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

Abstract

The present disclosure relates to solid sorbent materials functionalized with polyamines having oxygen-containing units selected from carbonyl units, hydroxyl units, and combinations thereof. Described herein are adsorbents functionalized with a polyamine having oxygen-containing units selected from carbonyl units, hydroxyl units, and combinations thereof, methods of making the adsorbents, and methods of using the adsorbents.

Description

Technical Field

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

[0002] Carbon capture using solid adsorbent materials offers a viable and technically advantageous alternative to conventional liquid amine-based carbon dioxide (CO2) capture methods. Compared to active liquid amines, solid adsorbents tend to have better adsorption capacity, lower regeneration energy requirements, reduced system complexity, and reduced environmental and safety risks.

[0003] There are two types of adsorbent materials based on the underlying adsorption mechanism. One is physical adsorbents and the other is chemical adsorbents. Physical adsorbents, such as activated carbon and zeolites, rely on van der Waals interactions to adsorb gaseous substances such as CO2 and water (H2O). Chemical adsorbents, particularly amine-functionalized silica particles and metal organic frameworks (MOFs), adsorb CO2 through reversible chemical reactions and the formation of ammonium carbamate, ammonium carbonate and / or ammonium bicarbonate. Although physical adsorbent materials are relatively mature compared to chemical adsorbent materials, a major disadvantage of physical adsorbent materials is that their CO2 adsorption capacity is significantly reduced due to interference from other polar molecules (such as H2O) that are inevitably present in the atmosphere and flue gases. In contrast, as a result of chemical bonding, chemical adsorbent materials generally have better adsorption selectivity for CO2 than for other interfering substances such as nitrogen (N2), oxygen (O2), methane and carbon monoxide (CO) relative to their physical adsorbent counterparts.

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

[0005] However, conventional CO₂ adsorbents tend to have high water absorption. For example, MOF-274 functionalized with spermine has a water absorption of approximately 35 wt% at conditions relevant for direct air capture, such as 25°C and 50% RH. The impact of water absorption on techno-economic analyses has generally been underappreciated because the amount of water adsorbed and desorbed can significantly increase the energy cost of a CO₂ capture plant of any size. For example, assuming an adsorption heat of 47 kJ / mol for HO, the energy cost for each ton of HO adsorbed would increase by at least 725 kWh for each ton of CO₂ captured due to the latent heat associated with HO desorption. Therefore, adsorbents with low water absorption are desirable.

[0006] In the present disclosure, solid adsorbent materials functionalized with polyamines having oxygen-containing units selected from carbonyl units, hydroxyl units, and combinations thereof are developed and demonstrated. The adsorbent materials developed in the present disclosure exhibit high adsorption capacity for carbon dioxide, low adsorption capacity for water, and low desorption residue under mild desorption conditions. Summary of the Invention

[0007] In one aspect, a functionalized adsorbent is provided that includes an adsorbent and at least one functionalized ligand including a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0008] In another aspect, a method for preparing a functionalized adsorbent is provided. The method comprises: (I) forming a mixture comprising: an adsorbent; at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof; optionally at least one functionalized ligand not comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof; an optional solvent; and an optional non-solvent; and (II) functionalizing the adsorbent.

[0009] In another aspect, a method for modifying a functionalized adsorbent is provided. The method comprises: (I) forming a mixture comprising: an adsorbent functionalized with at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof; and a reactant; and (II) reacting the reactant with the adsorbent functionalized with at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof to produce an adsorbent functionalized with at least one functionalized ligand that includes a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof.

[0010] In yet another aspect, a method of capturing at least one gas is provided. The method comprises: (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; and (II) capturing an amount of the at least one gas with the functionalized adsorbent. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] These and other features, aspects, and advantages of the present disclosure will be better understood when the following detailed description is read with reference to the accompanying drawings, in which like characters represent like parts throughout the several views, and in which:

[0012] Figure 1 Depicted is a method for preparing a Mg2(dobpdc)1(IPA) according to the present disclosure. 1.92 After digestion with 20 μL of 20% DC1 in D2O, 200 μL of D2O, and 600 μL of DMSO-d6 1 H NMR analysis results;

[0013] Figure 2 depicts scanning electron microscope (SEM) images of exemplary MOF-274 prepared using salicylic acid (left) and fluorosalicylic acid (right) as crystal growth inhibitors according to the present disclosure;

[0014] Figure 3 depicts a powder X-ray diffraction spectrum of MOF-274 synthesized according to the present disclosure using 4,4'-biphenyldiphenol as a crystal growth inhibitor;

[0015] Figure 4 Depicted are SEM images of exemplary MOF-274 prepared in accordance with the present disclosure without (left) and with 9.24 wt% 4,4′-biphenyldiphenol (right);

[0016] Figure 5 depicts a powder X-ray diffraction spectrum of MOF-274 synthesized according to the present disclosure using BPYDC as a crystal growth inhibitor;

[0017] Figure 6 depicts SEM images of exemplary MOF-274 prepared using BPYDC as a crystal growth inhibitor (incorporated at 0.13 wt%, 2.29 wt%, and 24.78 wt%) according to the present disclosure;

[0018] Figure 7 depicts a powder X-ray diffraction spectrum of MOF-274 synthesized according to the present disclosure using BPYDM as a crystal growth inhibitor;

[0019] Figure 8 depicts SEM images of exemplary MOF-274 prepared according to the present disclosure using BPYDM as a crystal growth inhibitor (incorporated at 1.17 wt%, 3.43 wt%, and 6.80 wt%);

[0020] Figure 9 Depicted is a method for preparing a Mg2(dobpdc)1(spermine) according to the present disclosure. 1.01 Performed after digestion with 20 μL 20% DC1 in D2O, 200 μL D2O, and 600 μL DMSO-d6 1 Results of H NMR analysis. 1 H NMR (DMSO-d 6, D2O)δ7.84(dd,2H),7.67(dd,2H),6.98(dd,2H),2.90(m,12H),1.93(m,4H),1.65(s,4H);

[0021] Figure 10 Depicted is the reaction of 1,2-butylene oxide:spermine (O / N) in 600 μL CD3OD containing residual methanol (3.35 ppm) according to the present disclosure. 1 H NMR analysis results. 1 H NMR(CD3OD)δ3.58(m,1.06H),2.67-2.4(m,14.08H),1.66(m,4H),1.54(m,6.28H),0.96(m,3.24H);

[0022] Figure 11 Depicted is the reaction of β-methylhydroxy-tetramine according to the present disclosure in 600 μL D2O. 1 H NMR analysis results. 1 HNMR(D2O)δ3.6-3.5(dd,1.91H),3.01(m,0.99H),2.55-2.95(m,9.94H),1.82(m,2H),1.65(m,4.10H);

[0023] Figure 12 Depicted is the reaction of HC:spermine in 600 μL CD3OD containing residual methanol (3.35 ppm) according to the present disclosure. 1 H NMR analysis results. Peaks used to estimate the amount of functionalization - 1 H NMR (CD3OD): δ 2.94-2.74 (10H, spermine) and 0.94 (t, 3H, HC). The structure is drawn for simplicity. O / N ratio is 0.38 (see calculation below);

[0024] Figure 13Depicted is a method for preparing a Mg2(dobpdc)1(0.48HC:spermine) according to the present disclosure. 0.52 Performed after digestion with 20 μL 20% DCl in D2O, 200 μL D2O, and 600 μL DMSO-d6 1 Results of H NMR analysis. 1 H NMR (DMSO-d 6, D2O) δ 7.87 (dd, 2H), 7.71 (dd, 2H), 7.01 (d, 2H), 2.99-2.87 (m, 12H), 1.97-1.91 (m, 4H), 0.79-0.75 (6H). Peak integration for estimating amine loading is shown. Peaks (*) derived from the solvent toluene, peaks (#) derived from the spermine fragment of the amine, and peaks (triangles) derived from the -CH3 peaks of the hexyl chain are marked as indicated;

[0025] Figure 14 Depicted is a synthetic scheme for the covalent functionalization of amines to γ-Al2O3 according to the present disclosure;

[0026] Figure 15 TGA traces of γ-Al2O3 and GLYMO-functionalized γ-Al2O3 in different solvents according to the present disclosure are depicted. In toluene, GLYMO functionalization is approximately 14 wt% (green trace). In ethanol, various loadings of GLYMO (25 wt%, 50 wt%, and 100 wt%) show GLYMO loading between 18 wt% and 20 wt%.

[0027] Figure 16 depicts TGA traces of pure γ-Al2O3 and γ-Al2O3 functionalized with different amines according to the present disclosure;

[0028] Figure 17 Depicted are TGA traces of pure γ-Al2O3 and γ-Al2O3 synthesized in a one-pot process modified with GLYMO and further functionalized with spermine (GE324-1A) according to the present disclosure;

[0029] Figure 18 Depicted are water isotherms (gH2O / g adsorbent) at 25°C for adsorbents functionalized with pristine amine 2-3-2 and 1,2-butylene oxide-modified amine 2-3-2 according to the present disclosure;

[0030] Figure 19 Depicted are water isotherms (number of H2O / amine groups) at 25°C for adsorbents functionalized with pristine amine 2-3-2 and 1,2-butylene oxide-modified amine 2-3-2 according to the present disclosure;

[0031] Figure 20Depicted are water isotherms (gH2O / g adsorbent) at 25°C for adsorbents functionalized with pristine amine 2-3-2 and (2,2,2-trifluoroethyl)ethylene oxide (TFEO)-modified amine 2-3-2 according to the present disclosure;

[0032] Figure 21 Depicted are water isotherms (number of H2O / amine groups) at 25°C for adsorbents functionalized with pristine amine 2-3-2 and TFEO-modified amine 2-3-2 according to the present disclosure;

[0033] Figure 22 Depicted are water isotherms (gH2O / g adsorbent) at 25°C for adsorbents functionalized with spermine and epoxide-modified spermine according to the present disclosure;

[0034] Figure 23 Depicted are water isotherms (expressed as the amount of H2O / amine group) at 25°C for adsorbents functionalized with spermine and epoxide-modified spermine according to the present disclosure;

[0035] Figure 24 Depicted are water isotherms (gH2O / g adsorbent) at 25°C for adsorbents functionalized with spermine versus epoxide post-synthesis modification according to the present disclosure;

[0036] Figure 25 Depicted are water isotherms (number of H2O / amine groups) at 25°C for adsorbents functionalized with spermine versus epoxide post-synthesis modification according to the present disclosure;

[0037] Figure 26 Depicted is the water isotherm (gH2O / g adsorbent) at 25°C for an adsorbent functionalized with β-methylhydroxy-tetramine (GE327-A3117D) according to the present disclosure;

[0038] Figure 27 The IUPAC classification of isotherms is described.

[0039] Figure 28 Depicted is the water isotherm (gH2O / g adsorbent) at 25°C for γ-Al2O3 functionalized with spermine (GE320-184A) according to the present disclosure;

[0040] Figure 29 Depicted is the water isotherm (gH2O / g adsorbent) at 25°C for γ-Al2O3 functionalized with 1,2-butylene oxide-modified spermine (GE321-184B) according to the present disclosure;

[0041] Figure 30Depicted is the water isotherm (gH2O / g adsorbent) at 25°C for γ-Al2O3 modified with GLYMO and further functionalized with spermine (GE324-1A) synthesized according to the one-pot process of the present disclosure;

[0042] Figure 31 Depicted are the dry CO2 isotherms of GE302 (amine 2-3-2) according to the present disclosure: solid circles (25°C) and open circles (120°C) versus the dry CO2 isotherms of GE314 (-OH-containing amine 2-3-2): solid squares (25°C) and open squares (120°C);

[0043] Figure 32 Depicted are CO2 isotherms (gCO2 / g adsorbent) at 25°C for adsorbents functionalized with spermine and epoxide-modified spermine according to the present disclosure;

[0044] Figure 33 Depicted are CO2 isotherms (expressed as the amount of CO2 per amine group) at 25°C for adsorbents functionalized with spermine and epoxide-modified spermine according to the present disclosure;

[0045] Figure 34 Depicted are CO2 isotherms (gCO2 / g adsorbent) at 25°C for adsorbents functionalized with pristine amine 2-3-2 and 1,2-butylene oxide-modified amine 2-3-2 according to the present disclosure;

[0046] Figure 35 Depicted are the CO2 isotherms (expressed as the amount of CO2 per amine group) at 25°C for adsorbents functionalized with pristine amine 2-3-2 and 1,2-butylene oxide-modified amine 2-3-2 according to the present disclosure;

[0047] Figure 36 Depicted are CO2 isotherms (gCO2 / g adsorbent) at 25°C for adsorbents functionalized with pristine amine 2-3-2 and TFEO-modified amine 2-3-2 according to the present disclosure;

[0048] Figure 37 Depicted are the CO2 isotherms (expressed as the amount of CO2 / amine group) at 25°C for adsorbents functionalized with pristine amine 2-3-2 and TFEO-modified amine 2-3-2 according to the present disclosure;

[0049] Figure 38 Depicted is the CO2 isotherm (gCO2 / g adsorbent) at 25°C for γ-Al2O3 functionalized with spermine (GE320-184A) according to the present disclosure;

[0050] Figure 39Depicted is the CO2 isotherm (gCO2 / g adsorbent) at 25°C for γ-Al2O3 functionalized with 1,2-butylene oxide-modified spermine (GE321-184B) according to the present disclosure;

[0051] Figure 40 depicts CO2 uptake and H2O uptake of the GE314 membrane according to the present disclosure over adsorption time;

[0052] Figure 41 Depicted is the desorption curve of a MOF-based adsorbent functionalized with pristine spermine (GE5-A369) according to the present disclosure;

[0053] Figure 42 Depicts the desorption curve of a MOF-based adsorbent functionalized with -OH-containing spermine (GE296-A366A) according to the present disclosure;

[0054] Figure 43 Depicts the desorption curve of a MOF-based adsorbent functionalized with -OH-containing spermine (GE301-A370A) according to the present disclosure;

[0055] Figure 44 Depicted is the desorption curve of a MOF-based adsorbent functionalized with pristine amine 2-3-2 (GE302-A377) according to the present disclosure;

[0056] Figure 45 Depicted is the desorption curve of a MOF-based adsorbent (powder) functionalized with an -OH-containing amine 2-3-2 (GE314) according to the present disclosure;

[0057] Figure 46 Depicts the desorption curve of a MOF-based adsorbent (membrane) functionalized with an -OH-containing amine 2-3-2 (GE314) according to the present disclosure;

[0058] Figure 47 is a flow chart of an exemplary method according to the present disclosure;

[0059] Figure 48 is a flow chart of an exemplary method according to the present disclosure;

[0060] Figure 49 is a flow chart of an exemplary method according to the present disclosure;

[0061] Figure 50 is a flow chart of an exemplary method according to the present disclosure; and

[0062] Figure 51 is a flow chart of an exemplary method according to the present disclosure.

[0063] Unless otherwise indicated, the drawings provided herein are intended to illustrate features of the embodiments of the present disclosure. It is believed that these features are applicable to a wide variety of systems including one or more embodiments of the present disclosure. Therefore, the drawings are not intended to include all conventional features known to those of ordinary skill in the art required to practice the embodiments disclosed herein. DETAILED DESCRIPTION

[0064] Described herein are solid adsorbent materials functionalized with polyamines having oxygen-containing units selected from carbonyl units, hydroxyl units, and combinations thereof. The adsorbent materials developed in the present disclosure exhibit high adsorption capacity for carbon dioxide, low adsorption capacity for water, and low desorption residue under mild desorption conditions.

[0065] In general, the functionalized adsorbents according to the present disclosure can be used with any suitable composition, system, and method known in the art that facilitates the formation of functionalized adsorbents. The functionalized adsorbents are not limited to any specific embodiment disclosed herein. Exemplary compositions, systems, and methods are disclosed in PCT / US2023 / 082729, the contents of which are incorporated herein by reference.

[0066] In some embodiments, the functionalized adsorbent comprises a first type of functionalized ligand, wherein the first type of functionalized ligand comprises at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof. Generally speaking, the at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof can include any such suitable ligand that promotes the formation of the functionalized adsorbent described herein. The at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof can include only one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof, or two or more functionalized ligands each comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof.

[0067] In some embodiments, the at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof comprises at least one amine selected from the group consisting of a primary amine, a secondary amine, a tertiary amine, and combinations thereof. In some embodiments, the at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof comprises at least one primary amine or at least one secondary amine.

[0068] In some embodiments, the at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentamines, hexamines, polyamines, and combinations thereof.

[0069] In general, the polyamine can include any number of amine groups known in the art to be suitable for promoting the formation of functionalized adsorbents. In some embodiments, the polyamine includes a total number of amine groups in the range of about 2 to about 10. In some embodiments, the polyamine includes a total number of amine groups in the range of about 2 to about 6. In some embodiments, the polyamine includes a total number of amine groups in the range of about 2 to about 4. In some embodiments, the polyamine includes 2, 3, 4, 5, 6, 7, 8, 9, or 10 amine groups.

