The dicarboxylic acid linker is selected from the group consisting of 1,3-dicarboxylic acid, 2,9-dichlorofluorubin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, and combinations thereof.

[0024] 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.

[0025] As another example, in at least some embodiments, the MOF linker can be 1,1-dioxide-perillo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, meso-1,2,3,4-butane tetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, or the like. The tetracarboxylic acid linker is selected from the group consisting of carboxylic 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.

[0026] In an exemplary embodiment, the MOF linker is 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc) and / or 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- In some embodiments, dobpdc includes 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid, its monocarboxylate form, its dicarboxylate form, its monophenoxide form, its diphenoxide form, and combinations thereof.

[0027] In some embodiments, the MOF linker is one or more of the linkers shown below.

[0028] [ka]

[0029] [ka]

[0030] [ka]

[0031] 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 Mg2(dobpdc).

[0032] In some embodiments, the functionalized sorbent is a functionalized MOF compound of formula (I): M x L y F A a F B b (Formula I) During the ceremony, M is a MOF metal or metal-containing cluster; L is a MOF linker, F A is one or more functionalized ligands containing aminosilicone groups; F B is one or more functionalized ligands that do not contain aminosilicone groups, x is a number in the range of 1 to 6, y is a number between 1 and 6, a is a number greater than 0 and less than or equal to 2, b is a number in the range of 0 to 2.

[0033] In some embodiments, the functionalized sorbent comprises a second type of functionalizing ligand, and the second type of functionalizing ligand comprises one or more functionalizing ligands that do not contain aminosilicone groups. In some embodiments, the functionalized sorbent also comprises one or more functionalizing ligands that do not contain aminosilicone groups. In general, the one or more functionalizing ligands that do not contain aminosilicone groups can comprise any suitable ligand that contributes to the functionalized sorbent described herein. The one or more functionalizing ligands that do not contain aminosilicone groups can comprise only one functionalizing ligand that does not contain aminosilicone groups, or can comprise two or more functionalizing ligands that do not contain aminosilicone groups.

[0034] In some embodiments, the one or more functionalized ligands that do not contain aminosilicone groups are selected from the group consisting of amine ligands, monoamine ligands, diamine ligands, triamine ligands, tetraamine ligands, pentaamine ligands, hexaamine ligands, polyamine ligands, alkylamine ligands, and aminoalcohol 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-propanediamine, bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane (spermidine), triethylenetetramine, N,N'-bis(2-aminoethyl)-1,3-propanediamine, 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, N,N'-bis(3-aminopropyl)-1,4-diaminobutane (spermine), tetraethylenepentamine, and / or combinations thereof.

[0035] Generally, the one or more functionalizing ligands comprising an aminosilicone group and the one or more functionalizing ligands not comprising an aminosilicone group can be present in any suitable ratio known in the art to contribute to the functionalized sorbents described herein. In some embodiments, the ratio is selected from the group consisting of a molar ratio, a weight ratio, and a volume ratio. In some embodiments, the one or more functionalizing ligands comprising an aminosilicone group and the one or more functionalizing ligands not comprising an aminosilicone group are present in a ratio ranging from about 10:1 to about 1:10. In some embodiments, the one or more functionalizing ligands comprising an aminosilicone group and the one or more functionalizing ligands not comprising an aminosilicone group are present in a ratio ranging from about 9:1 to about 1:9. In some embodiments, the one or more functionalizing ligands comprising an aminosilicone group and the one or more functionalizing ligands not comprising an aminosilicone group are present in a ratio ranging from about 8:1 to about 1:8. In some embodiments, the one or more functionalizing ligands comprising an aminosilicone group and the one or more functionalizing ligands not comprising an aminosilicone group are present in a ratio ranging from about 7:1 to about 1:7. In some embodiments, the one or more functionalized ligands comprising an aminosilicone group and the one or more functionalized ligands not comprising an aminosilicone group are present in a ratio ranging from about 6:1 to about 1:6. In some embodiments, the one or more functionalized ligands comprising an aminosilicone group and the one or more functionalized ligands not comprising an aminosilicone group are present in a ratio ranging from about 5:1 to about 1:5. In some embodiments, the one or more functionalized ligands comprising an aminosilicone group and the one or more functionalized ligands not comprising an aminosilicone group are present in a ratio ranging from about 4:1 to about 1:4. In some embodiments, the one or more functionalized ligands comprising an aminosilicone group and the one or more functionalized ligands not comprising an aminosilicone group are present in a ratio ranging from about 3:1 to about 1:3. In some embodiments, the one or more functionalized ligands comprising an aminosilicone group and the one or more functionalized ligands not comprising an aminosilicone group are present in a ratio ranging from about 2:1 to about 1:2. In some embodiments, the one or more functionalized ligands comprising an aminosilicone group and the one or more functionalized ligands not comprising an aminosilicone group are present in a 1:1 ratio.

[0036] In some embodiments, the one or more functionalized ligands that include aminosilicone groups are present in a lesser amount than the one or more functionalized ligands that do not include aminosilicone groups.

[0037] In some embodiments, the one or more functionalized ligands comprising an aminosilicone group and the one or more functionalized ligands 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.

[0038] In many embodiments, the one or more functionalizing ligands containing aminosilicone groups can be any suitable one or more functionalizing ligands containing aminosilicone groups known in the art that are conducive to the functionalized sorbents described herein.

[0039] In some embodiments, the one or more functionalized ligands comprising an aminosilicone group comprise one or more amines selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof. In some embodiments, the one or more functionalized ligands comprising an aminosilicone group comprise one or more primary amines or one or more secondary amines.

[0040] In some embodiments, the one or more functionalized ligands comprising aminosilicone groups comprise one or more amines selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentaamines, hexaamines, polyamines, and combinations thereof.

[0041] In some embodiments, the one or more functionalized ligands comprising an aminosilicone group comprise one or more aminosilicones 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.

[0042] In some embodiments, the one or more functionalized ligands comprising an aminosilicone group comprise a symmetrical structure. In some embodiments, the one or more functionalized ligands comprising an aminosilicone group comprise an asymmetrical structure.

[0043] In some embodiments, when one or more functionalized ligands comprising aminosilicone groups comprise a disiloxane group, the one or more functionalized ligands comprising aminosilicone groups comprise the same amine on either side of the disiloxane group. In some embodiments, when one or more functionalized ligands comprising aminosilicone groups comprise a disiloxane group, the one or more functionalized ligands comprising aminosilicone groups comprise different amines on either side of the disiloxane group.