[0070] In some embodiments, the at least one oxygen-containing unit is selected from the group consisting of primary hydroxyl units, secondary hydroxyl units, tertiary hydroxyl units, and combinations thereof.

[0071] In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof is a reaction product. In some embodiments, the reaction product comprises a primary hydroxyl unit and is formed by the reaction between the polyamine and the oxetane. In some embodiments, the reaction product comprises a secondary hydroxyl unit and is formed by the reaction between the polyamine and the epoxide. In some embodiments, the reaction product comprises a tertiary hydroxyl unit and is formed by a direct synthesis reaction.

[0072] In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof is obtained before MOF functionalization by pre-load modification (PLM). In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof is obtained after MOF functionalization by post-synthesis modification (PSM).

[0073] In some embodiments, the functionalized adsorbent has a Type II, or Type III, or Type IV isotherm for pure water. In some embodiments, the functionalized adsorbent has a Type II isotherm for pure water. In some embodiments, the functionalized adsorbent has a Type III isotherm for pure water. In some embodiments, the functionalized adsorbent has a Type IV isotherm for pure water.

[0074] In some embodiments, the functionalized adsorbent has an average water absorption of <1 H2O molecule / amine at high relative humidity. In some embodiments, high relative humidity refers to a relative humidity of 50% and above at ambient temperature (such as, but not limited to, -20°C to 40°C). In some embodiments, high relative humidity refers to a relative humidity of 60% and above at ambient temperature (such as, but not limited to, -20°C to 40°C). In some embodiments, high relative humidity refers to a relative humidity of 70% and above at ambient temperature (such as, but not limited to, -20°C to 40°C). In some embodiments, high relative humidity refers to a relative humidity of 60% and above at a temperature in the range of 40°C to 60°C. In some embodiments, high relative humidity refers to a relative humidity of 70% and above at a temperature in the range of 40°C to 60°C. In some embodiments, high relative humidity refers to a relative humidity of 70% and above at a temperature in the range of 60°C and above.

[0075] In some embodiments, the functionalized adsorbent has a desorption temperature of 120°C or less, preferably 110°C or less, or more preferably 100°C or less.

[0076] In some embodiments, the LogP of at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof is -1.0 or greater. In some embodiments, the LogP of at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof is -0.5 or greater. In some embodiments, the LogP of at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof is 0 or greater. In some embodiments, the LogP of at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof is 0.5 or greater. As used herein, LogP is the logarithm (base 10) of the partition coefficient (P), where the partition coefficient is defined as the ratio of the organic (oil) phase concentration to the aqueous phase concentration of a material.

[0077] In some embodiments, the functionalized adsorbent includes a second type of functionalized ligand, wherein the second type of functionalized ligand includes at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof. In some embodiments, the functionalized adsorbent further includes at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof. Generally speaking, the at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof can include any such suitable ligand that promotes the formation of the functionalized adsorbent described herein. The at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof can include only one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof, or two or more functionalized ligands that each do not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof.

[0078] In some embodiments, at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof is selected from the group consisting of a polyamine ligand comprising at least one cyclic unit, an aminosilicone ligand, an amine ligand, a monoamine ligand, a diamine ligand, a triamine ligand, a tetraamine ligand, a pentamine ligand, a hexamine ligand, a polyamine ligand, an alkylamine ligand, and an amino alcohol ligand. Exemplary ligands include, but are not limited to, ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, di(N-methyl)ethylenediamine, N-isopropylethylenediamine, N,N-dimethyl-N-methylethylenediamine, di(N,N-dimethyl)ethylenediamine, N,N-diisopropylethylenediamine, 2,2-dimethyl-1,3-diaminopropane, 1,3-diaminopentane, diethylenetriamine, N-(2-aminoethyl) -1,3-propylenediamine, bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane (spermidine), triethylenetetramine, N,N′-bis(2-aminoethyl)-1,3-propylenediamine, 1,2-bis(3-aminopropylamino)ethane, N,N′-bis(3-aminopropyl)-1,3-propylenediamine, N,N′-bis(3-aminopropyl)-1,4-diaminobutane (spermidine), tetraethylenepentamine and / or combinations thereof.

[0079] In some embodiments, the at least one functionalized ligand comprising a polyamine containing at least one cyclic unit can be any suitable at least one functionalized ligand comprising a polyamine containing at least one cyclic unit known in the art to facilitate formation of the functionalized adsorbents described herein.

[0080] In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises at least one amine selected from the group consisting of a primary amine, a secondary amine, a tertiary amine, and combinations thereof. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises at least one primary amine or at least one secondary amine.

[0081] In some embodiments, the at least one functionalized ligand comprising a polyamine containing at least one cyclic unit comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentamines, hexamines, polyamines, and combinations thereof.

[0082] In some embodiments, at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises a symmetrical structure. In some embodiments, at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises an asymmetrical structure.

[0083] In some embodiments, at least one cyclic unit is selected from the group consisting of alicyclic units, aromatic units, and combinations thereof.

[0084] In some embodiments, polyamines comprising at least one cyclic unit are described herein. In some embodiments, the polyamines comprising at least one cyclic unit are functionalized ligands. In some embodiments, the polyamines comprising at least one cyclic unit are functionalized ligands for functionalizing adsorbents.

[0085] In many embodiments, the functionalized ligand comprising a polyamine comprises at least one cyclic unit according to formula (CI):

[0086]

[0087] in:

[0088] B, C, and D each independently comprise at least one amine group;

[0089] x, y, and z are each independently 0 or 1; and

[0090] A comprises an aromatic ring structure according to formula (C-II), or an alicyclic structure according to formula (C-III):

[0091]

[0092] in:

[0093] n is an integer ranging from about 3 to about 8;

[0094] m is an integer in the range of about 3 to about 5; and

[0095] A 1 、A 2 、A 3 and A 4 Each independently includes at least one of carbon, oxygen, and silicon.

[0096] In some embodiments, A 1 、A 2 、A 3 and A 4 Each independently selected from the group consisting of:

[0097] a carbon substituted with at least one substituent selected from the group consisting of hydrogen, B, C, D, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C3-C6 branched chain alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0098] unsubstituted oxygen;

[0099] silicon substituted with at least one substituent selected from the group consisting of hydrogen, B, C, D, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; and

[0100] A combination of them.

[0101] In some embodiments, B, C, and D each independently comprise a structure according to Formula (C-IV):

[0102] E t ——F u ——G v ——H w (Formula C-IV)

[0103] in:

[0104] t, u, v, and w are each independently an integer in the range of about 0 to about 10; and

[0105] E, F, G and H are each independently selected from the group consisting of:

[0106] Substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C3-C6 branched-chain alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl and C6 alkyl;

[0107] NH2, NHR1 and NR1R2,

[0108] wherein R1 and R2 are each independently selected from the group consisting of substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl and C6 alkyl; and

[0109] A combination of them.

[0110] In some embodiments, the polyamine comprises at least two cyclic units, wherein the polyamine comprises a polycyclic structure connected by at least one linking group selected from the group consisting of: substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl and C6 alkyl.

[0111] In some embodiments, the polyamine includes at least one bicyclic unit.

[0112] In some embodiments, the polyamine comprises at least two cyclic units, wherein the polyamine comprises a bridged polycyclic structure comprising at least one bridging group selected from the group consisting of: substituted or unsubstituted C1-C6 linear alkyl groups, substituted or unsubstituted C3-C6 branched alkyl groups, C1 alkyl groups, C2 alkyl groups, C3 alkyl groups, C4 alkyl groups, C5 alkyl groups, and C6 alkyl groups.

[0113] In some embodiments, the polyamine includes at least one bridged cyclic unit.

[0114] In some embodiments, t, u, v, and w are each independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0115] In some embodiments, n is 3, 4, 5, 6, 7, or 8.

[0116] In some embodiments, m is 3, 4, or 5.

[0117] In some embodiments, at least one of x, y, and z is 1. In some embodiments, at least two of x, y, and z are 1. In some embodiments, x, y, and z are each 1.

[0118] In general, each of B, C, and D can be bonded to any suitable A atom that facilitates the formation of a functionalized adsorbent according to the present disclosure. In many embodiments, each of B, C, and D is bonded to an independent atom of an A cyclic unit. In some embodiments, each of B, C, and D is bonded to an A atom. 1 、A 2 、A 3 and A 4 of independent atoms combined.

[0119] In some embodiments, the polyamine includes at least one substituent at a substituent position selected from the group consisting of the 1,2 (ortho) position, the 1,3 (meta) position, the 1,4 (para) position, and combinations thereof.

[0120] In some embodiments, at least two of B, C, and D are arranged in the ortho position in the A cyclic unit. In some embodiments, at least two of B, C, and D are arranged in the meta position in the A cyclic unit. In some embodiments, at least two of B, C, and D are arranged in the para position in the A cyclic unit.

[0121] In some embodiments, the polyamine includes an isomer selected from the group consisting of cis isomers, trans isomers, R-enantiomers, S-enantiomers, and combinations thereof.

[0122] In some embodiments, at least two of B, C, and D are different. In some embodiments, B, C, and D are different.

[0123] In some embodiments, at least two of B, C, and D are the same. In some embodiments, B, C, and D are the same.

[0124] In some embodiments, the polyamine includes at least one heteroalicyclic ring unit. In some embodiments, the polyamine includes at least one heteroalicyclic ring unit that does not contain nitrogen. In some embodiments, the polyamine includes at least one heteroalicyclic ring unit in which the heteroatom is not nitrogen.

[0125] In general, the polyamine can include any number of amine groups known in the art to be suitable for promoting the formation of functionalized adsorbents. In some embodiments, the polyamine includes a total number of amine groups in the range of about 2 to about 10. In some embodiments, the polyamine includes a total number of amine groups in the range of about 2 to about 6. In some embodiments, the polyamine includes a total number of amine groups in the range of about 2 to about 4. In some embodiments, the polyamine includes 2, 3, 4, 5, 6, 7, 8, 9, or 10 amine groups.

[0126] In some embodiments, the polyamine is a compound selected from the group consisting of

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133] as well as

[0134] A combination of them.

[0135] The following exemplary polyamines have cyclic units according to the present disclosure:

[0136] Aliphatic cyclic (6-cyclic) amines:

[0137] GE201 (mixture of cis and trans); GE182 (trans); GE200 (cis); 1,4-cyclohexanediamine (p-CHD) (mw: 114; bp = 197°C).

[0138]

[0139] GE181; GE187 (mixture of cis and trans); GE199 (cis); 1,3-cyclohexanediamine (m-CHD) (mw: 114; bp = 194°C).

[0140]

[0141] GE202 (mixture of cis and trans); GE203 (cis); GE209 (trans); 1,2-cyclohexanediamine (o-CHD) (mw: 114; bp = 194°C).

[0142]

[0143] Di / tri / tetramine:

[0144] GE221-A2109; 1,3,5-cyclohexanedryltrimethylamine (CHTM) (mw = 171.316; bp = 309°C)

[0145]

[0146] GE254; GE255 (BPDCH)

[0147]

[0148] 3-Ring-3

[0149]

[0150] Primary / Secondary / Tertiary Amines:

[0151] N,N-dimethylcyclohexanediamine (N2MCHD) (mw: 142.24; bp at 18 mmHg = 80°C)

[0152]

[0153] Cis or trans isomers and chirality:

[0154] (R,R)-1,2-cyclohexanediamine (trans)

[0155]

[0156] (S,S)-cyclohexanediamine (trans)

[0157]

[0158] (R,S)-Cyclohexanediamine (cis)

[0159]

[0160] Different lengths:

[0161] GE193 (mixture of isomers); 1,4-bis(aminomethyl)-cyclohexane (BAMCH) (mw: 142.24; bp = 239°C)

[0162]

[0163] GE206 (mixture of isomers); 1,3-bis(aminomethyl)-cyclohexane (mBAMCH) (mw: 142.24; bp = 240°C)

[0164]

[0165] GE248; GE249 (BEDCH)

[0166]

[0167] Structures with multiple ring units:

[0168] GE216; 4,4'-Methylenebis(2-methylcyclohexylamine) (mixture of isomers) (MCHA)

[0169]

[0170] Asymmetric structure:

[0171] GE205 (mixture of isomers); 4-(aminomethyl)cyclohexylamine (AMCHA)

[0172]

[0173] GE240; 4-(2-aminoethyl)cyclohexylamine (mixture of cis and trans forms) (ACHEA)

[0174]

[0175] GE256; N-(3-aminopropyl)cyclohexylamine (BPDCH)

[0176]

[0177] Mixed amines:

[0178] GE234; GE235; mixture of 1,4-bis(aminomethyl)cyclohexane (BAMCH) and spermine

[0179]

[0180] GE236; GE237; Mixture of 1,4-bis(aminomethyl)cyclohexane (BAMCH) and spermidine

[0181]

[0182] GE285; GE291; a mixture of BEDCH and spermine

[0183]

[0184] replace:

[0185] GE208; Isophorone diamine (IPRDA) (mw: 170.3; bp = 252.9°C)

[0186]

[0187] Bridged double ring structure:

[0188] GE214 Bis(aminomethyl)norbornane (BAMNB) (mixture of isomers) (mw: 154.25; bp = 259°C)

[0189]

[0190] Heterocyclic amines:

[0191] GE204; [(2S,5R)-5-(Aminomethyl)oxolan-2-yl]methanamine; Tetrahydrofuran-2,5-diamine (AMTHF) (mw: 130.18)

[0192]

[0193] Aromatic (6) amine / substituted

[0194] GE183, GE184; m-XYD (mw: 136; bp = 265°C)

[0195]

[0196] GE185; GE186; GE189; p-phenylenediamine (p-XYD) (mw: 136; bp = 230°C)

[0197]

[0198] Primary / Secondary / Tertiary Amines:

[0199] GE225; N-methyl-1-[4-(methylaminomethyl)phenyl]methanamine (Me-p-XYD) (mw: 164.20)

[0200]

[0201] Mixed amines:

[0202] GE226; GE227; mixture of p-phenylenediamine (p-XYD) and 1,3,5-benzenetriyltrimethylamine (BTM)

[0203]

[0204] GE247; GE251; p-phenylenediamine (p-XYD) and N 1 ,N 1 A mixture of '-((1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(propane-1,3-diamine) (APAP)

[0205]

[0206] Heteroaromatic amines:

[0207] GE195; 2,5-bis(aminomethyl)furan (mw: 126.16 g / mol, bp = 230°C).

[0208]

[0209] GE217; Tetrafluoro-p-phenylenediamine (TF-p-XYD) (MW: 2018.16)

[0210]

[0211] Di / Tri / Tetra / Penta / Hexamine

[0212] GE220-A2107; 1,3,5-Benzenetriyltrimethylamine (BTM) (mw: 165.24; bp = 329°C)

[0213]

[0214] GE222; GE223 (Ph-3-ED)

[0215]

[0216] GE252; GE253 (Ph-3-PD)

[0217]

[0218] In some embodiments, the polyamine is selected from the group consisting of:

[0219]

[0220]

[0221] Cyclohexanediamine, and

[0222] A combination of them.

[0223] In some embodiments, the at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof comprises at least one aminosilicone selected from the group consisting of a linear aminosilicone, a cyclic aminosilicone, a branched aminosilicone, an amino-substituted siloxane, a linear amino-substituted disiloxane, a cyclic amino-substituted disiloxane, a linear amino-substituted trisiloxane, a cyclic amino-substituted trisiloxane, a linear amino-substituted tetrasiloxane, a cyclic amino-substituted tetrasiloxane, a linear amino-substituted polysiloxane, a cyclic amino-substituted polysiloxane, a silsesquioxane, a polyoctahedral silsesquioxane, and combinations thereof.

[0224] In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group comprises a symmetrical structure. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group comprises an asymmetrical structure.

[0225] In some embodiments, when the at least one functionalized ligand comprising an aminoorganosilicon group comprises a disiloxane group, the at least one functionalized ligand comprising an aminoorganosilicon group comprises the same amine on either side of the disiloxane group. In some embodiments, when the at least one functionalized ligand comprising an aminoorganosilicon group comprises a disiloxane group, the at least one functionalized ligand comprising an aminoorganosilicon group comprises a different amine on either side of the disiloxane group.

[0226] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group is an amino-substituted siloxane of formula (AI), formula (A-II), formula (A-III), formula (A-IV), formula (AV), or formula (A-VI).

[0227]

[0228]

[0229]

[0230] in:

[0231] R1, R2, R3, R4, R9, R 10 、R 13 、R 14 and R 18 each independently selected from the group consisting of hydrogen, substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted branched-chain alkyl, substituted or unsubstituted C3-C6 branched-chain alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0232] R5, R6, R 11 、R 15 and R 17 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C1-C6 straight chain alkyl group, a substituted or unsubstituted C3-C6 branched chain alkyl group, a C1 alkyl group, a C2 alkyl group, a C3 alkyl group, a C4 alkyl group, a C5 alkyl group, and a C6 alkyl group,

[0233] R7, R8, R 12 and R 16 Each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C1-C6 straight chain alkyl group, a substituted or unsubstituted C3-C6 branched chain alkyl group, a C1 alkyl group, a C2 alkyl group, a C3 alkyl group, a C4 alkyl group, a C5 alkyl group, a C6 alkyl group, and a substituent of formula (A-VII)

[0234]

[0235] in:

[0236] The wavy bond indicates the bonding position to Formula (AI) or Formula (A-II) or Formula (A-III) or Formula (A-IV) or Formula (AV) or Formula (A-VI);

[0237] R 19 、R 20 、R 21 、R 22 、R 23 and R 24 each independently selected from the group consisting of hydrogen, substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted branched-chain alkyl, substituted or unsubstituted C3-C6 branched-chain alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted C1-C6 straight-chain heteroalkyl, substituted or unsubstituted branched-chain heteroalkyl, substituted or unsubstituted C3-C6 branched-chain heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0238] R 25 and R 26 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C1-C3 straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C3-C6 branched chain alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl and substituted or unsubstituted C4-C6 cycloalkyl, or when taken together, R 25 and R 26 forming a monocyclic ring selected from the group consisting of heterocycloalkyl and heteroaryl;

[0239] R 27 、R 28 and R 29 each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, a C1 alkyl group, a C2 alkyl group, a C3 alkyl group, a C4 alkyl group, a C5 alkyl group, a C6 alkyl group, an ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2CH2-;

[0240] R 30Selected from the group consisting of hydrogen, substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C1-C3 straight-chain alkyl, substituted or unsubstituted branched-chain alkyl, substituted or unsubstituted C3-C6 branched-chain alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl and heteroaryl;

[0241] j is an integer ranging from 0 to 20;

[0242] k is an integer ranging from 0 to 20;

[0243] m is an integer in the range of 0 to 20; and

[0244] n is an integer ranging from 0 to 20.

[0245] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group is selected from the group consisting of:

[0246]

[0247]

[0248]

[0249]

[0250]

[0251] Generally speaking, the at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof and the at least one functionalized ligand not comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof can be present in any suitable ratio known in the art to promote the formation of the functionalized adsorbent described herein. In some embodiments, the ratio is selected from the group consisting of a molar ratio, a weight ratio, and a volume ratio. In some embodiments, the at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof and the at least one functionalized ligand not comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof are present in a ratio ranging from about 10:1 to about 1:10. In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof and at least one functionalized ligand excluding a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof are present in a ratio ranging from about 9:1 to about 1:9. In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof and at least one functionalized ligand excluding a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof are present in a ratio ranging from about 8:1 to about 1:8. In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof and at least one functionalized ligand excluding a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof are present in a ratio ranging from about 7:1 to about 1:7. In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof and at least one functionalized ligand not comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof are present in a ratio ranging from about 6: 1 to about 1: 6. In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof and at least one functionalized ligand not comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof are present in a ratio ranging from about 5: 1 to about 1: 5.In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof and at least one functionalized ligand excluding a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof are present in a ratio ranging from about 4:1 to about 1:4. In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof and at least one functionalized ligand excluding a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof are present in a ratio ranging from about 3:1 to about 1:3. In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof and at least one functionalized ligand excluding a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof are present in a ratio ranging from about 2:1 to about 1:2. In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof and at least one functionalized ligand not comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof are present in a ratio of about 1:1.

[0252] In some embodiments, the at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof is present in an amount less than the at least one functionalized ligand not comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0253] In some embodiments, at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof and at least one functionalized ligand not comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof are present in a ratio of about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, or about 1:10.

[0254] In general, the adsorbent can be any suitable adsorbent known in the art to facilitate the functionalized adsorbents described herein. In some embodiments, the adsorbent is selected from the group consisting of coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCPs), covalent organic framework (COF) compounds, zeolitic imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open frameworks, network chemistry, silica particles, zeolites, silicon-aluminum-phosphates (SAPOs), aluminum-phosphates (AlPOs), polyaromatic frameworks (PAFs), activated carbons, molecular organic solids, and combinations thereof.

[0255] As used herein, MOF compounds are a class of compounds that include metal ions or clusters coordinated with organic ligands to form one-dimensional, two-dimensional, or three-dimensional structures. The metal ions or clusters act as connectors and are bound by multidirectional organic ligands, which act as connectors in the network structure. MOF compounds have modular properties that allow for synthetic tunability, providing fine chemicals and structural control. Properties such as porosity, stability, particle morphology, and conductivity can be customized for specific applications.

[0256] In many embodiments, the adsorbent is a MOF compound comprising a MOF metal or metal-containing cluster and a MOF linker.

[0257] In some embodiments, the MOF metal can be any suitable MOF metal known in the art to promote the functionalized adsorbents described herein. In other embodiments, the MOF metal is a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, their ions, their hydrates, their salts, their halides, their fluorides, their chlorides, their bromides, their iodides, their nitrates, their acetates, their sulfates, their phosphates, their carbonates, their oxides, their formates, their carboxylates, and combinations thereof. In some embodiments, the MOF metal includes Mg.

[0258] In some embodiments, the MOF metal-containing cluster can be any suitable MOF metal-containing cluster known in the art to facilitate the functionalized adsorbents described herein. In some embodiments, the MOF metal-containing cluster comprises a MOF metal node and a linker strut, wherein the MOF metal and the linker are each as defined herein. In other embodiments, the MOF metal-containing cluster comprises a MOF metal-oxygen cluster.

[0259] In some embodiments, the MOF linker can be any suitable MOF linker known in the art to facilitate the functionalization of the adsorbents described herein. Generally, the geometry and connectivity of the linker contribute to the structure of the resulting MOF compound. Adjusting the linker geometry, length, ratio, and functional groups can tailor the size, shape, and internal surface properties of the MOF compound for the intended application.

[0260] In some embodiments, the MOF linker is a linker selected from the group consisting of a polytopic linker, a dihedral linker, a trihedral linker, a tetrahedral linker, a pentahedral linker, a hexahedral linker, a heptahedral linker, an octahedral linker, a mixed linker, a desymmetrized linker, a metal linker, an N-heterocyclic linker, and combinations thereof.

[0261] In at least some embodiments, the MOF linker is a linker selected from the group consisting of: a polyhedral linker, 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H4dobpdc), 4,4′-dioxybiphenyl-3,3′-dicarboxylate (dobpdc 4- )、4,4″-dioxy-[1,1′:4′,1″-terphenyl]-3,3″-dicarboxylate (dotpdc 4- ), 2,5-dioxyphenyl-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-dobdc 4- )、3,3′-dioxy-biphenyl-4,4′-dicarboxylate (p-carboxylate-dobpdc 4- ), 4,4′-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4′-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4′-dihydroxyazobenzene-3,3′-dicarboxylic acid (H4OSA), their protonated, partially and fully deprotonated forms, and combinations thereof. As another example, in some embodiments, the MOF linker is a linker selected from the group consisting of dicarboxylates (e.g., terephthalic acid), tricarboxylates (e.g., 1,3,5-benzenetricarboxylic acid), azolium salts, tetrazolium salts, and combinations thereof.

[0262] As another example, in some embodiments, the MOF linker is a dicarboxylic acid linker selected from the group consisting of 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, terephthalic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinone quinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4′-diaminophenylmethane-3,3′-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic acid, pentane-3,3-carboxylic acid, 4,4′-diamino-1,1′-diphenyl-3,3′-dicarboxylic acid, 4,4′-diaminodiphenyl-3,3′-dicarboxylic acid, benzidine-3,3′-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1′-dinaphthyl-8,8′-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4′-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloro Quinoline-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-benzoylphenyl-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2′-biquinoline-4,4′-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenonedicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4′-diaminodiphenyl ether diimide dicarboxylic acid, 4,4′-diaminodiphenylmethane diimide dicarboxylic acid, 4,4′-diaminodiphenylsulfone diimide dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 8-methoxy-2,3-naphthalene dicarboxylic acid, 8-nitro-2,3-naphthalene dicarboxylic acid, 8-sulfo-2,3-naphthalene dicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2′-3′-diphenyl-p-terphenyl-4,4″-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene -2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-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′-dihydroxydicarboxylic acid Benzene-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorescein-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.

[0263] As another example, in 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.

[0264] As another example, in some embodiments, the MOF linker is a tetracarboxylic acid linker selected from the group consisting of 1,1-dioxide-perylene[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, 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, 1,4,7,1 0,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, and combinations thereof.

[0265] In this exemplary embodiment, the MOF linker is 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H4dobpdc) and / or 4,4′-dioxybiphenyl-3,3′-dicarboxylate (dobpdc 4- In some embodiments, DOBPDC includes 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid, its monocarboxylate form, its dicarboxylate form, its monophenolate form, its diphenolate form, and combinations thereof. In some embodiments, the MOF linker is one or more of the following linkers:

[0266]

[0267]

[0268]

[0269] and / or

[0270]

[0271] In some embodiments, the MOF compound is a MOF compound of the MOF-74 family. In some embodiments, the MOF compound is a MOF compound of the MOF-274 family. In some embodiments, the MOF compound is a MOF compound of the MOF-303 family. In some embodiments, the MOF compound is Mg2(dobpdc).

[0272] In some embodiments, the functionalized adsorbent is a functionalized MOF compound of formula (SI)

[0273]

[0274] in:

[0275] M is the MOF metal or metal-containing cluster;

[0276] L is the MOF linker;

[0277] F A is a functionalized ligand comprising at least one polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof;

[0278] F B is a functionalized ligand that does not include at least one polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof;

[0279] x is a value in the range of 1 to 6;

[0280] y is a value in the range of 1 to 6;

[0281] a is a value greater than 0 and less than or equal to 2; and

[0282] b is a value in the range of 0 to 2.

[0283] In some embodiments, the functionalized sorbent comprises a metal organic framework (MOF) wherein a first amine of the polyamine is attached to a first metal site of the MOF, and optionally wherein a second amine of the polyamine is attached to a second metal site of the MOF.

[0284] In some embodiments, the functionalized sorbent does not include a MOF.

[0285] In some embodiments, the functionalized adsorbent comprises a non-MOF adsorbent. In some embodiments, the functionalized adsorbent comprises a mesoporous oxide support. In some embodiments, the functionalized adsorbent comprises a mesoporous oxide support selected from the group consisting of silica, alumina, zirconia, and combinations thereof. In some embodiments, the functionalized adsorbent comprises a porous polymer.

[0286] In some embodiments, the functionalized sorbent does not include a non-MOF.

[0287] In general, amine-functionalized MOFs tend to have better CO2 capacities than other adsorbents at low CO2 concentrations, such as those associated with DAC, expressed as the amount of CO2 captured per weight of adsorbent, such as gCO2 / g adsorbent or mmolCO2 / g adsorbent. Non-MOFs such as mesoporous silica and alumina can be less expensive and may have improved kinetics compared to other adsorbents.

[0288] The amines can be physically impregnated, which imparts low stability, or can be chemically grafted, which provides higher stability but lower CO2 capacity, depending on which amine is chosen.

[0289] One or more of a reduction in adsorbent particle size, an increase in adsorbent aspect ratio, and aqueous adsorbent synthesis results in an adsorbent with significantly improved CO2 absorption kinetics.

[0290] Generally, the adsorbent can comprise any suitable particle size known in the art to facilitate functionalizing the adsorbent as described herein. In some embodiments, the adsorbent has an average particle length of ≤ 5 μm. In some embodiments, the adsorbent has an average particle length of ≤3 μm, ≤2.9 μm, ≤2.8 μm, ≤2.7 μm, ≤2.6 μm, ≤2.5 μm, ≤2.4 μm, ≤2.3 μm, ≤2.2 μm, ≤2.1 μm, ≤2 μm, ≤1.9 μm, ≤1.8 μm, ≤1.7 μm, ≤1.6 μm, ≤1.5 μm, ≤1.4 μm, ≤1.3 μm, ≤1.2 μm, ≤1.1 μm, ≤1 μm, ≤0.9 μm, ≤0.8 μm, ≤0.7 μm, ≤0.6 μm, ≤0.5 μm, ≤0.4 μm, ≤0.3 μm, ≤0.2 μm, or ≤0.1 μm. In some embodiments, the adsorbent has an average particle length of ≥5 μm. In some embodiments, the adsorbent has an average particle length of ≥3 μm, ≥2.9 μm, ≥2.8 μm, ≥2.7 μm, ≥2.6 μm, ≥2.5 μm, ≥2.4 μm, ≥2.3 μm, ≥2.2 μm, ≥2.1 μm, ≥2 μm, ≥1.9 μm, ≥1.8 μm, ≥1.7 μm, ≥1.6 μm, ≥1.5 μm, ≥1.4 μm, ≥1.3 μm, ≥1.2 μm, ≥1.1 μm, ≥1 μm, ≥0.9 μm, ≥0.8 μm, ≥0.7 μm, ≥0.6 μm, ≥0.5 μm, ≥0.4 μm, ≥0.3 μm, ≥0.2 μm, or ≥0.1 μm.

[0291] Generally, the adsorbent may comprise any suitable aspect ratio known in the art that facilitates the functionalized adsorbents described herein. As used herein, aspect ratio is the ratio between the average width of the adsorbent and the average length of the adsorbent. In some embodiments, the adsorbent has an aspect ratio ranging from about 0 to about 1. In some embodiments, the adsorbent has an aspect ratio of ≤1, ≤0.9, ≤0.8, ≤0.7, ≤0.6, ≤0.5, ≤0.4, ≤0.3, ≤0.2, or ≤0.1. In some embodiments, the adsorbent has an aspect ratio of ≥0.9, ≥0.8, ≥0.7, ≥0.6, ≥0.5, ≥0.4, ≥0.3, ≥0.2, ≥0.1, or ≥0.

[0292] In some embodiments, the particle size is a single particle size.Single particle size measurements can be performed according to any suitable means known in the art, such as by measuring particle size in an SEM image.

[0293] In some embodiments, the particle size measurement is an average particle size measurement.Average particle size measurements can be made according to any suitable means known in the art, such as by analyzing particle size distribution information.

[0294] Generally, the particle size of the adsorbent can be controlled, altered, or reduced according to any suitable technique known in the art to facilitate the functionalization of the adsorbents described herein. In some embodiments, suitable techniques for controlling, altering, or reducing particle size include mechanical grinding (e.g., mortar and pestle), use of a microfluidizer, dry milling, wet milling, chemical size reduction (e.g., incorporation of crystal growth inhibitors), acoustic cavitation, hydrodynamic cavitation, and combinations thereof.

[0295] Generally, the adsorbent can be in any suitable form known in the art to facilitate the functionalization of the adsorbent described herein. In some embodiments, the adsorbent is in a form selected from the group consisting of a powder, a pellet, a composite material, a composite material mixed with a binder, a membrane, a coating, an aqueous coating, a packed bed, a column, a monolith, and combinations thereof.

[0296] The exemplary embodiments described herein include an adsorbent system. Generally, the adsorbent system can be any suitable adsorbent system known in the art that facilitates the functionalized adsorbents described herein. In some embodiments, the adsorbent system includes a functionalized adsorbent and an optional binder. In some embodiments, the adsorbent system is disposed on a polymeric membrane.

[0297] In some embodiments, the adsorbent system is in the form of a coating formulation. The coating formulation can be in the form of a solution, an emulsion, or a combination thereof. When in the form of a solution, the binder is water-soluble. When in the form of an emulsion, the binder is not water-soluble. The coating formulation can comprise a binder and optionally at least one additive. In some embodiments, the at least one additive is selected from the group consisting of silica particles, clay particles, alumina particles, and combinations thereof. In some embodiments, the binder comprises at least one water-based binder selected from the group consisting of water-based epoxy resins, water-based acrylic resins, water-soluble polymers, and combinations thereof.

[0298] In some embodiments, the adsorbent system comprises at least one contactor. In some embodiments, the adsorbent system comprises more than one contactor. In some embodiments, the adsorbent system comprises a contactor configured for an adsorption cycle and a contactor configured for a desorption cycle. The contactor can be any suitable contactor known in the art that facilitates the functionalized adsorbents described herein. In some embodiments, the adsorbent is integrated into at least one channel of the contactor. In some embodiments, the contactor is made of the adsorbent itself. In some embodiments, the contactor is coated with an adsorbent system. In some embodiments, the contactor comprises more than one adsorbent coating, wherein at least one adsorbent coating is an adsorbent system.

[0299] In some embodiments, the adsorbent system includes a skeleton. The skeleton can be any suitable skeleton known in the art that promotes the functionalized adsorbent described herein. The skeleton can be included in a contactor or between two contactors. The skeleton can be composed of one component or more than one component. In some embodiments, the skeleton is an air skeleton. In some embodiments, the configuration of the skeleton is selected from the group consisting of a polygonal configuration, a rectangular configuration, a square configuration, a circular configuration, an asymmetric configuration, and a combination thereof. In some embodiments, the adsorbent system is mounted on the skeleton.