[0044] In some embodiments, the one or more functionalized ligands comprising an aminosilicone group are amino-substituted siloxanes of the following formula (II), (III), (IV), (V), (VI), or (VII):

[0045] [ka]

[0046] [ka] During the ceremony, R1, R2, R3, R4, R9, R10, R13, R14 and R18 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; R5, R6, R11, R15 and R17 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C1-C6 linear alkyl, a substituted or unsubstituted C3-C6 branched alkyl, a C1 alkyl, a C2 alkyl, a C3 alkyl, a C4 alkyl, a C5 alkyl and a C6 alkyl; R7, R8, R12 and R16 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C1-C6 linear alkyl, a substituted or unsubstituted C3-C6 branched alkyl, a C1 alkyl, a C2 alkyl, a C3 alkyl, a C4 alkyl, a C5 alkyl, a C6 alkyl and a substituent of formula (VIII):

[0047] [ka] During the ceremony, The wavy bond indicates the bonding position to formula (II) or formula (III) or formula (IV) or formula (V) or formula (VI) or formula (VII), R19, ​​R20, R21, R22, R23 and R24 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted C1-C6 linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; R25 and R26 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C1-C3 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl and substituted or unsubstituted C4-C6 cycloalkyl, or R25 and R26 together form a monocycle selected from the group consisting of heterocycloalkyl or heteroaryl; R27, R28 and R29 are each independently selected from the group consisting of a direct bond, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ether, -OH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2- and -NHCH2CH2CH2CH2-; R30 is selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C1-C3 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl; j is an integer from 0 to 20, k is an integer from 0 to 20, m is an integer from 0 to 20; n is an integer from 0 to 20.

[0048] In some embodiments, the one or more functionalizing ligands comprising an aminosilicone group are selected from the following group:

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] In general, the sorbent can be in any suitable form known in the art that is conducive to the functionalized sorbents described herein, hi some embodiments, the sorbent is in a form selected from the group consisting of a powder, a pellet, a composite, a composite mixed with a binder, a film, a coating, a packed bed, a column, a monolith, and combinations thereof.

[0056] Exemplary embodiments described herein include a sorbent system. Generally, the sorbent system can be any suitable sorbent system known in the art that is conducive to the functionalized sorbents described herein. In some embodiments, the sorbent system includes a functionalized sorbent and, optionally, a binder. In some embodiments, the sorbent system is disposed on a polymer film.

[0057] In some embodiments, the sorbent system includes one or more contactors. In some embodiments, the sorbent system includes two or more contactors. In some embodiments, the sorbent system includes a contactor for an adsorption cycle and a contactor for a desorption cycle. The contactors can be any suitable contactor known in the art that is conducive to the functionalized sorbents described herein. In some embodiments, the sorbent is incorporated into one or more channels of the contactor. In some embodiments, the contactor is made from the sorbent itself. In some embodiments, the contactor is coated with a sorbent system. In some embodiments, the contactor includes two or more sorbent coatings, one or more of which is a sorbent system.

[0058] In some embodiments, the sorbent system includes a frame. The frame can be any suitable frame known in the art that is conducive to the functionalized sorbents described herein. The frame can be included within a contactor or between two contactors. The frame can be comprised of one piece or more pieces. In some embodiments, the frame is an air frame. In some embodiments, the frame has a configuration selected from the group consisting of a polygonal configuration, a rectangular configuration, a square configuration, a circular configuration, an asymmetric configuration, and combinations thereof. In some embodiments, the sorbent system is mounted in the frame.

[0059] In some embodiments, the sorbent system includes one or more concentrators. The concentrators can be any suitable concentrator known in the art that is conducive to the functionalized sorbents described herein. The concentrators can be passive or active concentrators.

[0060] In some embodiments, the sorbent system includes one or more components configured to drive a fluid flow. The components configured to drive a fluid flow can be any suitable fluid flow-driven component known in the art that is conducive to the functionalized sorbents described herein. In some embodiments, the components configured to drive a fluid flow are selected from the group consisting of pumps, fans, and combinations thereof.

[0061] In some embodiments, the sorbent system includes one or more components configured to alter temperature. The components configured to alter temperature can be any suitable temperature-altering component known in the art that is conducive to the functionalized sorbents described herein. In some embodiments, the components configured to alter temperature are selected from the group consisting of heaters, coolers, and combinations thereof.

[0062] In some embodiments, the sorbent system includes one or more components configured to convey a fluid. The components configured to convey a fluid can be any suitable fluid-conducting component known in the art that is conducive to the functionalized sorbents described herein. In some embodiments, the component configured to convey a fluid is selected from the group consisting of a pipe, a porous pipe, a plastic porous pipe, a polymeric porous pipe, a metal porous pipe, a composite porous pipe, and combinations thereof.

[0063] In general, the functionalized sorbents may be used for any suitable purpose known in the art conducive to the use of the functionalized sorbents described herein. In some embodiments, the functionalized sorbents are used in sorbent systems. In some embodiments, the functionalized sorbents are used in carbon sorbent systems. In some embodiments, the functionalized sorbents are used in moisture sorbent systems. In some embodiments, the functionalized sorbents are used in carbon sorbent systems in the presence of water. In some embodiments, the functionalized sorbents are used for gas capture. In some embodiments, the functionalized sorbents are used for post-combustion capture of CO2 and / or direct air capture of CO2.

[0064] Exemplary embodiments described herein include methods for making sorbent systems. Generally, functionalized sorbents are made by any suitable synthetic method known in the art that is conducive to the functionalized sorbents described herein.

[0065] In many embodiments, the method of making a sorbent system includes functionalizing the sorbent with one or more functionalizing ligands that include an aminosilicone group. In some embodiments, the method of making a sorbent system includes functionalizing the sorbent with two or more functionalizing ligands that each include an aminosilicone group, where the aminosilicone groups are different from one another. In some embodiments, the method of making a sorbent system further includes functionalizing the sorbent with one or more functionalizing ligands that do not include an aminosilicone group. In some embodiments, the method of making a sorbent system includes controlling the ratio of the one or more functionalizing ligands that include an aminosilicone group to the one or more functionalizing ligands that do not include an aminosilicone group.

[0066] In some embodiments, the method of preparing a sorbent system further comprises annealing the functionalized sorbent. Annealing the sorbent system may remove excess ligand. In some embodiments, annealing the functionalized sorbent comprises annealing the functionalized sorbent at an elevated temperature. In some embodiments, annealing the sorbent comprises annealing the sorbent at a temperature of about 50°C to about 400°C. In some embodiments, annealing the sorbent comprises annealing the sorbent at a temperature of about 100°C to about 300°C. In some embodiments, annealing the sorbent comprises annealing the sorbent at a temperature of about 150°C to about 250°C.

[0067] 1 is an exemplary method flowchart 110. In this exemplary embodiment, method flowchart 110 illustrates exemplary steps of an embodiment of a method described herein, but is not intended to limit the embodiment of the method. In the exemplary embodiment, the method includes forming (112) a mixture including a sorbent, one or more functionalized ligands comprising aminosilicone groups, optionally one or more functionalized ligands not comprising aminosilicone groups, an optional solvent, and an optional non-solvent. The method also includes functionalizing (114) the sorbent.

[0068] In some embodiments, the method includes (I) forming a mixture (112) that includes a sorbent, one or more functionalizing ligands that include aminosilicone groups, optionally one or more functionalizing ligands that do not include aminosilicone groups, optionally a solvent, and optionally a non-solvent, and (II) functionalizing the sorbent (114).

[0069] In some embodiments, functionalizing the sorbent (114) includes agitating the mixture.

[0070] In some embodiments, functionalizing 114 the sorbent comprises functionalizing 114 the sorbent in the presence of an inert gas.

[0071] In some embodiments, functionalizing (114) the sorbent comprises functionalizing (114) the sorbent at a temperature in a range from about 0° C. to about 100° C. In some embodiments, functionalizing (114) the sorbent comprises functionalizing (114) the sorbent at a temperature in a range from about 20° C. to about 80° C. In some embodiments, functionalizing (114) the sorbent comprises functionalizing (114) the sorbent at a temperature in a range from about 20° C. to about 60° C.

[0072] In some embodiments, functionalizing 114 the sorbent comprises functionalizing 114 the sorbent for about 1 minute to about 7 days, hi some embodiments, functionalizing 114 the sorbent comprises functionalizing 114 the sorbent for about 1 hour to about 3 days.

[0073] In some embodiments, the sorbent is desolvated prior to functionalization 114. In some embodiments, the sorbent is dried prior to functionalization 114.

[0074] In some embodiments, the sorbent is annealed after functionalization (114). In some embodiments, annealing the sorbent comprises annealing the sorbent at an elevated temperature. In some embodiments, annealing the sorbent comprises annealing the sorbent at a temperature between about 50°C and about 400°C. In some embodiments, annealing the sorbent comprises annealing the sorbent at a temperature between about 100°C and about 300°C. In some embodiments, annealing the sorbent comprises annealing the sorbent at a temperature between about 150°C and about 250°C.

[0075] In some embodiments, the sorbent is prepared by the method disclosed in U.S. Provisional Patent Application No. 63 / 399251. In some embodiments, the one or more functionalized ligands comprising aminosilicone groups are prepared by the method disclosed in U.S. Provisional Patent Application No. 63 / 386231.

[0076] 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.

[0077] Generally, a non-solvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, the non-solvent is a liquid component included in the reaction mixture. In some embodiments, the non-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, the non-solvent is selected from the group consisting of organic solvents, aqueous solvents, and combinations thereof.

[0078] In some embodiments, the non-solvent aids in functionalization. In some embodiments, the selectivity of functionalization is controlled by relative solubility. For example, one or more sorbents or amines may have different solubility in the liquid-based reaction mixture compared to another sorbent or amine or functionalized sorbent. Thus, relative solubility introduces reaction and / or reagent limitations.

[0079] In many embodiments, the method may include appropriate process steps known in the art that contribute to the success of the methods described herein. Such process steps include, but are not limited to, washing, drying, filtering, purifying, separating, centrifuging, and combinations thereof. Some embodiments further include washing the functionalized sorbent. Some embodiments further include purifying the functionalized sorbent. In some embodiments, the purification includes distillation, vacuum distillation, and / or the use of heat.

[0080] Exemplary embodiments described herein include methods for collecting one or more gases.

[0081] FIG. 2 is an exemplary method flowchart 210. In an exemplary embodiment, method flowchart 210 illustrates exemplary steps of an embodiment of a method described herein and is not intended to limit the scope of the method. The method includes receiving (212) a gas source containing one or more gases with a functionalized sorbent, the functionalized sorbent including a sorbent and one or more functionalizing ligands including aminosilicone groups. In some embodiments, the functionalized sorbent includes two or more functionalizing ligands each including an aminosilicone group, the aminosilicone groups being different from one another. In some embodiments, the functionalized sorbent further includes one or more functionalizing ligands that do not include aminosilicone groups. The method also includes capturing (214) a quantity of the one or more gases with the functionalized sorbent.

[0082] In some embodiments, the method includes (I) receiving (212) a gas source comprising one or more gases with a functionalized sorbent, where the functionalized sorbent comprises a sorbent and one or more functionalizing ligands comprising aminosilicone groups, and (II) capturing (214) a quantity of the one or more gases with the functionalized sorbent.

[0083] Generally, the gas source can be any suitable gas source known in the art conducive to the methods described herein, hi some embodiments, the gas source is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, and combinations thereof.

[0084] Generally, the one or more gases can be any suitable gas known in the art conducive to the methods described herein, hi some embodiments, the one or more gases are selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefinic gases, and combinations thereof.

[0085] In some embodiments, the one or more gases are present in the feed gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v). In some embodiments, the one or more gases are present in the feed gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v). In some embodiments, the one or more gases are present in the feed gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v). In some embodiments, the one or more gases are present in the feed gas in an amount greater than 10% (v / v).

[0086] In some embodiments, the one or more gases are present in the feed gas in an amount ranging from about 100 ppmv to about 1000 ppmv, hi some embodiments, the one or more gases are present in the feed gas in an amount ranging from about 300 ppmv to about 5000 ppmv.

[0087] In some embodiments, the one or more gases comprise water vapor. In some embodiments, the one or more gases comprise water vapor in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, the one or more gases comprise water vapor in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, the one or more gases comprise water vapor in an amount ranging from about 0.5% (v / v) to about 15% (v / v). In some embodiments, the one or more gases comprise water vapor in an amount ranging from about 0.5% (v / v) to about 4% (v / v). In some embodiments, the one or more gases comprise water vapor in an amount ranging from about 4% (v / v) to about 15% (v / v).

[0088] In some embodiments, one or more gases are present in the feed gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v) and in the presence of water vapor. In some embodiments, one or more gases are present in the feed gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v) and in the presence of water vapor. In some embodiments, one or more gases are present in the feed gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v) and in the presence of water vapor. In some embodiments, one or more gases are present in the feed gas in an amount greater than about 10% (v / v) and in the presence of water vapor. In some embodiments, water vapor is present in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.5% (v / v) to about 10% (v / v).

[0089] In some embodiments, collecting 214 a quantity of one or more gases with a functionalized sorbent comprises adsorbing 214 a quantity of one or more gases with a functionalized sorbent. In some embodiments, collecting 214 a quantity of one or more gases with a functionalized sorbent comprises adsorbing 214 a quantity of one or more gases with a functionalized sorbent in the presence of water vapor.

[0090] In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is between about 1% (v / v) and about 100% (v / v) of the one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is between about 10% (v / v) and about 90% (v / v) of the one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is between about 20% (v / v) and about 80% (v / v) of the one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is between about 30% (v / v) and about 70% (v / v) of the one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is in the range of about 40% (v / v) to about 60% (v / v) of the one or more gases present in the feed gas.

[0091] In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is in the range of about 1% (v / v) to about 25% (v / v) of the one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is in the range of about 1% (v / v) to about 20% (v / v) of the one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is in the range of about 1% (v / v) to about 15% (v / v) of the one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is in the range of about 1% (v / v) to about 10% (v / v) of the one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is in the range of about 1% (v / v) to about 5% (v / v) of the one or more gases present in the feed gas.

[0092] In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is between about 80% (v / v) and about 100% (v / v) of the one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is between about 85% (v / v) and about 100% (v / v) of the one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is between about 90% (v / v) and about 100% (v / v) of the one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (214) by the functionalized sorbent is between about 95% (v / v) and about 100% (v / v) of the one or more gases present in the feed gas.