[0300] In some embodiments, the adsorbent system includes at least one concentrator. The concentrator can be any suitable concentrator known in the art that facilitates the functionalized adsorbent described herein. The concentrator can be a passive concentrator or an active concentrator.

[0301] In some embodiments, the adsorbent system includes at least one component configured to drive fluid flow. The component configured to drive fluid flow can be any suitable component configured to drive fluid flow known in the art that facilitates the functionalized adsorbents described herein. In some embodiments, the component configured to drive fluid flow is selected from the group consisting of a pump, a fan, and combinations thereof.

[0302] In some embodiments, the adsorbent system includes at least one component configured to change temperature. The component configured to change temperature can be any suitable component configured to change temperature known in the art to facilitate the functionalized adsorbents described herein. In some embodiments, the component configured to change temperature is selected from the group consisting of a heater, a cooler, and combinations thereof.

[0303] In some embodiments, the adsorbent system includes at least one component configured to transport a fluid. The component configured to transport a fluid can be any suitable component configured to transport a fluid known in the art that facilitates the functionalized adsorbents described herein. In some embodiments, the component configured to transport a fluid is selected from the group consisting of a pipe, a perforated pipe, a plastic perforated pipe, a polymer perforated pipe, a metal perforated pipe, a composite perforated pipe, and combinations thereof.

[0304] In general, the functionalized adsorbents may be used for any suitable purpose known in the art that facilitates the use of the functionalized adsorbents described herein. In some embodiments, the functionalized adsorbents are used in adsorbent systems. In some embodiments, the functionalized adsorbents are used in carbon capture adsorbent systems. In some embodiments, the functionalized adsorbents are used in moisture adsorbent systems. In some embodiments, the functionalized adsorbents are used in carbon capture adsorbent systems in the presence of water. In some embodiments, the functionalized adsorbents are used to capture gases. In some embodiments, the functionalized adsorbents are used for post-combustion CO capture and / or direct air capture CO capture.

[0305] Exemplary embodiments described herein include methods of making adsorbent systems. Generally, the functionalized adsorbents can be prepared according to any suitable synthesis method known in the art that facilitates the functionalized adsorbents described herein.

[0306] In many embodiments, a method of preparing an adsorbent system comprises preparing an adsorbent and optionally functionalizing the adsorbent with at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0307] In some embodiments, the method of preparing an adsorbent system comprises functionalizing the adsorbent with at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof. In some embodiments, the method of preparing an adsorbent system comprises functionalizing the adsorbent with at least two functionalized ligands each comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof, wherein the polyamines containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof are different from each other. In some embodiments, the method of preparing an adsorbent system further comprises functionalizing the adsorbent with at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof. In some embodiments, the method of preparing an adsorbent system comprises controlling the ratio between at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof and at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof.

[0308] In some embodiments, the method of preparing the adsorbent system further comprises annealing the functionalized adsorbent. Annealing the adsorbent system may remove excess ligand. In some embodiments, annealing the functionalized adsorbent comprises annealing the functionalized adsorbent at an elevated temperature. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 50°C to about 400°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 100°C to about 300°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 150°C to about 250°C.

[0309] Figure 47 47 is an exemplary process flow diagram 4710. In this exemplary embodiment, process flow diagram 4710 depicts exemplary steps of the process embodiments described herein and is not intended to limit these process embodiments. In this exemplary embodiment, the process includes forming 4712 a mixture comprising: an adsorbent precursor; a crystal growth inhibitor; an optional solvent; and an optional non-solvent. The process also includes reacting 4714 the mixture. The adsorbent has an average particle length of ≤ 3 μm.

[0310] Forming 4712 the mixture can be performed by any suitable means known in the art. In some embodiments, all components are added simultaneously. In some embodiments, at least one component is added at a different time than the other components.

[0311] In some embodiments, the adsorbent precursor comprises a MOF linker and a MOF metal or metal-containing cluster. The adsorbent precursor can be formed prior to the mixture forming 4712 and added to the mixture as a single component, or can be formed in situ in the mixture during the mixture forming 4712. For example, the MOF linker can be deprotonated separately and then added or deprotonated in situ. Similarly, the MOF metal or metal-containing cluster can be preformed and then added or formed in situ.

[0312] In some embodiments, the solvent includes an aqueous solvent. In some embodiments, the solvent includes water. Using an aqueous solvent can provide several benefits. In particular, compared with at least some known methods for preparing MOF compounds, using an aqueous solvent has the advantages of scalability, safety, cost and waste disposal. In addition, MOF compounds prepared with aqueous solvents are generally easier to purify than the same MOF compounds prepared according to known methods, such as by solvent washing. This improved purification is derived from the removal of the strongly bound solvent molecules (e.g., DMF) utilized for preparing the same MOF compounds according to known methods, and it is relatively easy to remove solvent molecules (e.g., water) from the MOF compounds described herein. In addition, the purified MOF compounds do not include strongly bound solvent molecules that reduce gas absorption, surface area and / or total pore volume. Finally, purification is improved by requiring a purification method with less toxicity.

[0313] In some embodiments, the solvent is an organic solvent. In some embodiments, the solvent is a mixture of an organic solvent and an aqueous solvent.

[0314] Typically, a non-solvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, a non-solvent is a liquid-based component contained in the reaction mixture. In some embodiments, a non-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, a non-solvent is selected from the group consisting of an organic solvent, an aqueous solvent, and combinations thereof.

[0315] In some embodiments, the crystal growth inhibitor is selected from the group consisting of salicylic acid, 4-fluorosalicylic acid, 4,4'-biphenyldiphenol, 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC), 2,2'-bipyridine-5,5'-dimethanol (BPYDM), benzoic acid, biphenyldiphenol, bipyridine, and combinations thereof.

[0316] Figure 484810 is an exemplary process flow diagram. In this exemplary embodiment, process flow diagram 4810 depicts exemplary steps of the process embodiments described herein and is not intended to limit these process embodiments. In this exemplary embodiment, the process includes forming 4812 a mixture comprising: an adsorbent; at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; optionally at least one functionalized ligand not comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; an optional solvent; and an optional non-solvent. The process also includes functionalizing 4814 the adsorbent.

[0317] In some embodiments, functionalizing 4814 the adsorbent includes stirring the mixture.

[0318] In some embodiments, functionalizing 4814 the adsorbent includes functionalizing 4814 the adsorbent in the presence of an inert gas.

[0319] In some embodiments, functionalizing 4814 the adsorbent includes functionalizing 3514 the adsorbent at a temperature in the range of about 0° C. to about 100° C. In some embodiments, functionalizing 4814 the adsorbent includes functionalizing 3514 the adsorbent at a temperature in the range of about 20° C. to about 80° C. In some embodiments, functionalizing 4814 the adsorbent includes functionalizing 3514 the adsorbent at a temperature in the range of about 20° C. to about 60° C.

[0320] In some embodiments, functionalizing 4814 the adsorbent includes functionalizing 4814 the adsorbent for a time in a range from about 1 minute to about 7 days. In some embodiments, functionalizing 4814 the adsorbent includes functionalizing 4814 the adsorbent for a time in a range from about 1 hour to about 3 days.

[0321] In some embodiments, the adsorbent is desolvated prior to functionalization 4814. In some embodiments, the adsorbent is dry prior to functionalization.

[0322] In some embodiments, the adsorbent is annealed after functionalization 4814. In some embodiments, annealing the adsorbent includes annealing the adsorbent at an elevated temperature. In some embodiments, annealing the adsorbent includes annealing the adsorbent at a temperature in the range of about 50° C. to about 400° C. In some embodiments, annealing the adsorbent includes annealing the adsorbent at a temperature in the range of about 100° C. to about 300° C. In some embodiments, annealing the adsorbent includes annealing the adsorbent at a temperature in the range of about 150° C. to about 250° C.

[0323] 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.

[0324] Typically, a non-solvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, a non-solvent is a liquid-based component contained in the reaction mixture. In some embodiments, a non-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, a non-solvent is selected from the group consisting of an organic solvent, an aqueous solvent, and combinations thereof.

[0325] In some embodiments, the non-solvent facilitates functionalization. In some embodiments, the selectivity of functionalization is controlled by relative solubility. For example, one or more adsorbents or amines may have different solubility in a liquid-based reaction mixture compared to another adsorbent or amine or functionalized adsorbent. Thus, relative solubility introduces limiting reactions and / or reagents.

[0326] In many embodiments, the method may also include any other suitable processing steps known in the art that promote the success of the methods described herein. Such processing steps may include, but are not limited to, only washing, drying, filtering, purification, separation, centrifugation, and any combination thereof. In some embodiments, the method further includes washing the functionalized adsorbent. In some embodiments, the method further includes purifying the functionalized adsorbent. In some embodiments, purification includes using distillation, vacuum distillation, and / or heating.

[0327] Exemplary embodiments described herein include methods of modifying functionalized adsorbents.

[0328] Figure 49 4910 is an exemplary method flow diagram. In this exemplary embodiment, method flow diagram 4910 depicts exemplary steps of method embodiments described herein and is not intended to limit these method embodiments. In this exemplary embodiment, the method includes forming 4912 a mixture comprising: an adsorbent functionalized with at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; and a reactant. The method also includes reacting 4914 the reactant with the adsorbent functionalized with at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof to produce an adsorbent functionalized with at least one functionalized ligand that includes a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0329] Generally speaking, the reactant can include any suitable reactant known in the art to promote the formation of the functionalized adsorbent described herein. In many embodiments, the reactant comprises at least one functional group capable of reacting with the polyamine to form at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0330] In some embodiments, the reactant comprises at least one functional group selected from the group consisting of an epoxy group, an epoxy group comprising a fluorine atom, a 3-membered ring epoxy group, a monoepoxy group, a diepoxy group, an oxetane group, a 4-membered ring oxetane group, and combinations thereof.

[0331] In some embodiments, the reactant is selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-pentane oxide, 1,2-hexane oxide, 1,2-heptane oxide, 1,2-octane oxide, 2,2,2-(trifluoroethyl)ethylene oxide, diepoxyethane, 4-aminooxetane, 4-(aminomethyl)oxetane, and combinations thereof.

[0332] In some embodiments, reacting 4914 includes stirring the mixture.

[0333] In some embodiments, reacting 4914 includes reacting 4914 in the presence of an inert gas.

[0334] In some embodiments, reacting 4914 comprises reacting 4914 at a temperature in the range of about 0° C. to about 100° C. In some embodiments, reacting 4914 comprises reacting 4914 at a temperature in the range of about 20° C. to about 80° C. In some embodiments, reacting 4914 comprises reacting 4914 at a temperature in the range of about 20° C. to about 60° C.

[0335] In some embodiments, reacting 4914 comprises reacting 4914 for a time in the range of about 1 minute to about 7 days. In some embodiments, reacting 4914 comprises reacting 4914 for a time in the range of about 1 hour to about 3 days.

[0336] In some embodiments, the adsorbent is desolvated prior to reaction 4914. In some embodiments, the adsorbent is dry prior to reaction 4914.

[0337] In some embodiments, the adsorbent is annealed after reaction 4914. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at an elevated temperature. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 50° C. to about 400° C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 100° C. to about 300° C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 150° C. to about 250° C.

[0338] In some embodiments, reacting 4914 includes reacting 4914 in the presence of a solvent or a non-solvent.

[0339] 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.

[0340] Typically, a non-solvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, a non-solvent is a liquid-based component contained in the reaction mixture. In some embodiments, a non-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, a non-solvent is selected from the group consisting of an organic solvent, an aqueous solvent, and combinations thereof.

[0341] In some embodiments, the non-solvent facilitates functionalization. In some embodiments, the selectivity of functionalization is controlled by relative solubility. For example, one or more adsorbents or amines may have different solubility in a liquid-based reaction mixture compared to another adsorbent or amine or functionalized adsorbent. Thus, relative solubility introduces limiting reactions and / or reagents.

[0342] In many embodiments, the method may also include any other suitable processing steps known in the art that promote the success of the methods described herein. Such processing steps may include, but are not limited to, only washing, drying, filtering, purification, separation, centrifugation, and any combination thereof. In some embodiments, the method further includes washing the functionalized adsorbent. In some embodiments, the method further includes purifying the functionalized adsorbent. In some embodiments, purification includes using distillation, vacuum distillation, and / or heating.

[0343] Exemplary embodiments described herein include methods of capturing at least one gas.

[0344] Figure 505010 is an exemplary method flow diagram. In this exemplary embodiment, method flow diagram 5010 depicts exemplary method steps of method embodiments described herein and is not intended to limit these method embodiments. The method includes receiving 5012 a gas source comprising at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent includes: an adsorbent; and at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof. In some embodiments, the functionalized adsorbent includes at least two functionalized ligands, each comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof, wherein the polyamines containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof are different from each other. In some embodiments, the functionalized adsorbent further includes at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof. The method also includes capturing 5014 a quantity of the at least one gas with the functionalized adsorbent. The adsorbent can have an average particle length of ≤3 μm.

[0345] In some embodiments, the method comprises: (I) receiving 5012 a gas source comprising at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; and (II) capturing 5014 an amount of the at least one gas with the functionalized adsorbent.

[0346] Generally, the gas source can be any suitable gas source known in the art to facilitate the methods described herein. In some embodiments, the gas source is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0347] Generally, the at least one gas can be any suitable gas known in the art to facilitate the methods described herein. In some embodiments, the at least one gas is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0348] In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 100% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 40% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 15% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount greater than 10% (v / v).

[0349] In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 100 ppmv to about 1000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 200 ppmv to about 1000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 300 ppmv to about 5000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 200 ppmv to about 500 ppmv.

[0350] In some embodiments, the at least one gas does not include water vapor.

[0351] In some embodiments, the at least one gas comprises water vapor. In some embodiments, the at least one gas comprises water vapor in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, the at least one gas comprises water vapor in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, the at least one gas comprises water vapor in an amount ranging from about 0.5% (v / v) to about 15% (v / v). In some embodiments, the at least one gas comprises water vapor in an amount ranging from about 0.5% (v / v) to about 4% (v / v). In some embodiments, the at least one gas comprises water vapor in an amount ranging from about 4% (v / v) to about 15% (v / v).

[0352] In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v) and water vapor is present. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v) and water vapor is present. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v) and water vapor is present. In some embodiments, the at least one gas is present in the source gas in an amount greater than about 10% (v / v) and water vapor is present. In some embodiments, water vapor is present in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.5% (v / v) to about 10% (v / v).

[0353] In some embodiments, capturing 5014 an amount of the at least one gas with a functionalized adsorbent includes adsorbing an amount of the at least one gas with a functionalized adsorbent. In some embodiments, capturing 5014 an amount of the at least one gas with a functionalized adsorbent includes adsorbing an amount of the at least one gas with a functionalized adsorbent in the presence of water vapor.

[0354] In some embodiments, the amount of at least one gas captured 5014 with the functionalized adsorbent is in the range of about 1% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 5014 with the functionalized adsorbent is in the range of about 10% (v / v) to about 90% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 5014 with the functionalized adsorbent is in the range of about 20% (v / v) to about 80% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 5014 with the functionalized adsorbent is in the range of about 30% (v / v) to about 70% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 5014 with the functionalized sorbent is in a range from about 40% (v / v) to about 60% (v / v) of the at least one gas present in the source gas.

[0355] In some embodiments, the amount of at least one gas captured 5014 with the functionalized adsorbent is in the range of about 1% (v / v) to about 25% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 5014 with the functionalized adsorbent is in the range of about 1% (v / v) to about 20% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 5014 with the functionalized adsorbent is in the range of about 1% (v / v) to about 15% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 5014 with the functionalized adsorbent is in the range of about 1% (v / v) to about 10% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 5014 with the functionalized sorbent is in a range from about 1% (v / v) to about 5% (v / v) of the at least one gas present in the source gas.

[0356] In some embodiments, the amount of at least one gas captured 5014 with the functionalized adsorbent is in the range of about 80% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 5014 with the functionalized adsorbent is in the range of about 85% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 5014 with the functionalized adsorbent is in the range of about 90% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 5014 with the functionalized adsorbent is in the range of about 95% (v / v) to about 100% (v / v) of the at least one gas present in the source gas.

[0357] In some embodiments, the source gas is modified to change the amount of water vapor. In some embodiments, changing the amount of water vapor includes increasing the amount of water vapor. In some embodiments, changing the amount of water vapor includes reducing the amount of water vapor. In some embodiments, increasing the amount of water vapor includes adding or injecting water vapor into the source gas. In some embodiments, reducing the amount of water vapor includes removing water vapor from the source gas by evaporation, condensation, and / or pre-adsorption. In some embodiments, changing the amount of water vapor includes exhaust gas recirculation (EGR) and / or mixing.