[0093] In some embodiments, the feed gas is adjusted 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 decreasing the amount of water vapor. In some embodiments, increasing the amount of water vapor includes adding or injecting water vapor into the feed gas. In some embodiments, decreasing the amount of water vapor includes removing water vapor from the feed gas by evaporation, condensation, and / or pre-adsorption. In some embodiments, changing the amount of water vapor includes exhaust gas recirculation (EGR) and / or blending.

[0094] In many embodiments, the functionalized sorbent, the feed gas, one or more gases, or a combination thereof, is at a particular 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.

[0095] In some embodiments, the method includes an adsorption cycle. In some embodiments, the method includes a desorption cycle. In some embodiments, one or more of the functionalized sorbent, the feed gas, the one or more gases, or combinations thereof, are at a temperature in a range from about 0° C. to about 150° C. during the gas adsorption cycle. In some embodiments, one or more of the functionalized sorbent, the feed gas, the one or more gases, or combinations thereof are at a temperature in a range from about 60° C. to about 250° C. during the gas desorption cycle.

[0096] In some embodiments, the method includes controlling the temperature. The temperature can be controlled for the functionalized sorbent, the feed gas, the one or more gases, or a combination thereof.

[0097] SUMMARY OF THE INVENTION Exemplary embodiments described herein encompass methods for recovering one or more gases from a gas source.

[0098] FIG. 3 is an exemplary method flowchart 310. In this exemplary embodiment, method flowchart 310 illustrates basic method steps for exemplary embodiments described herein and is not intended to limit the scope of the method embodiments. The method includes receiving (312) a gas source containing one or more gases with a functionalized sorbent, the functionalized sorbent including a sorbent and one or more functionalizing ligands including aminosilicone groups. In some embodiments, the functionalized sorbent includes two or more functionalizing ligands each including an aminosilicone group, and the aminosilicone groups are different from one another. In some embodiments, the functionalized sorbent further includes one or more functionalizing ligands that do not include aminosilicone groups. The method also includes capturing (314) a quantity of the one or more gases with the functionalized sorbent. The method also includes releasing (316) the one or more gases from the functionalized sorbent.

[0099] In some embodiments, the method includes (I) receiving a gas source comprising one or more gases with a functionalized sorbent (312), where the functionalized sorbent comprises a sorbent and one or more functionalizing ligands comprising aminosilicone groups; (II) capturing an amount of the one or more gases with the functionalized sorbent (314); and (III) releasing the one or more gases from the functionalized sorbent (316).

[0100] In some embodiments, releasing one or more gases from the functionalized sorbent (316) comprises releasing one or more gases from the functionalized sorbent with a purge gas. In some embodiments, releasing one or more gases from the functionalized sorbent (316) comprises subjecting the functionalized sorbent to a temperature or pressure change.

[0101] In some embodiments, the one or more gases are released from the functionalized sorbent into a receiving gas (316). In some embodiments, the receiving gas is selected from the group consisting of air, N2, steam, and combinations thereof. In some embodiments, the receiving gas is removed from the presence of the functionalized sorbent after receiving the one or more gases. In some embodiments, the receiving gas has an enriched concentration of the one or more gases compared to the source gas.

[0102] Additional aspects of the disclosed technology are presented in the following embodiments section.

[0103] [Embodiment Item 1] A functionalized sorbent comprising: a sorbent; one or more functionalized ligands containing aminosilicone groups; A functionalized sorbent comprising:

[0104] [Embodiment 2] 1. A method for producing a sorbent, the method comprising: (I) forming a mixture comprising a sorbent, one or more functionalized ligands comprising aminosilicone groups, optionally one or more functionalized ligands not comprising aminosilicone groups, optionally a solvent, and optionally a non-solvent; and (II) Functionalizing the sorbent A method comprising:

[0105] [Embodiment 3] 1. A method for collecting one or more gases, the method comprising: (I) receiving a gas source comprising one or more gases with a functionalized sorbent, the functionalized sorbent comprising: sorbents, and one or more functionalized ligands containing aminosilicone groups and (II) capturing a quantity of one or more gases with a functionalized sorbent; A method comprising:

[0106] [Embodiment 4] 1. A method for recovering one or more gases, the method comprising: (I) receiving a gas source comprising one or more gases with a functionalized sorbent, the functionalized sorbent comprising: sorbents, and one or more functionalized ligands containing aminosilicone groups and (II) capturing a quantity of one or more gases with a functionalized sorbent; (III) releasing one or more gases from the functionalized sorbent; A method comprising:

[0107] [Embodiment 5] The functionalized sorbent of any one of embodiments 1 through 4, further comprising one or more functionalizing ligands that do not contain aminosilicone groups.

[0108] [Embodiment 6] 6. The functionalized sorbent of any one of embodiments 1 through 5, wherein the one or more functionalized ligands containing aminosilicone groups and the one or more functionalized ligands not containing aminosilicone groups are present in a ratio ranging from about 10:1 to about 1:10.

[0109] [Embodiment 7] 7. The functionalized sorbent of any one of claims 1 through 6, wherein the sorbent is selected from the group consisting of coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCPs), covalent organic framework (COF) compounds, zeolitic imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open frameworks, network chemistries, silica particles, zeolites, silicoaluminophosphates (SAPOs), aluminophosphates (AlPOs), polyaromatic ring frameworks (PAFs), activated carbon, molecular organic solids, and combinations thereof.

[0110] [Embodiment 8] The functionalized sorbent of any one of paragraphs 1 through 7, wherein the functionalized sorbent is a functionalized MOF compound of formula (I): M x L y F A a F B b (Formula I) During the ceremony, M is a MOF metal or metal-containing cluster; L is a MOF linker, F A is one or more functionalized ligands containing aminosilicone groups; F B is one or more functionalized ligands that do not contain aminosilicone groups, x is a number in the range of 1 to 6, y is a number between 1 and 6, a is a number greater than 0 and less than or equal to 2, b is a number in the range of 0 to 2.

[0111] [Embodiment Item 9] The functionalized sorbent of any one of embodiments 1 through 8, 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, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof.

[0112] [Embodiment Item 10] The MOF linker is a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4”-dioxide-[1,1':4',1”-terphenyl]-3,3”-dicarboxylate (dotpdc 4- ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-DOBDC 4- ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4-), 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), dicarboxylate, terephthalic acid, tricarboxylate, 1,3,5-benzenetricarboxylic acid, azolate, tetrazolate, 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-butanedicarboxylic acid Diene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic 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, diimidedicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis-(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxo Imidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cisdicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenone dicarboxylic acid, Pluriol E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diaminodiphenyletherdiimidedicarboxylic acid, 4,4'-diaminodiphenylmethanediimidedicarboxylic acid, 4,4'-diaminodiphenylsulfondiimidedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfonyl-2,3-naphthalenedicarboxylic acid, Sulfo-2,3-naphthalenedicarboxylic 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-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-Benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, 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-dichlorofluorubin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dicarboxylic acid Benzyl-1H-pyrrole-3,4-dicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazole dicarboxylic 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-pyridine Dicarboxylic acids, 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-perillo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, meso-1,2,3,4-butane tetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 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, The functionalized sorbent of any one of embodiments 1 through 9, comprising a linker selected from the group consisting of cyclopentane tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, a polytopic linker, a ditopic linker, a tritopic linker, a tetratopic linker, a pentatopic linker, a hexatopic linker, a heptatopic linker, an octatopic linker, a mixed linker, an asymmetric linker, a metallolinker, an N-heterocyclic linker, protonated forms thereof, partially or fully deprotonated forms thereof, and combinations thereof.

[0113] [Embodiment Item 11] The functionalized sorbent of any one of the first through tenth embodiments, wherein the one or more functionalizing ligands comprising aminosilicone groups comprise one or more amines selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof.

[0114] [Embodiment Item 12] The functionalized sorbent of any one of the first through eleventh embodiments, wherein the one or more functionalizing ligands comprising aminosilicone groups comprise one or more amines selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentaamines, hexaamines, polyamines, and combinations thereof.

[0115] [Embodiment Item 13] 13. The functionalized sorbent of any one of the preceding embodiments, wherein the one or more functionalizing ligands comprising aminosilicone groups comprise one or more aminosilicones 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, octahedral silsesquioxanes, and combinations thereof.

[0116] [Embodiment Item 14] The functionalized sorbent of any one of paragraphs 1 through 13, wherein the one or more functionalizing ligands comprising aminosilicone groups comprise a symmetrical structure.

[0117] [Embodiment Item 15] The functionalized sorbent of any one of paragraphs 1 through 13, wherein the one or more functionalizing ligands comprising aminosilicone groups comprise an asymmetric structure.

[0118] [Embodiment Item 16] The functionalized sorbent of any one of the first through fifth embodiments, wherein the one or more functionalizing ligands comprising an aminosilicone group are amino-substituted siloxanes of the following formula (II), (III), (IV), (V), (VI), or (VII):

[0119] [ka]

[0120] [ka] During the ceremony, R1, R2, R3, R4, R9, R10, R13, R14 and R18 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; R5, R6, R11, R15 and R17 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C1-C6 linear alkyl, a substituted or unsubstituted C3-C6 branched alkyl, a C1 alkyl, a C2 alkyl, a C3 alkyl, a C4 alkyl, a C5 alkyl and a C6 alkyl; R7, R8, R12 and R16 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C1-C6 linear alkyl, a substituted or unsubstituted C3-C6 branched alkyl, a C1 alkyl, a C2 alkyl, a C3 alkyl, a C4 alkyl, a C5 alkyl, a C6 alkyl and a substituent of formula (VIII):

[0121] [ka] During the ceremony, The wavy bond indicates the bonding position to formula (II) or formula (III) or formula (IV) or formula (V) or formula (VI) or formula (VII), R19, ​​R20, R21, R22, R23 and R24 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted C1-C6 linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; R25 and R26 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C1-C3 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl and substituted or unsubstituted C4-C6 cycloalkyl, or R25 and R26 together form a monocycle selected from the group consisting of heterocycloalkyl or heteroaryl; R27, R28 and R29 are each independently selected from the group consisting of a direct bond, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2- and -NHCH2CH2CH2CH2-; R30 is selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C1-C3 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl; j is an integer from 0 to 20, k is an integer from 0 to 20, m is an integer from 0 to 20; n is an integer from 0 to 20.

[0122] [Embodiment Item 17] The functionalized sorbent of any one of the first through sixth embodiments, wherein the one or more functionalizing ligands comprise an aminosilicone group selected from the group consisting of:

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] [Embodiment Item 18] A sorbent system comprising the functionalized sorbent of any one of paragraphs 1 through 17.

[0130] [Embodiment Item 19] The method of any one of embodiments 1 through 18, wherein functionalizing the sorbent comprises agitating the mixture.

[0131] [Embodiment Item 20] The method of any one of embodiments 1 through 19, wherein functionalizing the sorbent comprises functionalizing the sorbent in the presence of an inert gas.

[0132] [Embodiment Item 21] The method of any one of embodiments 1 through 20, wherein functionalizing the sorbent comprises functionalizing the sorbent at a temperature in the range of from about 0°C to about 100°C.

[0133] [Embodiment Item 22] The method of any one of embodiments 1 through 21, wherein functionalizing the sorbent comprises functionalizing the sorbent for about 1 minute to about 7 days.

[0134] [Embodiment Item 23] The method of any one of embodiments 1 through 22, wherein the sorbent is desolvated prior to functionalization.

[0135] [Embodiment Item 24] The method of any one of embodiments 1 through 23, wherein the sorbent is dried prior to functionalization.

[0136] [Embodiment Item 25] The method of any one of embodiments 1 through 24, wherein the sorbent is annealed after functionalization.

[0137] [Embodiment Item 26] The method of any one of paragraphs 1 to 25, wherein the solvent is selected from the group consisting of an organic solvent, an aqueous solvent, and combinations thereof.

[0138] [Embodiment Item 27] The method of any one of embodiments 1 through 26, wherein the gas source is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, and combinations thereof.

[0139] [Embodiment Item 28] The method of any one of embodiments 1 through 27, wherein the one or more gases are selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, and combinations thereof.

[0140] [Embodiment Item 29] 1. A method for recovering one or more gases, the method comprising: collecting one or more gases by the method of any one of embodiments 1 to 28; (III) releasing one or more gases from the functionalized sorbent. A method comprising:

[0141] [Embodiment Item 30] The method of any one of paragraphs 1 through 29, wherein the one or more gases are in the presence of water.

[0142] [Embodiment Item 31] The method of any one of embodiments 1 through 30, further comprising collecting an amount of water with a functionalized sorbent.

[0143] [Embodiment Item 32] The method of any one of embodiments 1 through 31, further comprising releasing water from the functionalized sorbent.

[0144] References herein to "some embodiments" should not be interpreted as excluding the existence of additional embodiments that also comprise the recited features. [Example]

[0145] Without further explanation, it is believed that those skilled in the art can utilize the present invention to its fullest extent from the above description. The following examples are merely illustrative and do not limit the present disclosure. The starting materials for the following examples are not necessarily prepared by the specific preparation procedures described in the procedures of other embodiments. Furthermore, numerical ranges described herein encompass all values ​​between the lower and upper limits. For example, when a range is stated as 10 to 50, values ​​such as 12 to 30, 20 to 40, and 30 to 50 are expressly recited herein. The starting materials for the following examples are not necessarily prepared by the specific preparation procedures described in the procedures of other embodiments. Furthermore, numerical ranges described herein encompass all values ​​between the lower and upper limits. For example, when a range is stated as 10 to 50, values ​​such as 12 to 30, 20 to 40, and 30 to 50 are intended to be expressly recited herein. These are merely examples of what is specifically intended, and it is understood that all possible combinations of numerical values ​​between the stated lower and upper limits are expressly recited herein.