[0358] In many embodiments, the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof are at a temperature. Each temperature can be varied to facilitate the methods described herein. Each temperature can have a uniform temperature profile, a gradient temperature profile, a discrete temperature profile, or a combination thereof.

[0359] In some embodiments, the method includes an adsorption cycle. In some embodiments, the method includes a desorption cycle. In some embodiments, during the gas adsorption cycle, at least one of the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof is at a temperature in the range of about -40°C to about 150°C. In some embodiments, during the gas desorption cycle, at least one of the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof is at a temperature in the range of about 60°C to about 250°C. Each adsorption module or submodule can have a uniform temperature profile, a gradient temperature profile, or a discrete temperature profile.

[0360] In some embodiments, the method includes controlling temperature.The temperature of the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof can be controlled.

[0361] Exemplary embodiments described herein include methods of collecting at least one gas from a gas source.

[0362] Figure 51 5110 is an exemplary method flow diagram. In this exemplary embodiment, method flow diagram 5110 depicts exemplary method steps of method embodiments described herein and is not intended to limit these method embodiments. The method includes receiving 5112 a gas source comprising at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent includes: an adsorbent; and at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof. In some embodiments, the functionalized adsorbent includes at least two functionalized ligands, each comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof, wherein the polyamines containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof are different from each other. In some embodiments, the functionalized adsorbent further includes at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof. The method also includes capturing 5114 a quantity of the at least one gas with the functionalized adsorbent. The method also includes releasing 5116 the at least one gas from the functionalized adsorbent. The adsorbent may have an average particle length of ≤ 3 μm.

[0363] In some embodiments, the method comprises: (I) receiving 5112 a gas source comprising at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; (II) capturing 5114 an amount of the at least one gas with the functionalized adsorbent; and (III) releasing 5116 the at least one gas from the functionalized adsorbent.

[0364] In some embodiments, releasing 5116 at least one gas from the functionalized adsorbent comprises purging the at least one gas from the functionalized adsorbent with a purge gas. In some embodiments, releasing 5116 at least one gas from the functionalized adsorbent comprises receiving a change in temperature or pressure at the functionalized adsorbent.

[0365] In some embodiments, at least one gas is released 5116 from the functionalized adsorbent into a receiving gas. In some embodiments, the receiving gas is selected from the group consisting of air, N2, steam, and combinations thereof. In some embodiments, after receiving the at least one gas, the receiving gas is removed from the presence of the functionalized adsorbent. In some embodiments, the receiving gas has a higher concentration of the at least one gas than the source gas.

[0366] Example

[0367] Without further detailed description, it is believed that one skilled in the art can utilize the present invention to the greatest extent possible using the foregoing description. Therefore, the following examples are to be construed as illustrative only and not to limit the present disclosure in any way. The starting materials used in the following examples may not necessarily be prepared by a specific preparation run, the procedures for which are described in other examples. It should also be understood that any numerical ranges described herein include all values ​​from the lower limit to the upper limit. For example, if a range is stated as 10 to 50, it is intended that values ​​such as 12 to 30, 20 to 40, or 30 to 50 are explicitly listed in this specification. These are merely examples of specific intent, and all possible combinations of numerical values ​​between and including the lowest and highest values ​​listed are considered to be explicitly stated in this application.

[0368] Synthesis of MOF adsorbents

[0369] Example A1. General procedure for MOF and adsorbent synthesis.

[0370] First, the MOF is synthesized by an aqueous formulation, washed three times with water, and washed three times with isopropyl alcohol. The reaction can be carried out using a non-aqueous solvent such as a dimethylformamide (DMF) / methanol (MeOH) mixture, an aqueous solvent, or both, as disclosed in PCT / US2022 / 082243, the contents of which are incorporated herein by reference. The material is then dried by vacuum filtration to obtain approximately 70% to 75% solvated material. To prepare the material for loading, it is desolvated in a vacuum oven at 120°C overnight to reduce the alcohol content to 0.5-1 equivalents of isopropyl alcohol (IPA) per metal site, thereby protecting the open metal sites from oxidation while also removing excess solvent from the pores of the MOF. Figure 1 As shown, through 1 H NMR determines how much residual solvent (e.g., Mg2(dobpdc)1(alcohol)) is still present in the MOF. x ), the exact molar amount of MOF can be determined. Therefore, by adding 1-4 equivalents of amine in a non-polar solvent, a MOF with Mg2(dobpdc)1(amine) x The material of composition. Figure 2 Shown is an SEM image of an exemplary MOF-274 (sample ID# A2111) prepared according to the standard aqueous procedure.

[0371] Example A2. General method for analysis of amine content by NMR.

[0372] To digest the amine-added MOF, 10 mg of material was added to a vial along with 20 μL of 35% DC1 in D2O, 200 μL of D2O, and 600 μL of DMSO-d6. The vial was sonicated to dissolve the framework and 1 H NMR. By comparing the backbone ligand peak (H4dobpdc) with the amine peak 1 H NMR integration was used to determine the loading amount.

[0373] Example A3. Particle size reduction.

[0374] The particle size or length of the rod-shaped crystals can be reduced by a number of options, including but not limited to mechanical grinding such as a mortar and pestle, use of a microfluidizer, dry or wet milling, or by chemical means such as incorporation of crystal growth inhibitors. Table 1 summarizes the particle size and aspect ratio of MOF-274 prepared according to some embodiments.

[0375] Table 1. Average particle size and aspect ratio of MOF-274 prepared with and without crystal growth inhibitors.

[0376]

[0377] Example A4. General procedure for the synthesis of small-sized MOF-274 using a crystal growth inhibitor.

[0378] Mg2(dobpdc) is synthesized by first dissolving x moles of H4dobpdc, y moles of a synthetic crystal growth inhibitor, and (x)*4+(y)*2 moles of NaOH in water by heating to 60°C. Exemplary synthetic crystal growth inhibitors include, but are not limited to, salicylic acid (SA), 4-fluorosalicylic acid (FSA), 4,4'-bisphenol (BP), 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC), and 2,2'-bipyridine-5,5'-dimethanol (BPYDM). The molar amount of the crystal growth inhibitor can range from 0.1 mol% to 50 mol% relative to 99.9 mol% to 50 mol% of H4dobpdc. Mg2(dobpdc) is added to the deprotonated solution of the linker and the crystal growth inhibitor. 2+ Aqueous solution of salt in which the counter anion is NO3 - 、Cl - Br - 、SO4 -2 、OAc - , O -2 、Otf - Mg 2+ The addition of salt can be performed quickly (e.g., <1 minute) or dropwise over an extended period of time (e.g., >1 hour). Heat to 97° C. and reflux under N 2 for 12 to 16 hours. The white precipitate is washed three times with water and three times with isopropanol and stored in a solvated form for further use.

[0379] Example A5. Exemplary procedure for the synthesis of small-sized MOF-274 using salicylic acid as a crystal growth inhibitor.

[0380] Mg2(dobpdc) was prepared on a 300 mL scale. First, the linker, crystal growth inhibitor, and base were added to a 500 mL round-bottom flask and heated to dissolve in water. In this example, sodium hydroxide (76 mmol, 3.04 g), H4dobpdc (18 mmol, 4.94 g), and salicylic acid (2 mmol, 0.276 g) were dissolved in water (220 mL) in a flask by stirring and heating to 60°C under N2 until the solution became clear. Next, Mg(NO3)2 hexahydrate (45 mmol, 11.54 g) was dissolved in 80 mL of water in a separate container and quickly added to the deprotonated linker solution to precipitate the MOF. The mixture was reacted in an open flask at ambient pressure and gently refluxed at about 97°C for 12 to 16 hours. The reaction produced the MOF compound Mg2(dobpdc)(salicylate) x, which was subsequently washed three times with water, three times with isopropanol, and stored in alcohol. To measure the surface area, the material was activated at 250°C to obtain the highest absorption. For each individual batch, the reaction produced 4.2 g to 4.7 g (72% to 81% yield) of Mg2(dobpdc)(salicylate) x The material can be desolvated at 85 °C and loaded normally as conventional MOF-274. Figure 3 Shown are SEM images of exemplary MOF-274 prepared using salicylic acid (left) and fluorosalicylic acid (right) as crystal growth inhibitors.

[0381] Example A6. Exemplary procedure for the synthesis of small-sized MOF-274 using 4,4'-bisphenol as a crystal growth inhibitor.

[0382] Mg2(dobpdc) was prepared on a 20 mL scale. First, the linker, crystal growth inhibitor, and base were added to a 20 mL scintillation vial and heated to dissolve in water. In this example, sodium hydroxide (4 mmol, 0.160 g), H4dobpdc (0.9 mmol, 0.247 g), and 4,4'-bisphenol (0.1 mmol, 0.019 g) were dissolved in water (10 mL) in a vial by stirring and heating to 60°C until the solution became clear. Next, Mg(NO3)2 hexahydrate (2 mmol, 0.512 g) was dissolved in 5 mL of water in a separate container and quickly added to the deprotonated linker solution to precipitate the MOF. The mixture was reacted in a vial at ambient pressure and gently refluxed at about 97°C for 12-16 hours. The reaction produced the MOF compound Mg2(dobpdc)(BP) x , which was subsequently washed three times with water, three times with isopropanol, and stored in alcohol. To measure the surface area, the material was activated at 250°C to obtain the highest absorption. The reaction produced yields of Mg2(dobpdc)(BP) ranging from 37% to 72%, depending on the amount of inhibitor used. x The material can be desolvated at 85 °C and loaded normally as conventional MOF-274. Figure 4 Figure 2 shows the powder X-ray diffraction spectrum of MOF-274 synthesized using 4,4'-biphenyldiphenol as a crystal growth inhibitor, where the MOF-274 phase is retained at 50 mol% BP input. Figure 5 As shown, the incorporation of 4,4'-biphenyldiphenol significantly reduced the particle size.

[0383]

[0384] Example A7. Exemplary procedure for the synthesis of small-sized MOF-274 using BPYDC as a crystal growth inhibitor.

[0385] Mg2(dobpdc) was prepared on a 20 mL scale. First, the linker, crystal growth inhibitor, and base were added to a 20 mL scintillation vial and heated to dissolve in water. In this example, sodium hydroxide (4 mmol, 0.160 g), H4dobpdc (0.9 mmol, 0.247 g), and 2,2'-bipyridine-5,5'-dicarboxylic acid (0.1 mmol, 0.024 g) were dissolved in water (10 mL) in a vial by stirring and heating to 60°C until the solution became clear. Next, Mg(NO3)2 hexahydrate (2 mmol, 0.512 g) was dissolved in 5 mL of water in a separate container and quickly added to the deprotonated linker solution to precipitate the MOF. The mixture was reacted in a vial at ambient pressure and gently refluxed at about 97°C for 12-16 hours. The reaction produced the MOF compound Mg2(dobpdc)(BPYDC) x , which was subsequently washed three times with water, three times with isopropanol, and stored in alcohol. To measure the surface area, the material was activated at 250°C to obtain the highest absorption. The reaction produced Mg2(dobpdc)(BPYDC) in yields between 68% and 74%, depending on the amount of inhibitor used. x The material can be desolvated at 85 °C and loaded normally as conventional MOF-274. Figure 5 The powder X-ray diffraction spectrum of MOF-274 synthesized using 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC) as a crystal growth inhibitor is shown. When BPYDC is input up to 50 mol%, the MOF-274 phase is retained. Figure 6 As shown, the incorporation of BPYDC significantly reduced the particle size.

[0386]

[0387] Example A8. Exemplary procedure for the synthesis of small-sized MOF-274 using BPYDM as a crystal growth inhibitor.

[0388] Mg2(dobpdc) was prepared on a 20 mL scale. First, the linker, crystal growth inhibitor, and base were added to a 20 mL scintillation vial and heated to dissolve in water. In this example, sodium hydroxide (4 mmol, 0.160 g), H4dobpdc (0.9 mmol, 0.247 g), and 2,2'-bipyridine-5,5'-dimethanol (0.1 mmol, 0.022 g) were dissolved in water (10 mL) in a vial by stirring and heating to 60°C until the solution became clear. Next, Mg(NO3)2 hexahydrate (2 mmol, 0.512 g) was dissolved in 5 mL of water in a separate container and quickly added to the deprotonated linker solution to precipitate the MOF. The mixture was reacted in a vial at ambient pressure and gently refluxed at about 97°C for 12-16 hours. The reaction produced the MOF compound Mg2(dobpdc)(BPYDM) x , which was subsequently washed three times with water, three times with isopropanol, and stored in alcohol. To measure the surface area, the material was activated at 250°C to obtain the highest absorption. The reaction produced yields of Mg2(dobpdc)(BPYDM) ranging from 53% to 81%, depending on the amount of inhibitor used. x . Figure 7 Figure 2 shows the powder X-ray diffraction spectra of MOF-274 synthesized using 2,2'-bipyridyl-5,5'-dimethanol (BPYDM) as a crystal growth inhibitor. The particle length of MOF-274 initially decreases with increasing BPYDM incorporation. However, as Figure 8 As shown, further increasing the BPYDM loading leads to an increase in particle length and a decrease in aspect ratio.

[0389]

[0390]

[0391] Example A9. Bare MOF Example: Improving the Kinetics of CO2 Absorption.

[0392] Comparative Example-1 (Comparative-1): A bare MOF sample with ID A2173 was prepared using aqueous solvent (H2O) following the general procedure described in Example A1.

[0393] Comparative Example-2 (Comparative-2): A bare MOF sample with ID A315B was prepared following the general procedure described in Example A5, but using non-aqueous solvent DMF.

[0394] Inventive Example-1 (Inventive Example-1): A bare MOF sample with ID A2177 was prepared by following the general procedure described in Example A1 using aqueous solvent (H2O).

[0395] Inventive Example-2 (Inventive-2): A bare MOF sample with ID A316 was prepared following the general procedure described in Example A5, but using salicylic acid (SA) as the crystal growth inhibitor and an aqueous solvent (H2O).

[0396] Inventive Example-3 (Inventive-3): A bare MOF sample with ID A39C was prepared following the general procedure described in Example A5, but using salicylic acid (SA) as the crystal growth inhibitor and an aqueous solvent (H2O).

[0397] Table 2 summarizes the synthesis details, particle size, aspect ratio, and CO2 absorption performance measured at a concentration of 4.5 vol% dry CO2. The combination of reduced particle size, increased aspect ratio, and aqueous MOF synthesis clearly leads to MOFs with significantly improved CO2 absorption kinetics.

[0398] Table 2. MOF synthesis details, particle size, aspect ratio, and CO2 performance.

[0399]

[0400] A solid adsorbent material functionalized with a polyamine having oxygen-containing units selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof.

[0401] Example B1. General procedure for the preparation of oxygen-containing amines.

[0402] Oxygen-containing amines can be prepared by direct synthesis. Non-limiting methods of direct synthesis include modifying non-oxygen-containing amines before MOF functionalization and modifying non-oxygen-containing amines after MOF functionalization. These methods of modifying non-oxygen-containing amines before and after MOF functionalization are referred to as pre-loaded modification (PLM) and post-synthesis modification (PSM), respectively.

[0403] Example B2. General method for preload modification (PLM) of functionalized amines using epoxides.

[0404] A 17 wt % methanol aqueous solution of 1 equivalent of amine is placed in a 20 mL scintillation vial. Then, 0.01 to 4 equivalents of functionalized oxirane (epoxide) are added to the methanol solution. The solution is stirred overnight at room temperature. After at least 12 hours, the solvent is removed via a rotary evaporator. The amine is dried in an 80 ° C vacuum oven for 4 hours. NMR samples are prepared in deuterated methanol (CD3OD) to determine the functionalization ratio. For example, 1 equivalent of spermine (2 mmol, 0.405 g) is added to a 20 mL scintillation vial and dissolved in 3 mL of methanol. Then, 1 equivalent of 1,2-butylene oxide (2 mmol, 174 μL) is added and the solution is stirred at room temperature for 18 hours. Methanol is removed via a rotary evaporator to produce 0.27 1,2-butylene oxide:spermine in a quantitative yield.

[0405] Example B3. General support of PLM amines comprising secondary alcohol units (eg, via epoxides).

[0406] Unless otherwise indicated, the following examples were performed using mechanically ground MOF [Mg2(dobpdc)], which had an average particle size of 0.48 μm (D50) as measured by a Malvern Zetasizer. Exemplary amines comprising secondary alcohol units were prepared by ring-opening an amine with an epoxide. Amines comprising secondary alcohol units can also be prepared by other means, such as direct synthesis.

[0407] A 20 mL scintillation vial was charged with 1 to 2.2 equivalents of a functionalized amine at an O / N ratio of 0.01 to 1 and dissolved in 5 mL of toluene. 1 equivalent of Mg2(dobpdc)(IPA) was then desolvated overnight in a vacuum oven at 120°C. x Add to a vial. The slurry was then placed on a hot plate and stirred at 300 to 400 rpm at 60°C overnight. The material was cooled to room temperature and transferred to a conical tube. The material was decelerated at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was dried in a vacuum oven at 120°C overnight to obtain Mg2(dobpdc) loaded with β-alcohol functionalized amine. Excess amine or surface amine (if any) can be removed by annealing at an elevated temperature. In addition, annealing may also help the amine chain to reorganize and eventually reach a stable configuration and attach to the metal site. Digest the material and use 1 H NMR was used to determine the initial and final loading amounts after annealing.