[0146] Example 1. Synthesis of MOF compound 1 A 20 mL scintillation vial was charged with two equivalents of 1,3-bis(aminoethylaminomethyl)tetramethyldisiloxane (AEAM, 0.556 g, 2 mmol, 2 equiv.) and dissolved in 5 mL of toluene. Next, 0.320 g (1 mmol) of Mg2(dobpdc), which had been desolvated overnight in a vacuum oven at 120 °C, was added to the vial. The slurry was stirred at 300-400 rpm on a hot plate at 60 °C for 3 days. The material was cooled to room temperature and transferred to a conical tube. The material was allowed to settle at 4000 rpm for 2 minutes, then the solvent was decanted and resuspended in another 10 mL of toluene for 4-6 hours. The material was centrifuged, decanted, and dried overnight in a vacuum oven at 120 °C to yield 0.4881 g of MOF compound 1 (84% yield, Mg2(dobpdc)(AEAM)). 0.94 ).

[0147] H NMR analysis was performed on the final material after digestion with 20 μL of 35% DCl in D2O, 200 μL of D2O, and 600 μL of DMSO-d6. H NMR (DMSO-d6, D2O) δ: 7.87 (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).

[0148] Example 2. Synthesis of MOF compound 2 A 250 mL three-necked round-bottom flask was charged with spermine (1.406 g, 0.0069 mol, 1.2 equiv.) dissolved in 60 mL toluene and sparged with N2 via a gas dispersion tube for 30 minutes. Next, 1.846 g (0.0058 mol, 1 equiv.) of Mg2(dobpdc), which had been desolvated overnight in a vacuum oven at 120 °C, was added to the vessel. The slurry was stirred at 300 rpm at 60 °C under N2 for 3 days. The material was cooled to room temperature and collected by vacuum filtration. The filter cake was added to another 100 mL of toluene, stirred at room temperature for 2 hours, and filtered. The material was then placed in a glass container and dried overnight in a vacuum oven at 120 °C to yield 2.738 g of MOF compound 2 (90.3% yield, Mg2(dobpdc)(spermine)). 1.01 ).

[0149] H NMR analysis was performed on the final material after digestion with 20 μL of 35% DCl in D2O, 200 μL of D2O, and 600 μL of DMSO-d6. H NMR (DMSO-d6, D2O) δ: 7.86 (dd, 2H), 7.69 (dd, 2H), 6.99 (dd, 2H), 2.98-2.88 (m, 12H), 1.93 (m, 4H), 1.65 (bs, 4H).

[0150] Example 3. Synthesis of MOF compound 3 A 1 L three-necked round-bottom flask was charged with spermine (13.25 g, 0.065 mol, 3 equiv.) dissolved in 220 mL of toluene and sparged with N2 for 30 minutes using a gas dispersion tube. Next, Mg2(dobpdc) (7.0 g, 0.022 mol, 1 equiv.), which had been desolvated overnight in a vacuum oven at 120 °C, was added to the vessel. The slurry was sparged with N2 for an additional 30 minutes and stirred at 300-400 rpm under N2 at 60 °C for 3 days. The material was cooled to room temperature and collected by vacuum filtration. The filter cake was added to another 300 mL of toluene, stirred at room temperature for 4-6 hours, and filtered. This step was repeated once more. The material was then placed in a glass container and dried overnight in a vacuum oven at 120 °C to yield 8.25 g of MOF compound 3 (67.1% yield, Mg2(dobpdc)(spermine)). 1.2 ).

[0151] H NMR analysis was performed on the final material after digestion with 20 μL of 35% DCl in D2O, 200 μL of D2O, and 600 μL of DMSO-d6. H NMR (DMSO-d6, D2O) δ: 7.85 (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).

[0152] Example 4. Synthesis of MOF compound 4 A 20 mL scintillation vial was charged with one equivalent of spermidine (0.0526 g, 0.36 mmol) and dissolved in 5 mL of toluene. Next, 0.160 g (0.36 mmol) of Mg2(dobpdc)(IPA)2, which had been desolvated overnight in a vacuum oven at 120 °C, was added to the vial. The slurry was stirred overnight at 300–400 rpm on a hot plate at 60 °C. The material was cooled to room temperature and transferred to a conical tube. The material was then spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the material was resuspended in another 10 mL of toluene for 4–6 hours. The material was centrifuged, decanted, and dried overnight in a vacuum oven at 120 °C to yield 0.139 g of MOF compound 4 (80.1% yield, Mg2(dobpdc)(spermidine)). 1.08 ).

[0153] H NMR analysis was performed on the final material after digestion with 20 μL of 35% DCl in D2O, 200 μL of D2O, and 600 μL of DMSO-d6. H NMR (DMSO-d6, D2O) δ: 7.85 (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).

[0154] Example 5. Method for Varying the Amount of Functionalized Ligand with and without Aminosilicone Groups Metal-organic frameworks (MOFs) are synthesized using an aqueous preparation method, followed by washing three times with water and three times with a solvent (e.g., isopropyl alcohol). The material is then dried by vacuum filtration to yield approximately 70-75% solvated material. The exact molar amount of MOF can be determined by determining how much residual solvent is present in the MOF. One such method is to measure the solvent peak (e.g., Mg2(dobpdc)1(alcohol)) by 1H NMR. x ) analysis.

[0155] H NMR analysis was performed on Mg2(dobpdc)1(IPA) 1.92 after digestion with 20 μL of 35% DCl (in D2O), 200 μL of D2O, and 600 μL of DMSO-d6. H NMR (DMSO-d6, D2O) δ: 7.86 (dd, 2H), 7.69 (dd, 2H), 6.99 (dd, 2H), 3.75 (m, 1H), 1.00 (d, 6H).

[0156] (MOF metal) by adding x equivalents of one or more functionalized ligands that do not contain aminosilicone groups (e.g., spermine) as the limiting reagent and one or more functionalized ligands that contain aminosilicone groups (e.g., AEAM) as the excess reagent. x (MOF linker) y (One or more functionalized ligands that do not contain aminosilicone groups) z (One or more functionalized ligands containing aminosilicone groups) 1-z It is possible to form a substance having the following composition.

[0157] Example 6. Synthesis of MOF compound 5 A 1 L three-necked round-bottom flask was charged with spermine (3.14 g, 0.016 mol, 0.5 equiv.), 1,3-bis(aminoethylaminomethyl)tetramethyldisiloxane (AEAM, 6.48 g, 0.023 mol, 0.75 equiv.), and 310 mL of toluene and sparged with N2 via a gas dispersion tube for 30 minutes. Next, 10 g (0.031 mol, 1 equiv.) of Mg2(dobpdc), which had been desolvated overnight in a vacuum oven at 120 °C, was added to the vessel. The slurry was sparged with N2 for an additional 30 minutes and stirred at 300–400 rpm under N2 at 60 °C for 3 days. The material was cooled to room temperature and collected by vacuum filtration. The filter cake was added to another 300 mL of toluene, stirred at room temperature for 4–6 hours, and filtered. This material was placed in a glass container and dried overnight in a vacuum oven at 120 °C to give 12.8 g of MOF compound 5 (75% yield, Mg(dobpdc)(spermine) 0.65 (AEAM) 0.35 ).

[0158] H NMR analysis was performed on the final material after digestion with 20 μL of 35% DCl in D2O, 200 μL of D2O, and 600 μL of DMSO-d6. H NMR (DMSO-d6, D2O) δ: 7.85 (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).

[0159] Example 7. Synthesis of MOF compound 6 A 20 mL scintillation vial was charged with spermidine (0.0363 g, 0.25 mmol, 0.5 equiv.) and 1,3-bis(aminoethylaminomethyl)tetramethyldisiloxane (AEAM, 0.1044 g, 0.375 mmol, 0.75 equiv.) dissolved in 5 mL of toluene. Next, 0.160 g (0.5 mmol) of Mg2(dobpdc), which had been desolvated overnight in a vacuum oven at 120 °C, was added to the vial. The slurry was stirred at 300-400 rpm on a hot plate at 60 °C for 3 days. The material was cooled to room temperature and transferred to a conical tube. The material was then spun at 4000 rpm for 2 minutes, the solvent was decanted, and the material was resuspended in another 10 mL of toluene for 4-6 hours. This was centrifuged, decanted, and dried overnight in a vacuum oven at 120 °C to give 0.166 g of GE140 (64% yield, Mg(dobpdc)(spermidine) 0.68 (AEAM) 0.37 ).

[0160] H NMR analysis was performed on the final material after digestion with 20 μL of 35% DCl in D2O, 200 μL of D2O, and 600 μL of DMSO-d6. H NMR (DMSO-d6, D2O) δ: 7.86 (dd, 2H), 7.69 (dd, 2H), 6.99 (dd, 2H), 3.22-3.16 (m, 2.96H), 2.97-2.78 (m, 5.44H), 2.38 (s, 1.48H), 1.92 (m, 1.36H), 1.61 (m, 2.72H), 0.17 (s, 4.44H).

[0161] Example 8. Performance comparison The equilibrium CO2 capacities (g CO2 / g sorbent) measured at 4.5% (v / v) CO2 and 400 ppmvCO2 for MOF sorbents functionalized with pure AEAM (as in MOF compound 1), pure spermine (as in MOF compound 3), and hybrid amine (as in MOF compound 5) as a function of spermine loading are shown in Figures 4 and 5, respectively. 4.5% (v / v) corresponds to post-combustion capture (PCC) conditions, such as those in natural gas combined cycle post-combustion capture, while 400 ppmvCO2 corresponds to direct air capture (DAC) conditions. These figures show that under PCC conditions of 4.5% (v / v) CO2 (Figure 4), the maximum CO2 capacity increases with increasing spermine percentage. Under DAC conditions of 400 ppmvCO2, the hybrid amine-based sorbent exhibits higher capacities than the two pure amine-based materials (Figure 5). Furthermore, CO2 productivity, calculated by normalizing CO2 uptake at a given cycle time in gCO2 / (gsorbent × hr), shows a strong dependence on the choice of ligand. The hybrid amine sorbent MOF compound 5 exhibits significantly improved productivity compared to sorbents with only one constituent amine under both PCC (Figure 6) and DAC (Figure 7) conditions.

[0162] Furthermore, the hybrid amine sorbent MOF compound 5 showed a significant decrease in CO2 absorption at elevated temperatures such as 120 °C (Figure 8), suggesting that it is easier to regenerate than pure spermine sorbents (e.g., MOF compound 3).

[0163] Similar performance improvements are observed with spermidine-based sorbent materials. Figures 9 and 10 show the equilibrium CO2 capacity and productivity at 4.5% (v / v) CO2 concentration as a function of spermidine loading for sorbent materials functionalized with pure AEAM (as in MOF compound 1), pure spermidine (as in MOF compound 4), and hybrid amine (as in MOF compound 6). 4.5% (v / v) corresponds to post-combustion capture conditions (PCC conditions), and 400 ppmvCO2 corresponds to direct air capture conditions (DAC conditions). These figures show that, under PCC conditions at 4.5% (v / v) CO2 concentration, increasing spermidine percentage increases the maximum CO2 capacity. However, the hybrid amine sorbent, MOF compound 6, has the highest productivity compared to sorbents with only one constituent amine. Furthermore, two sorbent materials with AEAM (MOF compound 1 with pure AEAM and MOF compound 6 with hybrid amine) show significantly reduced HO / CO ratios compared to pure spermidine sorbents (e.g., MOF compound 4) (Figure 11).

[0164] Having described the significant advantages of functionalizing a sorbent with one or more functionalizing ligands that contain aminosilicone groups and, optionally, one or more functionalizing ligands that do not contain aminosilicone groups, the materials and methods of the present disclosure are broadly applicable to a wide variety of sorbents and functionalizing ligands.

[0165] Unless otherwise stated, approximation terms such as "approximately," "substantially," and "about" used herein indicate that the modified term is not absolute or precise, but merely an approximation that would be obvious to one of ordinary skill in the art. Thus, values ​​modified by terms such as "approximately," "substantially," and "substantially" are not limited to their exact numerical values. In at least some cases, approximation terms correspond to the accuracy of the instrument used to measure the value. Furthermore, unless otherwise stated, terms such as "first," "second," and "second" are merely descriptive terms used herein and do not impose numerical, positional, or hierarchical requirements on the entity to which they are attached. Furthermore, for example, a reference to "second" does not require or exclude the presence of, for example, a "first" or less, or a "third" or more.

[0166] Although specific features of various embodiments of the invention may be shown in some drawings and not in others, this is for convenience only. References herein to "some embodiments" should not be interpreted as excluding the existence of additional embodiments that possess the recited features. Consistent with the principles of the invention, any feature shown in one drawing may be referenced and / or claimed in combination with any feature shown in any other drawing.

[0167] This specification has used examples to disclose the invention, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using the devices or systems and practicing the methods. The patentable scope of the disclosure is defined by the claims, and may include other examples that would be obvious to those skilled in the art. Such other examples are within the scope of the claims if they have elements that do not literally differ from the claims, or equivalent elements that differ only insubstantially from the literal language of the claims.

[0168] It will be apparent to those skilled in the art that some substituents in the present disclosure are optional, relying on the presence of other substituents. For example, in Formula II, when R is a direct bond, R and R are optional substituents not present in the compound. Similarly, in Formula II, when n is 0, R and R are direct bonds, and R, R, and R are optional substituents not present in the compound. The optional substitution values ​​in one embodiment do not limit the presence of substituents in other embodiments.

[0169] As used herein, the term "alkyl," whether used alone or in a compound name, such as "haloalkyl," includes straight-chain or branched alkyls such as methyl, ethyl, n-propyl and i-propyl, or the various butyl, pentyl, or hexyl isomers. An alkyl defined by the number of carbon atoms (e.g., C alkyl) is understood to have that number of carbon atoms and is not further limited.

[0170] The term "heteroalkyl," as used herein, refers to an alkyl chain in which one or more of the elements forming the backbone of the chain is other than carbon.

[0171] As used herein, "aminoalkyl" includes those in which the N-group is substituted with a straight or branched alkyl.