[0408] Example B4. General method for analysis of amine content by NMR.

[0409] To digest the amine-added MOF, 10 mg of material was added to a vial along with 20 μL of a 20% deuterium chloride (DCl) solution in heavy water (D2O), 200 μL of D2O, and 600 μL of DMSO-d6. The vial was sonicated to dissolve the framework and 1 H NMR. By comparing the backbone ligand peak (H4dobpdc) with the amine peak 1 H NMR integration was used to determine the loading amount. Figure 9 In the example spectrum of GE5-A369 shown, the ligand peaks from δ 7.9-7.0 ppm are all integrated for 2H. The peaks corresponding to spermine at δ 1.65 ppm and 1.93 ppm are integrated for a total of 8.22. By dividing the total integral by the theoretical number of protons (8), the relative proton content of the loaded product to one ligand, Mg2(dobpdc)(spermine), can be obtained. 1.01 ratio.

[0410] Example B5. General method for analysis of oxygen to amine (O / N) ratios using NMR.

[0411] Generally, the functionalized amine was dissolved in 600 μL of CD3OD and the parent amine was prepared by 1 HNMR determination of oxygen and nitrogen ratio. Figure 10 For NMR in the , the peak at 1.66 ppm was assigned to 4H (c). The amount of functionalization can be determined by the CH3 peak at δ 0.96 ppm (a) or the hydrogen attached to the beta (β)-alcohol at δ 3.58 ppm (e).

[0412]

[0413] Example B6. General method for preload modification (PLM) of functionalized amines using oxetanes.

[0414] A 20 mL scintillation vial is charged with 1 equivalent of an amine and 0.01 to 4 equivalents of a functionalized oxetane, dissolved in 3 mL of anhydrous toluene. 0.01 to 4 equivalents of a lanthanide-based Lewis acid catalyst, such as ytterbium (III) trifluoromethanesulfonate [Yb(OTf)3], is then added and stirred at 80°C for 24 to 48 hours. The product settles out of the solvent as a viscous liquid. The solvent is decanted and 5 mL of deionized water is added to dissolve the product, allowing the catalyst byproducts to settle out. The aqueous solution is filtered and the water layer is removed via rotary evaporation. The amine is dried in a vacuum oven at 120°C for 24 hours. NMR samples are prepared in deuterium oxide (DO) to determine the functionalization ratio.

[0415] The reaction scheme is described below.

[0416]

[0417] For example, asymmetric β-methylhydroxy-tetramine (2-4-3 or 2-3-4 carbon spacer) was synthesized via the ring-opening reaction of 4-aminooxetane with spermidine. 1 equivalent of spermidine (2 mmol, 314 μL) and 1 equivalent of 4-aminooxetane (2 mmol, 140 μL) were placed in a 20 mL scintillation vial and dissolved in 3 mL of anhydrous toluene. 0.5 equivalents of Yb(OTf)3 (1 mmol, 0.620 g) were then added to the vial and stirred at 80 ° C for 24 hours. The toluene was decanted and 5 mL of deionized water was added to dissolve the product, allowing the catalyst byproducts to settle out. The precipitate was filtered through a filter disc and the water layer was reduced by rotary evaporation. The β-methylhydroxy-tetramine was then dried in a vacuum oven at 120 ° C for 24 hours to produce the product in 92% yield ( Figure 11 ).

[0418] Example B7. Synthesis of hexanoyl chloride-modified spermine.

[0419] In a 20 ml scintillation vial, spermine (0.5 g, 2.47 mol) was dissolved in a dichloromethane / toluene (4 ml / 1 ml) solvent mixture and cooled to 0°C. Hexanoyl chloride (HC) (0.332 g, 2.47 mol) was added dropwise to the cold reaction mixture, forming a white precipitate. After 30 minutes, the ice bath was removed and the reaction mixture was stirred at room temperature overnight. Following the reaction, the solvent was evaporated to dryness to obtain the protonated salt of HC:spermine. This product was used in the next step without purification.

[0420] The reaction scheme is described below.

[0421]

[0422] The as-synthesized protonated salt (0.757 g, 0.0025 mol) was dissolved in 3 ml of methanol (0.42 g, 0.0075 mol) containing potassium hydroxide (KOH). After stirring overnight at room temperature, the solvent was evaporated under vacuum. To remove residual potassium chloride (KCl) salts, the resulting solid was further treated with tetrahydrofuran (THF). After filtering the remaining salts, the solvent was evaporated under vacuum. The product was obtained in a 94% yield.

[0423] Example B8. General method for analyzing the oxygen to amine ratio (O / N) of hexanoyl chloride (HC) modified amines by NMR.

[0424] Generally, the functionalized amine was dissolved in 600 μL of CD3OD and the parent amine was prepared by 1 HNMR determination of oxygen and nitrogen ratio. Figure 12In the NMR analysis, the peak between 2.6 and 2.7 ppm was set to an integration value of 10, as highlighted by one of the blue circles. The amount of functionalization can be determined by the CH peak at δ 0.94 ppm. Based on the formula mentioned above, the O / N ratio is approximately 0.38.

[0425] Example B9. Exemplary functionalized adsorbent materials.

[0426] Some exemplary adsorbent materials functionalized with different amines are shown in Table 3.

[0427] Table 3. Exemplary functionalized adsorbent materials, including preloaded modified (PLM) and post-synthesis modified (PSM) adsorbents.

[0428]

[0429]

[0430] Example B10. Synthesis of GE296-A366A.

[0431] A 20 mL scintillation vial was charged with 1.2 equivalents of 0.25 1,2-butylene oxide (EB): spermine (0.1229 g, 0.43 mmol) dissolved in 5 mL of toluene. 0.160 g (1 equivalent, 0.36 mmol) of Mg2(dobpdc)(IPA) was then desolvated overnight in a vacuum oven at 120°C. 2.05 Add to a vial. The slurry was then stirred at 300 to 400 rpm on a hot plate at 60°C overnight. The material was cooled to room temperature and transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was dried in a vacuum oven at 120°C overnight to obtain 0.201 g of GE296 (85% yield, Mg2(dobpdc) (0.22 EB: spermine) 1.01 ).

[0432] Example B11. Synthesis of GE301-A370A.

[0433] A 20 mL scintillation vial was charged with 1.5 equivalents of 0.25 1,2-octyloxydecane (EO):spermine (0.1795 g, 0.54 mmol) dissolved in 5 mL of toluene. 0.160 g (1 equivalent, 0.36 mmol) of Mg2(dobpdc)(IPA) was then desolvated overnight in a vacuum oven at 120°C. 2.05The slurry was then stirred at 300 to 400 rpm on a hot plate at 60°C overnight. The material was cooled to room temperature and then transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was dried in a vacuum oven at 120°C overnight to obtain 0.248 g of GE301 (84% yield, Mg2(dobpdc)(0.17 EO:spermine)). 1.04 ).

[0434] Example B12. Synthesis of GE308-A385B.

[0435] A 20 mL scintillation vial was charged with 1.5 equivalents of 0.46 (2,2,2-trifluoroethyl) oxirane (TFEO): N,N'-bis (2-aminoethyl) -1,3-propanediamine (0.1555 g, 0.54 mmol) and dissolved in 5 mL of toluene. 0.160 g (1 equivalent, 0.36 mmol) of Mg2(dobpdc)(IPA) was then desolvated overnight in a vacuum oven at 120°C. 2.05 The slurry was then stirred at 300 to 400 rpm on a hot plate at 60°C overnight. The material was cooled to room temperature and transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was dried in a vacuum oven at 120°C overnight to obtain 0.219 g of GE308 (81% yield, Mg2(dobpdc)(0.36TFEO:2-3-2) 1.06 ).

[0436] Example B13. Synthesis of GE314-A3107.

[0437] The MOF used to prepare GE314 was prepared using salicylic acid as a crystal growth inhibitor, and its average particle size was 0.24 μm as measured by Malvern Zetasizer. A 250 mL round-bottom flask was charged with 1.2 equivalents of 0.10 1,2-butylene oxide (EB): N, N'-bis(2-aminomethyl)-1,3-propanediamine (hereinafter referred to as "amine 2-3-2") (2.149 g, 10.9 mmol) and dissolved in 90 mL of toluene. Then, 4.5 g (1 equivalent, 9.1 mmol) of MOFMg2(dobpdc)(IPA) was desolvated overnight in a vacuum oven at 120 ° C. 2.9The slurry was then placed in a 60°C oil bath and stirred at 300 to 400 rpm overnight in a N2 atmosphere. After the material cooled to room temperature, it was filtered by vacuum filtration. The material was collected and dried in a vacuum oven at 120°C overnight to obtain 4.71 g of GE314 (86% yield, Mg2(dobpdc) (0.11 EB:2-3-2) 1.12 ).

[0438] Example B14. General Support of PLM Amines Including Primary Alcohol Units (eg, via Oxetane).

[0439] Unless otherwise indicated, the following examples were performed using mechanically ground MOF [Mg2(dobpdc)], which had an average particle size of 0.48 μm (D50) as measured by a Malvern Zetasizer. Exemplary amines comprising primary alcohol units were prepared by ring-opening an amine with an oxetane. Amines comprising primary alcohol units can also be prepared by other means, such as by direct synthesis.

[0440] A 20 mL scintillation vial was charged with 1 to 2.2 equivalents of a novel amine synthesized by reacting a functionalized oxetane with an amine and dissolved in 5 mL of solvent. 1 equivalent of Mg2(dobpdc)(IPA) was then desolvated overnight in a vacuum oven at 120°C. x Add to a vial. The slurry is then placed on a hot plate and stirred at 300 to 400 rpm at 50 to 60°C overnight. After the material has cooled to room temperature, it is transferred to a conical tube or rotary evaporated based on the loading method used. The material in the conical tube is spun down at 4000 rpm for 2 minutes and then decanted, or the material in the vial is rotary evaporated to remove the solvent. The sample is then dried in a vacuum oven at 120°C overnight to obtain Mg2(dobpdc) loaded with β-alcohol functionalized amines. Excess amines or surface amines, if any, can be removed by annealing at elevated temperatures. In addition, annealing may also help the amine chains to reorganize and ultimately reach a stable configuration and attach to the metal site. Digest the material and utilize 1 HNMR was used to determine the initial and final loading amounts after annealing.

[0441] Example B15. Synthesis of GE327-A3117D.

[0442] A 20 mL scintillation vial was charged with 1.2 equivalents of β-methylhydroxy-tetramine (2-4-3 or 2-3-4) (0.0886 g, 0.50 mmol) and dissolved in 5 mL of toluene. 0.160 g (1 equivalent, 0.34 mmol) of Mg2(dobpdc)(IPA) was then desolvated overnight in a vacuum oven at 120°C. 2.56Add to a vial. The slurry was then stirred on a hot plate at 50°C at 300 to 400 rpm overnight. The material was cooled to room temperature and the solvent removed via a rotary evaporator. The sample was dried in a vacuum oven at 120°C overnight to obtain 0.245 g of GE327-A3117D (99% yield, Mg2(dobpdc)(β-methylhydroxy-tetraamine)3).

[0443] Example B16. General Support of PLM Amines Including Carbonyl Units.

[0444] Unless otherwise indicated, the following examples were performed using mechanically ground MOF [Mg2(dobpdc)], which had an average particle size of 0.48 μm (D50) as measured by a Malvern Zetasizer. Exemplary amines comprising carbonyl units are prepared by reacting amines with acyl-containing compounds, including acyl halides, including acyl fluorides, acyl chlorides, acyl bromides, or acyl iodides, carboxylic acids, acid anhydrides, and the like. Amines comprising carbonyl units can also be prepared by other means, such as by direct synthesis.

[0445] Example B17. Synthesis of GE322-SG1-176.

[0446] A 20 mL scintillation vial was charged with 1.25 equivalents of 0.48 hexanoyl chloride (HC): spermine (0.1765 g, 0.587 mmol) and dissolved in 3 mL of toluene. 0.150 g (1 equivalent, 0.47 mmol) of Mg2(dobpdc)(IPA) was then desolvated overnight in a vacuum oven at 120°C. 1.76 Add to the vial. The reaction mixture was then placed on a hot plate and stirred at 300 to 400 rpm at 60°C overnight. After the vial cooled to room temperature, the reaction mixture was transferred to a 15 ml centrifuge tube. The upper solvent layer was decanted, and finally, the residue was dried in a vacuum oven at 120°C. NMR analysis yielded GE322-SG1-176 (90% yield, Mg2(dobpdc)(0.48HC:spermine) 0.52 )( Figure 13 ).

[0447] Example B18. General procedure for post-synthesis modification (PSM) of adsorbents.

[0448] A 20 mL scintillation vial was charged with 1 equivalent of adsorbent, i.e., MOF274 functionalized with amine. The adsorbent was dispersed in 5 mL of hexane. Then, 0.01 to 4 equivalents of functionalized ethylene oxide were added to the slurry in addition to 0.5 equivalents of ethanol per equivalent of functionalized ethylene oxide to catalyze the ring-opening reaction. The slurry was placed on a hot plate and stirred at 300 to 400 rpm at 50°C overnight. The material was cooled to room temperature and transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was then dried in a vacuum oven at 80°C overnight to obtain Mg2(dobpdc) loaded with secondary alcohol functionalized amine. The material was digested using 1 H NMR was used to determine the initial and final loading amounts after annealing.

[0449] Example B19. Synthesis of GE317-PSM.

[0450] For post-synthetic modification, a molecule having the formula Mg2(dobpdc)(spermine) was used. 1.02 GE5-A369#0. A 20 mL scintillation vial was charged with 0.200 g (0.97 mmol based on spermine) of GE5-A369#0 dispersed in 5 mL of hexane. Then, 2 equivalents of 1,2-butylene oxide (0.140 g, 0.169 mL, 1.94 mmol) and 1 equivalent of EtOH (56 μL) were added to the vial. The slurry was then placed on a hot plate and stirred at 300 to 400 rpm at 50°C overnight. The material was cooled to room temperature and transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was then dried in a vacuum oven at 80°C overnight to obtain 0.180 g of GE317-PSM (Mg2(dobpdc)(0.52EB:spermine) 1.04 ).

[0451] Example B20. Synthesis of GE319-PSM.

[0452] For post-synthetic modification, a molecule having the formula Mg2(dobpdc)(spermine) was used. 1.02GE5-A369#0. A 20 mL scintillation vial was charged with 0.200 g (0.97 mmol based on spermine) of GE5-A369#0 dispersed in 5 mL of hexane. Then, 2 equivalents of 2,2,2-trifluoroethyl)oxirane (0.2446 g, 0.191 mL, 1.94 mmol) and 1 equivalent of EtOH (56 μL) were added to the vial. The slurry was then placed on a hot plate and stirred at 300 to 400 rpm at 50°C overnight. The material was cooled to room temperature and transferred to a conical tube. The material was spun down at 4000 rpm for 2 minutes, the solvent was decanted, and the sample was then dried in a vacuum oven at 80°C overnight to obtain 0.265 g of GE319-PSM (Mg2(dobpdc)(0.51TFEO:spermine) 1.01 ).

[0453] Synthesis of non-MOF adsorbents

[0454] Example C1. General procedure for the synthesis of amine-functionalized γ-Al 2 O 3 : Amine loading by physical adsorption impregnation.

[0455] Prior to synthesis, γ-Al2O3 was thermally activated under vacuum at 120°C to remove physically adsorbed water. Afterward, the desired amount of amine was dissolved in MeOH and added to the γ-Al2O3. The reaction mixture was stirred at room temperature overnight. The solvent was then removed by applying a slow vacuum on a rotary evaporator. The resulting residue was further dried under vacuum at 100°C to yield the amine-loaded γ-Al2O3 material.

[0456] Example C2. Synthesis of GE320-184A (alumina functionalized with spermine by impregnation).

[0457] In a 20 ml scintillation vial, preactivated γ-Al2O3 (200 mg) was added. In a separate vial, spermine (50% by weight, 200 mg relative to γ-Al2O3) was dissolved in 3 ml of MeOH and then added to the γ-Al2O3. The slurry was then stirred at 370 rpm at room temperature overnight. Afterwards, the solvent was removed by applying a slow vacuum in a rotary evaporator. The resulting residue was then further dried under vacuum at 100°C to obtain GE320-184A.

[0458] Example C3. Synthesis of GE321-184B (alumina functionalized with -OH-containing spermine by impregnation).