[0172] As used herein, the term "halogen" or "halide," whether used alone or in the name of a compound, such as "haloalkyl," includes fluorine, chlorine, bromine, or iodine. Furthermore, when used in the name of a compound, such as "haloalkyl," the alkyl is partially or fully substituted with the same or different halogen atoms. Specific examples of "haloalkyl" include F3C, ClCH2, CF3CH2, and CF3CCl2. Terms such as "haloalkoxy" are defined similarly to the term "haloalkyl." Specific examples of "haloalkoxy" include CF3O, CCl3CHO, F2CHCH2CHO, and CF3CHO.

[0173] As used herein, the term "heterocyclic" refers to a ring in which one or more of the elements forming the ring backbone is other than carbon. Unless otherwise specified, a heterocyclic ring may be saturated, partially saturated, or fully unsaturated. Fully unsaturated heterocyclic rings satisfy Hückel's rule, and such rings are also referred to as "heteroaryl" or aromatic heterocyclic rings. A "saturated heterocyclic ring" refers to a heterocyclic ring that contains only single bonds between ring atoms.

[0174] As used herein, the term "aminosilicone group" encompasses functional groups that contain both siloxane groups containing Si-O-Si bonds (also called disiloxane groups) and amine groups.

[0175] 1 H NMR spectra are given in ppm downfield of tetramethylsilane, where "s" denotes singlet, "d" denotes doublet, "dd" denotes doublet of doublets, "ddd" denotes doublet of doublet of doublets, "t" denotes triplet, "m" denotes multiplet, and "br s" denotes broad singlet.

Claims

1. A functionalized sorbent, the functionalized sorbent comprising: sorbents, and one or more functionalized ligands comprising aminosilicone groups A functionalized sorbent comprising:

2. 10. The functionalized sorbent of claim 1, further comprising one or more functionalizing ligands that do not contain aminosilicone groups.

3. 3. The functionalized sorbent of claim 2, wherein the one or more functionalized ligands comprising aminosilicone groups and the one or more functionalized ligands not comprising aminosilicone groups are present in a ratio within the range of from about 10:1 to about 1:

10.

4. 10. The functionalized sorbent of claim 1, wherein the sorbent is selected from the group consisting of coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCPs), covalent organic framework (COF) compounds, zeolitic imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open framework structures, network chemistries, silica particles, zeolites, silicoaluminophosphates (SAPOs), aluminophosphates (AlPOs), polyaromatic ring frameworks (PAFs), activated carbon, molecular organic solids, and combinations thereof.

5. 2. The functionalized sorbent of claim 1, wherein the functionalized sorbent is a functionalized MOF compound of formula (I): M ｘ L ｙ F Ａ ａ F Ｂ ｂ (Formula I) During the ceremony, M is a MOF metal or metal-containing cluster; L is a MOF linker, F Ａ is one or more functionalized ligands containing aminosilicone groups; F Ｂ is one or more functionalized ligands that do not contain aminosilicone groups; x is a number ranging from 1 to 6, y is a number ranging from 1 to 6, a is a number greater than 0 and equal to or less than 2, b is a number ranging from 0 to 2.

6. 6. The functionalized sorbent of 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, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof.

7. The MOF linker is a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc ４－ ), 4,4"-dioxide-[1,1':4',1"-terphenyl]-3,3"-dicarboxylate (dotpdc ４－ ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc ４－ ), 4,6-dihydroxyisophthalic acid (m-dobdc ４－ ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc ４－ ), 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), dicarboxylates, terephthalic acid, tricarboxylates, 1,3,5-benzenetricarboxylic acid, azolates, tetrazolates, 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-butanedicarboxylic acid 1,4-dienedicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic 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, diimidedicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis-(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxo Imidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cisdicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenonedicarboxylic acid, Pluriol E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diaminodiphenyletherdiimidedicarboxylic acid, 4,4'-diaminodiphenylmethanediimidedicarboxylic acid, 4,4'-diaminodiphenylsulfonediimidedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfonyl-2,3-naphthalenedicarboxylic acid, sulfo-2,3-naphthalenedicarboxylic 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-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-Benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, 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-dichlorofluorubin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dicarboxylic acid Benzyl-1H-pyrrole-3,4-dicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazole dicarboxylic 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-pyridine Dicarboxylic acids, 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-perillo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, meso-1,2,3,4-butane tetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 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 6. The functionalized sorbent of claim 5, comprising a linker selected from the group consisting of cyclohexyl carboxylic acid, cyclopentane tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, polytopic linkers, ditopic linkers, tritopic linkers, tetratopic linkers, pentatopic linkers, hexatopic linkers, heptatopic linkers, octatopic linkers, mixed linkers, asymmetric linkers, metallolinkers, N-heterocyclic linkers, protonated forms, partially or fully deprotonated forms thereof, and combinations thereof.

8. 10. The functionalized sorbent of claim 1, wherein the one or more functionalizing ligands comprising aminosilicone groups comprise one or more amines selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof.

9. 10. The functionalized sorbent of claim 1, wherein the one or more functionalizing ligands comprising aminosilicone groups comprise one or more amines selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentaamines, hexaamines, polyamines, and combinations thereof.

10. 2. The functionalized sorbent of claim 1, wherein the one or more functionalizing ligands comprising aminosilicone groups comprise one or more aminosilicones 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, octahedral silsesquioxanes, and combinations thereof.

11. 10. The functionalized sorbent of claim 1, wherein the one or more functionalizing ligands comprising aminosilicone groups comprise a symmetrical structure.

12. The functionalized sorbent of claim 1 , wherein the one or more functionalizing ligands comprising aminosilicone groups comprise an asymmetric structure.

13. 2. The functionalized sorbent of claim 1, wherein the one or more functionalizing ligands comprising aminosilicone groups are amino-substituted siloxanes of the following formula (II), (III), (IV), (V), (VI), or (VII): 【Chemistry 1】 【Chemistry 2】 During the ceremony, R1, R2, R3, R4, R9, R10, R13, R14 and R18 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; R5, R6, R11, R15 and R17 are each independently selected from the group consisting of a direct bond, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl and C6 alkyl; R7, R8, R12 and R16 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C1-C6 linear alkyl, a substituted or unsubstituted C3-C6 branched alkyl, a C1 alkyl, a C2 alkyl, a C3 alkyl, a C4 alkyl, a C5 alkyl, a C6 alkyl and a substituent of the following formula (VIII): 【Transformation 3】 During the ceremony, The wavy bond indicates the bonding position to formula (II) or formula (III) or formula (IV) or formula (V) or formula (VI) or formula (VII), R19, ​​R20, R21, R22, R23 and R24 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted C1-C6 linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; R25 and R26 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C1-C3 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, and substituted or unsubstituted C4-C6 cycloalkyl, or R25 and R26 together form a monocycle selected from the group consisting of heterocycloalkyl or heteroaryl; R27, R28 and R29 are each independently selected from the group consisting of a direct bond, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2- and -NHCH2CH2CH2CH2-; R30 is selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C1-C3 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl; j is an integer from 0 to 20; k is an integer from 0 to 20; m is an integer from 0 to 20; n is an integer from 0 to 20.

14. 10. The functionalized sorbent of claim 1, wherein the one or more functionalizing ligands comprise an aminosilicone group selected from the group consisting of: 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】

15. A sorbent system comprising the functionalized sorbent of claim 1.

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