[0459] In a 20ml scintillation vial, γ-Al O (200mg) was added. In a separate vial, 0.25EB of spermine (50% by weight, 235mg relative to γ-Al O) was dissolved in 3ml of MeOH and then added to the γ-Al O. The slurry was then stirred at 370rpm at room temperature overnight. After this, the solvent was removed by applying a slow vacuum in a rotary evaporator. The resulting residue was then further dried under vacuum at 100°C to obtain GE321-184B.

[0460] The reaction scheme is Figure 14 Shown in.

[0461] Example C4. Synthesis of (3-glycidyloxypropyl)trimethoxysilane-modified γ-Al2O3: for covalent grafting of amines

[0462] (3-Glycidyloxypropyl)trimethoxysilane (GLYMO) was dissolved in toluene or ethanol / water / acetic acid (pH about 4) solvent mixture. The preactivated γ-Al2O3 sample was added to the GLYMO solution and heated with stirring at 90°C (toluene) or 40°C (ethanol / water / acetic acid) overnight. Thereafter, the reaction mixture was centrifuged and the residue was washed twice with hexane. The resulting product was further dried under vacuum at 90°C to obtain GLYMO-functionalized γ-Al2O3 ( Figure 14 Thermogravimetric analysis (TGA) was used to characterize the extent of GLYMO grafting ( Figure 15 ).

[0463] Example C5. Synthesis of SG1-177 (GLYMO functionalization in toluene).

[0464] In a 250 ml three-necked round-bottom flask, GLYMO (500 mg) was added, followed by 100 ml of toluene. A pre-activated γ-Al2O3 sample (500 mg) was added to the GLYMO solution and heated at 90°C overnight. Thereafter, the reaction mixture was centrifuged to remove the toluene, and the residue was washed twice with hexane to remove physically adsorbed GLYMO. The resulting residue was further dried under vacuum at 90°C to obtain GLYMO-functionalized γ-Al2O3 ( Figure 14 and Figure 15 ).

[0465] Example C6. Synthesis of GE323-184C (0.25EB: spermine-functionalized GLYMO grafted γ-Al2O3).

[0466] SG1-177 (200 mg) was added to a 20 ml scintillation vial. In a separate vial, 0.25 EB of spermine (50% by weight relative to SG1-177, 237 mg) was dissolved in 3 ml of MeOH and then added to the γ-Al2O3. The slurry was then stirred at 370 rpm at room temperature overnight. Thereafter, the solvent was removed by applying a slow vacuum on a rotary evaporator. The resulting residue was then further dried under vacuum at 100°C to yield GE323-184C.

[0467] The thermal stability of three amine-functionalized γ-Al2O3 adsorbents was investigated using TGA. Figure 16 The thermal stability of spermine attachment can be enhanced by using -OH-containing spermine modified with 1,2-butylene oxide and further grafted with GLYMO.

[0468] Example C7. Single-pot synthesis of (3-glycidyloxypropyl)trimethoxysilane-modified γ-Al2O3: for covalent grafting of amines.

[0469] To prevent crosslinking between partially hydrolyzed GLYMO and the amine before adding the support material, a single-pot reaction was performed by sequentially adding the individual components. In a 20 ml glass scintillation vial, spermine (200 mg, 0.988 mmol) and GLYMO (234 mg, 0.988 mmol) were dissolved in 3 ml of methanol. The reaction mixture was stirred at room temperature for 30 minutes. Thereafter, preactivated γ-Al2O3 (200 mg) was added to the reaction mixture, and the combined mixture was stirred at room temperature overnight. After the reaction, the MeOH was removed under slow vacuum on a rotary evaporator. The resulting residue was further dried under vacuum at 100°C for 12 hours to yield GE324-1A. Figure 17 Shown are the TGA traces of γ-Al2O3 and one-pot synthesized γ-Al2O3 modified with GLYMO and further functionalized with spermine.

[0470] Testing and characterization.

[0471] Example D1. General testing procedures.

[0472] The performance of CO2 and H2O adsorption was studied using a Dynamic Vapor Sorption Analyzer (DVS) gravimetric method. In the experiments presented in this disclosure, the gas and vapor used were CO2 and water, respectively. The DVS vacuum analyzer is designed to accurately measure the change in mass of a sample when it adsorbs precisely controlled concentrations of water and / or gas molecules. The sample is placed in a sample pan suspended from a microbalance (an empty pan is usually hung on the other side of the microbalance as a "reference"). The DVS vacuum controls and measures both the inlet and outlet flow rates of the adsorbate while recording the change in sample mass. The main instrument is a microbalance (UltraBalance TM ) is housed in a precisely temperature-controlled enclosure called an incubator. This ensures a highly stable instrument baseline and accurate control of vapor generation at the experimental temperature.

[0473] DVS gravimetric determination allows precise measurement of the isotherms of pure H2O and pure CO2. For wet CO2 adsorption, a double cycle sequential adsorption test protocol was developed. At the beginning of each test, the adsorbent material of interest was heated at 120 °C and below 10 - 5 The adsorption of water was carried out under a vacuum of 100 mbar for 60 minutes and then subjected to an activation (or regeneration) step. At a given temperature, a set partial pressure of water was introduced under vacuum in the absence of a carrier gas. The weight of the sample was measured directly and continuously using a Surface Measurement Systems ultraprecision microbalance with a resolution of 0.1 μg. All adsorption measurements in this disclosure were performed using a mass balance mode in which the mass balance standard was set to mass change per minute (dm / dt<0.0035). When water adsorption reached equilibrium, CO2 gas was introduced with a preset partial pressure target. The CO2 partial pressure can be adjusted to reflect the application conditions, i.e., 400 vppm for direct air capture (DAC) or 4.5% by volume for post combustion capture (PCC).

[0474] CO2 and HO adsorption performance can also be studied using a custom-made penetration test rig. This test rig features a sample chamber that holds the test sample in powder or coating form, and separate, calibrated temperature, CO2, and relative humidity (RH) sensors located at both the gas inlet before and the gas outlet after the sample chamber. The test rig measures individual breakthrough curves for CO2 and HO under dry or wet CO2 conditions with a preset RH level. The absorption can be calculated by integrating the breakthrough curves over time.

[0475] The CO2 absorption capacity or capacity is expressed as grams of CO2 absorbed per gram of adsorbent (gCO2 / g adsorbent). The CO2 absorption capacity can generally be considered to increase exponentially over time, which can be expressed as where Q maxand Q (t) are the equilibrium absorption amount and the absorption amount at a given adsorption time t (min), respectively. k is the characteristic of exponential growth, and its unit is 1 / min.

[0476] Mathematically, 1 / k in min is equal to reaching Q max In this work, 1 / k, which is more intuitive than k, is used to compare the kinetics or rate of CO2 absorption, that is, the smaller 1 / k is, the faster the CO2 absorption kinetics is.

[0477] Example D2. Water Adsorption Using Exemplary MOF-Based Adsorbents Functionalized with -OH-Containing Amines.

[0478] The water isotherms of some exemplary adsorbents functionalized with -OH-containing amines measured using DVS gravimetry at 25°C are Figures 18 to 26 The water uptake is expressed as a mass ratio, i.e., grams of H2O adsorbed per gram of adsorbent (gH2O / g adsorbent), and as a number ratio per amine functional group, i.e., the number of H2O molecules adsorbed per amine group, measured at 25°C and 50% relative humidity, and is summarized in Table 4.

[0479] Table 4. Water uptake of exemplary adsorbents, including preloaded modified (PLM) and post-synthesis modified (PSM) adsorbents, measured at 25°C and 50% relative humidity.

[0480]

[0481]

[0482] Regardless of PLM or PSM, the incorporation of -OH groups leads to many unexpected consequences, which are summarized as follows.

[0483] First, the amount of H2O absorption under fixed conditions (such as 50% relative humidity) can be reduced by incorporating -OH groups. This can be achieved by varying the length of the fatty component, such as 1,2-butylene oxide versus 1,2-octane oxide, using fluorinated reagents such as 2,2,2-(trifluoroethyl)ethylene oxide (TFEO), or varying the degree of incorporation (Tables 4 and Figures 18 to 25 ), or by modifying with oxetane to adjust the degree of reduction in H2O absorption ( Figure 26 ).

[0484] Second, the average number of H2O adsorbed per amine group can be adjusted or significantly reduced by incorporating -OH groups. This can be achieved by varying the length of the aliphatic component, such as 1,2-butylene oxide versus 1,2-octane oxide, using fluorinated reagents such as 2,2,2-(trifluoroethyl)ethylene oxide (TFEO), or varying the degree of incorporation (Tables 4 and Figures 18 to 25), to adjust the reduction degree of H2O adsorbed by each amine group.

[0485] Third, the shape of the water isotherm can be tuned by varying the reactants, the degree of incorporation, and the -OH content ( Figures 18 to 26 MOF-274 based adsorbents functionalized with pristine amines that do not contain any -OH groups tend to have type II or type IV isotherms as defined by IUPAC ( Figure 27 ), which has a clear region transitioning from monolayer uptake of HO to multilayer uptake of HO or even condensation. This transition region becomes less pronounced for adsorbents functionalized with amines containing -OH groups. Adsorbents with high -OH content exhibit water isotherms that are more like Type III than Type II or IV.

[0486] Example D3. Water adsorption using exemplary non-MOF-based adsorbents functionalized with -OH-containing amines.

[0487] The water isotherms of some exemplary non-MOF based adsorbents functionalized with -OH containing amines measured using DVS gravimetry at 25 °C are Figures 28 to 30 Shown in.

[0488] Example D4. Dry CO2 adsorption using exemplary MOF-based adsorbents functionalized with -OH-containing amines.

[0489] The dry CO2 isotherm measured at 25 °C using DVS gravimetry for an exemplary MOF-based adsorbent functionalized with -OH-containing amines is Figures 32 to 37 The CO2 absorption is expressed as a mass ratio, i.e., grams of CO2 absorbed per gram of adsorbent (gCO2 / g adsorbent), and as a CO2 number ratio per amine functional group, i.e., the average number of CO2 molecules per amine group measured at 25°C. The results are summarized in Table 5.

[0490] Table 5. Dry CO2 absorption of exemplary adsorbents measured at 25°C and 4 mBar and 10 mBar CO2 pressures.

[0491]

[0492] The incorporation of -OH groups led to a number of unexpected consequences, which are summarized below.

[0493] First, the presence of -OH groups can increase the dry CO2 absorption at low CO2 pressures relative to the corresponding amines without any -OH groups ( Figures 31 to 37 and Table 5 ).

[0494] Second, the degree of enhancement can be adjusted by varying the reactants or varying the degree of incorporation of -OH groups. When epoxide is incorporated at high levels, the enhancement becomes less pronounced. Without being bound by any particular theory, it is believed that this reduced significance is due to the addition of additional mass from the ring-opening reaction and increased steric effects due to the increased size of the amine.

[0495] Third, the shape of the dry CO2 isotherm can be tuned by varying the reactants, the degree of incorporation, and the -OH content. For example, the adsorbent functionalized with pristine exhibits a step-like isotherm, showing a rapid transition between 1 mBar and 10 mBar CO2 partial pressures ( Figures 32 to 33 ). For adsorbents functionalized with spermine containing -OH groups, this step becomes less pronounced or even disappears.

[0496] Example D5. Dry CO2 adsorption using an exemplary non-MOF-based adsorbent functionalized with an -OH-containing amine.

[0497] The dry CO2 isotherms measured at 25 °C using DVS gravimetry for spermine and for the exemplary non-MOF based adsorbent functionalized with -OH-containing spermine are Figures 38 to 39 Shown in.

[0498] remove Figure 16 In addition to the enhanced thermal stability shown in , the presence of -OH groups in GE321-184B significantly enhanced the dry CO2 absorption at low CO2 pressure relative to the control without any -OH groups (GE320-184A). Figures 38 to 39 ).

[0499] Example D6. Desorption residue of exemplary adsorbent material.

[0500] The dry CO2 absorption at 120°C and 100 mBar and 400 mBar CO2 partial pressures can be used to evaluate the desorption residue of each material. The incorporation of -OH groups can adjust the desorption residue at 100 mBar and 400 mBar CO2 pressures relative to the two comparative examples without any -OH groups (Table 6).

[0501] Table 6. Dry CO 2 uptake of exemplary adsorbents, including preloaded modified (PLM) and post-synthesis modified (PSM) adsorbents, measured at 120° C. and 100 mBar and 400 mBar CO 2 pressures.

[0502]

[0503]

[0504] Example D7. Measuring wet CO 2 adsorption of exemplary adsorbent materials using a breakthrough test setup.

[0505] Table 7 shows some exemplary adsorbent materials and their adsorption properties, which were measured using a breakthrough test setup under DAC-relevant co-adsorption conditions (25° C., 50% RH, and 400 vppm CO 2 ).

[0506] Table 7. Exemplary adsorbent materials and their adsorption performance under DAC-relevant co-adsorption conditions, including preloaded modified (PLM) adsorbents and post-synthesis modified (PSM) adsorbents.

[0507]

[0508]

[0509] Coatings using amine-functionalized adsorbents.

[0510] Example E1. General procedure for preparing coatings using amine-functionalized adsorbents.

[0511] The functionalized adsorbent material can be in any form, including but not limited to a powder, a composite material mixed with a binder, a film or coating, a packed bed, a column, and the like. In one embodiment, the functionalized adsorbent is present as a film or coating that also includes at least one binder. In another embodiment, the functionalized adsorbent is present as a film or coating that also includes at least one polymeric binder and at least one additive, including but not limited to clay particles, silica particles, alumina particles, and the like. In another embodiment, the functionalized adsorbent is present as a film or coating prepared using an organic solvent, including but not limited to xylene, p-xylene, o-xylene, ketones, ethanol, isopropanol, and the like. In another embodiment, the functionalized adsorbent is present as a film or coating prepared using water.

[0512] According to a typical procedure, a coating of an adsorbent-containing membrane can be prepared by the following steps: generating a slurry formulation comprising a solvent, a functionalized adsorbent, and a binder; optionally incorporating additional additives as needed to improve the slurry rheology and coating quality; applying the slurry to a substrate by a coating technique; drying the slurry to remove the solvent; and then optionally curing the slurry by heating, ultraviolet light, or the like.

[0513] The solvent may be an aqueous solvent or an organic solvent, or a mixture of an aqueous solvent and an organic solvent in any suitable ratio.

[0514] The binder may generally be a polymer that crosslinks upon curing, or include a precursor to the polymer (eg, a mixture of monomers, etc.).

[0515] The additive needs to be compatible with the solvent and the functionalized sorbent to facilitate attachment of the sorbent particles and uniform dispersion through the solvent.

[0516] Any suitable coating technique may be used, such as, but not limited to, spray coating, dip coating, flow coating, spin coating, drop coating, and the like.

[0517] Example E2. General procedure for water immersion test.

[0518] To a 15 mL Falcon tube, 1 mL of deionized water was added, along with 50 mg of adsorbent. The tube was sonicated for 5 minutes and then soaked for 30 minutes. The tube was centrifuged, decanted, and then dried in a vacuum oven at 120°C overnight. The material was digested using 1 H NMR was used to determine the loading after the leaching test. The change in amine loading was defined as the amine resistance to water immersion.

[0519] Example E3. Exemplary GE314 coating using an organic solvent.

[0520] Film samples of GE314 were prepared according to the following procedure. First, 0.05 g of Butvar B98, a binder, was dissolved in 2.5 g of ethanol. Then, 0.05 g of clay particles were added to the solution and stirred for 15 minutes. Next, 1 g of GE314 was added, and the slurry was vortexed for several minutes before being coated onto a 2-inch x 2-inch aluminum coupon. The coated sample was air-dried in a fume hood for 1 hour, followed by drying in a 90°C oven for 1 hour.

[0521] Figure 40 Figure 3 shows the CO2 and H2O uptake over time by the GE314 membrane. Under the test conditions, the CO2 adsorption kinetics (1 / k) was 33.8 min. The rapid kinetics were due in part to the use of small MOF particles with a D50 of 0.24 μm.

[0522] Example E4. Water immersion resistance.

[0523] Amine-functionalized adsorbent materials typically experience amine loss upon contact with liquid water. Improved tolerance of adsorbents to liquid water is desirable for practical use and applications.

[0524] In a CO2 capture device, the adsorbent material may be in any form, including but not limited to powders, composite materials mixed with binder materials, membranes, coatings, packed beds, and columns, etc. In some embodiments, the adsorbent is present as a coating on a substrate or contactor. The adsorbent coating may be formed by applying a preformed slurry of the adsorbent material with a binder and additives (as needed) in a solvent to a substrate. Water-based slurry or coating procedures are preferred over solvent-based slurry or coating procedures because the volatile organic compounds (VOCs) are zero or reduced, which requires the adsorbent material to tolerate liquid water. Additionally, as Figures 19 to 26 As shown, amine-functionalized adsorbents can exhibit Type IV water isotherms, indicating the potential for water condensation at high relative humidity. In principle, increased tolerance of adsorbent materials to liquid water can reduce potential degradation, amine loss, or leaching due to condensed water when the adsorbent is exposed to high humidity environments.

[0525] The adsorbent materials were evaluated for their tolerance to liquid water following the general procedure for water soaking tests. Table 8 shows the results of water soaking experiments for some exemplary adsorbent materials. The extent of amine loss due to water soaking can be adjusted by varying the reactant, the degree of incorporation, and the -OH content. For example, modification of spermine with TFEO significantly reduced amine loss upon water soaking, from 40.2% for the adsorbent functionalized with pristine spermine to 8.9% (GE319-PSM).

[0526] Another useful method for assessing solubility in water is to use the logP value, which is the logarithm (base 10) of the partition coefficient (P), where the partition coefficient is defined as the ratio of the organic (oil) phase concentration of a material to the aqueous phase concentration. LogP is widely used in the pharmaceutical and medical industries to help identify candidate drugs suitable for oral administration. LogP values ​​can be measured empirically or calculated using a number of software packages (e.g., ALOGPS2.1 used in this disclosure). Table 9 shows the LogP values ​​of some exemplary functionalized adsorbents versus the change in amine due to water immersion. Adsorbents functionalized with amines having larger positive LogP values ​​tend to have less amine loss.

[0527] Table 8. Variation of amine loading in water soak tests for exemplary adsorbent materials, including preloaded modified (PLM) and post-synthesis modified (PSM) adsorbents.

[0528]

[0529]

[0530] Table 9. Change in amine loading versus calculated LogP for exemplary adsorbent materials during water soak testing, including preloaded modified (PLM) and post-synthesis modified (PSM) adsorbents.

[0531]

[0532] Example E5. Exemplary coating of an amine-functionalized adsorbent using an aqueous formulation.

[0533] Membrane samples with amine-functionalized adsorbents that do not contain -OH groups were prepared using the following aqueous formulation procedure and a water-based epoxy binder. First, 0.2 g of Westcoat EC epoxy binder solution (46% solids) was added to 2.5 g of water. The mixture was vortexed for 2 minutes, and then 0.5 g of adsorbent was added. The slurry was vortexed and sonicated for 10 minutes before being coated onto 1 inch x 1 inch aluminum coupons. The coated coupons were air-dried on the bench for 24 hours to self-cure, and then dried in a 90°C oven for 1 hour. The amine content in the membrane was determined using 1H NMR as described above. The amine loading present in the final coating and its corresponding change as a result of the aqueous formulation process are summarized in Table 10. The amine loading of the original amine (such as spermine) decreased by 24.5%, while the amine loading of both the PLM-modified amine and the PSM-modified amine containing -OH groups showed almost no change.

[0534] Table 10. Amine loadings of exemplary adsorbents in epoxy-based waterborne coatings, including pre-loaded modified (PLM) and post-synthesis modified (PSM) adsorbents.

[0535]

[0536] Example E6. Desorption Temperature.

[0537] The CO2 desorption properties were studied by monitoring the CO2 desorption signal while gradually increasing the test bench temperature ( Figures 41 to 46 For each experiment, the adsorbent was subjected to adsorption to complete equilibrium under DAC relevant conditions (i.e., 25°C, 400 vppm CO2 and 50% RH). Figure 41 As shown, the MOF-based adsorbent functionalized with pure spermine (GE5-A369) exhibited multiple desorption peaks corresponding to desorption temperatures up to 100 °C. Figure 42 ) or 1,2-octane oxide (GE301-A370A) ( Figure 43 ) modified MOF-based adsorbent functionalized with -OH spermine can completely desorb at a reduced temperature of 80 °C. Compared with the original amine ( Figure 44 ), for powder ( Figure 45 ) and membrane ( Figure 46 ) Similar desorption temperature reduction was also observed for these two forms of MOF-based adsorbents functionalized with -OH-containing amines 2-3-2. Summary of the invention.

[0539] Described herein are the significant advantages of functionalizing adsorbents with at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof. Furthermore, the incorporation of -OH groups, whether a PLM or a PSM, leads to many of the unexpected results disclosed herein. The materials and methods disclosed herein are broadly applicable to a wide variety of adsorbents and functionalized ligands.

[0540] definition.

[0541] As used herein, references to “an exemplary embodiment” or “one embodiment” or “some embodiments” of the present disclosure are not intended to be interpreted as excluding the existence of additional embodiments that also incorporate the recited features.

[0542] When introducing elements of the various embodiments disclosed herein, the articles "a," "an," "the," and "said" are intended to mean that there are one or more of the elements. The terms "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0543] Unless otherwise indicated, approximate language as used herein, such as "substantially", "substantially" and "about" indicate that as one of ordinary skill in the art will recognize, the terms so modified may apply only to an approximate degree, rather than an absolute or perfect degree. Therefore, the values ​​modified by one or more terms (such as "about", "approximately" and "substantially") are not limited to the precise values ​​specified. In at least some cases, approximate language may correspond to the precision of the instrument used to measure the value. In addition, unless otherwise indicated, the terms "first", "second" etc. are used only as labels in this article and are not intended to impose order, position or hierarchical requirements on the items to which these terms are related. In addition, for example, a reference to a "second" item does not require or exclude the presence of, for example, a "first" or lower numbered item or a "third" or higher numbered item.

[0544] Unless otherwise indicated, approximate language as used herein, such as "substantially", "substantially" and "about" indicate that as one of ordinary skill in the art will recognize, the terms so modified may apply only to an approximate degree, rather than an absolute or perfect degree. Therefore, the values ​​modified by one or more terms (such as "about", "approximately" and "substantially") are not limited to the precise values ​​specified. In at least some cases, approximate language may correspond to the precision of the instrument used to measure the value. In addition, unless otherwise indicated, the terms "first", "second" etc. are used only as labels in this article and are not intended to impose order, position or hierarchical requirements on the items to which these terms are related. In addition, for example, a reference to a "second" item does not require or exclude the presence of, for example, a "first" or lower numbered item or a "third" or higher numbered item.

[0545] As used herein, the term "isomer" refers to molecules having the same molecular formula but different arrangements of atoms in space. Isomers include structural isomers and stereoisomers. Stereoisomers include (R)- and (S)-enantiomers and cis / trans diastereomers. Each compound disclosed in this disclosure, whether or not a specific isomer is depicted, discloses all individual isomers and every mixture of isomers.

[0546] As used herein, the term "alkyl", whether used alone or in compound words such as "haloalkyl", includes straight or branched chain alkyl groups such as methyl, ethyl, n-propyl and isopropyl, or different butyl, pentyl or hexyl isomers. Alkyl groups defined by a number of carbon atoms, such as C6 alkyl, are understood to have that many carbon atoms, but are not otherwise limited.

[0547] As used herein, the term "heteroalkyl" refers to an alkyl chain in which at least one of the atoms forming the backbone of the chain is other than carbon.

[0548] As used herein, "aminoalkyl" includes N groups substituted with straight or branched chain alkyl groups.

[0549] As used herein, the term "halogen" or "halide", whether used alone or in a compound word such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. In addition, when used in a compound word such as "haloalkyl", the alkyl group may be partially or completely substituted with the same or different halogen atoms. Examples of "haloalkyl" include F3C, ClCH2, CF3CH2 and CF3CCl2. The term "haloalkoxy" and the like are defined similarly to the term "haloalkyl". Examples of "haloalkoxy" include CF3O, CCl3CH2O, F2CHCH2CH2O and CF3CH2O.

[0550] As used herein, the term "heterocycle" refers to a ring in which at least one of the atoms forming the ring backbone is not carbon. Unless otherwise specified, a heterocycle can be saturated, partially unsaturated, or fully unsaturated. When a fully unsaturated heterocycle satisfies Hückel's rule, the ring is also referred to as a "heteroaryl" or aromatic heterocycle. A "saturated heterocycle" refers to a heterocycle containing only single bonds between ring members.

[0551] As used herein, the term "aminosilicone group" includes functional groups containing both an amine group and a siloxane group (also known as a disiloxane group), wherein the siloxane group includes a Si-O-Si linkage.

[0552] Ring-shaped cyclic units can be divided into two categories: alicyclic units and aromatic units. A cyclic unit is any chemical substance that has at least three atoms bonded to each other to form a closed ring structure. Some cyclic units are considered alicyclic because they are both aliphatic and cyclic. Aromatic units are also cyclic compounds with a closed ring structure. However, the key difference between alicyclic units and aromatic units is that aromatic units consist of sp atoms that are incorporated into a planar and conjugated ring system through the incorporation of delocalized π electrons. 2 heterogeneous atoms, while the alicyclic unit consists of sp, sp and t atoms that do not contain delocalized π electrons around the ring. 2 or sp 3 In addition, aromatic units or compounds generally follow Huckel's rule, that is, the total number of π electrons belonging to the cyclic unit or molecule of the ring can be equal to the formula "4N+2", where N can be any integer with a positive value.

[0553] As used herein, the term "polyamine" refers to a chemical compound having at least two amine groups. Thus, polyamines can include diamines, triamines, tetraamines, pentamines, hexamines, and combinations thereof.

[0554] As used herein, the term "hydroxyl unit" refers to an -OH group. The -OH group can be a primary -OH group, wherein the -OH group is bonded to a primary carbon atom to form a primary alcohol; a secondary -OH group, wherein the -OH group is bonded to a secondary carbon atom to form a secondary alcohol; or a tertiary -OH group, wherein the -OH group is bonded to a tertiary carbon atom to form a tertiary alcohol.

[0555] As used herein, the term "carbonyl unit" refers to a C=O group. The C=O group is not limited by surrounding bonds and functional groups and can form part of another functional group. For example, the C=O group can exist as part of an amide group, an aldehyde group, a ketone group, a thiocarboxylic acid group, or a carboxylic acid group.

[0556] 1H NMR spectra are reported in ppm downfield from tetramethylsilane; “s” indicates a singlet, “d” a doublet, “dd” a doublet of a doublet, “ddd” a doublet of a doublet of a doublet, “t” a triplet, “m” a multiplet, and “brs” a broad singlet.

[0557] Although specific features of various embodiments of the present invention may be shown in some drawings and not in others, this is for convenience only. In accordance with the principles of the present invention, any feature of a drawing may be referenced and / or claimed in conjunction with any feature of any other drawing.

[0558] While the invention has been described in terms of various specific embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the claims.

[0559] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.

[0560] It will be readily understood by those skilled in the art that some of the substituents disclosed herein depend on the presence of other substituents and are therefore optional. For example, in Formula AI, when R9 is a direct bond, R1 and R2 are optional substituents that are not present in the compound. Similarly, in Formula AI, when n is 0, in the presence of R9 and R 10 There is a direct bond between R3, R4 and R 11 is an optional substituent that is not present in the compound. The optional nature of a substituent in one embodiment does not limit the presence of a substituent in another embodiment.

[0561] Further aspects of the invention are provided by the subject matter of the following clauses:

[0562] Clause 1. A functionalized adsorbent comprising an adsorbent and at least one functionalized ligand, wherein the functionalized ligand comprises a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0563] Clause 2. The functionalized adsorbent according to the preceding clause, wherein the at least one oxygen-containing unit is selected from the group consisting of primary hydroxyl units, secondary hydroxyl units, tertiary hydroxyl units, and combinations thereof.

[0564] Clause 3. The functionalized adsorbent of any preceding clause, wherein the polyamine comprises at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof.

[0565] Clause 4. The functionalized sorbent of any preceding clause, wherein the polyamine comprises at least one amine selected from the group consisting of diamines, triamines, tetraamines, pentamines, hexamines, heptamines, octamines, and combinations thereof.

[0566] Clause 5. The functionalized adsorbent of any preceding clause, wherein the adsorbent comprises a metal organic framework (MOF).

[0567] Clause 6. The functionalized adsorbent of any preceding clause, wherein the adsorbent comprises a mesoporous oxide support.

[0568] Clause 7. The functionalized adsorbent of any preceding clause, comprising at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit.

[0569] Clause 8. The functionalized adsorbent of any preceding clause, wherein the adsorbent has an aspect ratio of ≥ 0.2.

[0570] Clause 9. The functionalized adsorbent of any preceding clause, wherein the adsorbent has an average particle length of ≤ 3 μm.

[0571] Clause 10. The functionalized adsorbent of any preceding clause, wherein the functionalized adsorbent has a Type II, or Type III, or Type IV isotherm for pure water.

[0572] Clause 11. The functionalized adsorbent according to any preceding clause, wherein the at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of carbonyl units, hydroxyl units, and combinations thereof has a LogP of -1.0 or greater.

[0573] Clause 12. The functionalized adsorbent according to any preceding clause, wherein the adsorbent is in a form selected from the group consisting of a powder, a pellet, a composite, a composite mixed with a binder, a membrane, a coating, an aqueous coating, a packed bed, a column, a monolith, and combinations thereof.

[0574] Clause 13. An adsorbent system comprising the functionalized adsorbent according to any preceding clause.

[0575] Item 14. A method of preparing a functionalized adsorbent. The method comprises: (I) forming a mixture comprising: an adsorbent; at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; optionally at least one functionalized ligand not comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; an optional solvent; and an optional non-solvent; and (II) functionalizing the adsorbent.

[0576] Clause 15. The method of any preceding clause, wherein the solvent comprises an aqueous solvent.

[0577] Clause 16. A method for modifying a functionalized adsorbent, the method comprising: (I) forming a mixture comprising: an adsorbent functionalized with at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; and a reactant; and (II) reacting the reactant with the adsorbent functionalized with at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof to produce an adsorbent functionalized with at least one functionalized ligand that includes a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof.

[0578] Clause 17. The method of any preceding clause, wherein the reactant comprises at least one functional group selected from the group consisting of an epoxy group, an epoxy group comprising a fluorine atom, a 3-membered ring epoxy group, a monoepoxy group, a diepoxy group, an oxetane group, a 4-membered ring oxetane group, and combinations thereof.

[0579] Clause 18. A method of capturing at least one gas. The method comprises: (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising a polyamine comprising at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; and (II) capturing an amount of the at least one gas with the functionalized adsorbent.

[0580] Clause 19. A method according to any preceding clause, wherein the gas source is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0581] Clause 20. The method according to any preceding clause, wherein the at least one gas is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0582] Clause 21. A method of collecting at least one gas from a gas source, the method comprising:

[0583] capturing the at least one gas according to a method according to any preceding clause, and

[0584] (III) releasing the at least one gas from the functionalized adsorbent.

Claims

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

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

3. The functionalized adsorbent according to any preceding claim, wherein the polyamine comprises at least one amine selected from the group consisting of diamines, triamines, tetraamines, pentamines, hexamines, heptamines, octamines, and combinations thereof.

4. The functionalized adsorbent according to any preceding claim, wherein the adsorbent comprises a metal organic framework (MOF).

5. The functionalized adsorbent according to any preceding claim, wherein the adsorbent comprises a mesoporous oxide support.

6. A functionalized adsorbent according to any preceding claim, comprising at least one functionalized ligand which does not comprise a polyamine containing at least one oxygen-containing unit.

7. The functionalized adsorbent according to any preceding claim, wherein the adsorbent (a) has an aspect ratio of ≥ 0.2; and / or (b) The adsorbent has an average particle length of ≤ 3 μm.

8. A functionalized adsorbent according to any preceding claim, wherein (a) the functionalized adsorbent has a Type II, Type III, or Type IV isotherm for pure water; and / or (b) the at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof has a LogP of -1.0 or greater; and / or (c) The adsorbent is in a form selected from the group consisting of powder, pellets, composite materials, composite materials mixed with a binder, membranes, coatings, packed beds, columns, monoliths, and combinations thereof.

9. An adsorbent system comprising the functionalized adsorbent according to any one of claims 1 to 8.

10. A method for preparing a functionalized adsorbent, the method comprising: (I) forming a mixture comprising: Adsorbent; at least one functionalized ligand comprising a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; optionally at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; optional solvent; and optional non-solvent; and (II) functionalizing the adsorbent.

11. A method for modifying a functionalized adsorbent, the method comprising: (I) forming a mixture comprising: an adsorbent functionalized with at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and combinations thereof; and reactants; and (II) reacting the reactant with the adsorbent functionalized with at least one functionalized ligand that does not include a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof to produce an adsorbent functionalized with at least one functionalized ligand that includes a polyamine containing at least one oxygen-containing unit selected from the group consisting of a carbonyl unit, a hydroxyl unit, and a combination thereof.

12. The method of claim 11, wherein the reactant comprises at least one functional group selected from the group consisting of an epoxy group, an epoxy group including a fluorine atom, a 3-membered ring epoxy group, a monoepoxy group, a diepoxy group, an oxetane group, a 4-membered ring oxetane group, and combinations thereof.

13. A method of capturing at least one gas, the method comprising: (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent is according to any one of claims 1 to 8; and (II) capturing a quantity of the at least one gas with the functionalized adsorbent.

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

15. A method of collecting at least one gas from a gas source, the method comprising: The method of claim 14(a) capturing the at least one gas, and (III) releasing the at least one gas from the functionalized adsorbent.

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