Adsorbent compositions, systems, and methods

Abstract

Described herein are adsorbents functionalized with ligands having amino silicone functional groups, methods of making the same, and methods of using the same. Also described herein are methods of making aminoalkyl-substituted disiloxanes and aminoalkyl-substituted disiloxanes produced by the methods. Also described herein are systems that facilitate optimized adsorption and desorption of carbon dioxide gas by an adsorbent bed using water-managed and functionalized adsorbents. Also described herein are systems and methods for modeling predicted performance of adsorbents in a post-combustion carbon capture system and for operating the post-combustion carbon capture system using one or more expected adsorbents based on carbon capture performance values determined by the modeling. Described herein are adsorbents functionalized with polyamines having cyclic units, methods of making the same, and methods of using the same.

Description

[0001] Related Applications

[0002] This application claims priority to U.S. Provisional Application Serial No. 63 / 386,231, filed on December 6, 2022, and also claims priority to International Application PCT / US2023 / 021542, filed on May 9, 2023, and also claims priority to International Application PCT / US2023 / 023746, filed on May 26, 2023, and also claims priority to U.S. Provisional Application Serial No. 63 / 592,783, filed on October 24, 2023, and also claims priority to U.S. Provisional Application Serial No. 63 / 596,069, filed on November 3, 2023, the contents of which are hereby incorporated by reference in their entirety. Technical Field

[0003] The present disclosure generally relates to adsorbents functionalized with ligands having aminoorganosilicon functional groups, methods for their preparation, and methods for their use. The present disclosure also generally relates to methods for preparing aminoalkyl-substituted disiloxanes and aminoalkyl-substituted disiloxanes produced by such methods. The present disclosure also generally relates to capture systems, and more particularly to systems that use water management and functionalized adsorbents to facilitate optimized adsorption and desorption of carbon dioxide gas in adsorption beds. The present disclosure also generally relates to modeling post-combustion or direct air carbon capture systems, and more particularly to systems and methods for modeling the expected performance of novel adsorbents (particularly metal-organic frameworks) in post-combustion or direct air carbon capture systems and for operating post-combustion or direct air carbon capture systems using one or more expected adsorbents based on carbon capture performance values determined by such modeling. The present disclosure also generally relates to adsorbents functionalized with polyamines having cyclic units, methods for their preparation, and methods for their use. Background Art

[0004] Solid adsorbents can be used for a variety of purposes. For example, they are particularly useful in carbon capture adsorbent systems, such as for point sources of carbon dioxide (CO2), post-combustion carbon capture (PCC), and direct air capture (DAC). Solid adsorbents for carbon capture provide a viable and technically and economically superior alternative to conventional liquid amine-based CO2 capture methods. For example, compared to active liquid amines, solid adsorbents tend to have better adsorption capacity, lower regeneration energy requirements, and reduced system complexity and environmental and safety risks.

[0005] Based on the underlying adsorption mechanisms, there are two types of adsorbent materials. The first type is physical adsorbents, which rely on non-covalent interactions (e.g., van der Waals interactions, dipole-dipole interactions, etc.) to adsorb gaseous substances such as CO2 and H2O. Examples of physical adsorbents include activated carbon, zeolites, and metal-organic frameworks (MOFs). The second type is chemical adsorbents, which adsorb CO2 through reversible chemical reactions and by forming ammonium carbamate, carbamic acid, ammonium carbonate, and / or ammonium bicarbonate. Examples of chemical adsorbents include amine-functionalized silica particles, amine-functionalized polymers and resins, amine-functionalized metal-organic frameworks (MOFs), and amine-functionalized covalent organic frameworks (COFs).

[0006] Due to chemical bonding, chemical adsorbent materials generally have better CO2 adsorption selectivity for interfering substances such as N2, methane, and CO compared to physical adsorbent materials. However, the effectiveness of chemical adsorbent systems may be limited by the compositional nature of the functionalized molecules that undergo the chemisorption and functionalization processes. Therefore, there is a need for functionalized adsorbents containing chemically and thermally stable molecular substances that selectively absorb CO2 with high capacity and fast kinetics.

[0007] Correspondingly, at least some known industrial and power generation methods can result in the generation of gas streams containing pollutants such as in the form of CO2. Therefore, a capture system can be used to facilitate the removal of pollutants from the gas stream before the exhaust stream is released into the atmosphere. For example, a carbon capture system can be used to attempt to capture CO2 and store it underground to reduce the amount of CO2 released into the atmosphere.

[0008] At least some known carbon capture systems can use adsorption beds to capture and release CO2. In some known systems, to improve the adsorption capacity and efficiency of the system, solid adsorbent materials can be used with the adsorption bed to enhance the adsorption and desorption of CO2, as opposed to other known systems that use liquid amine-based CO2 capture methods. However, the effectiveness of chemical adsorbent systems is generally limited by functionalization and detailed operating conditions.

[0009] To facilitate an increase in the amount of CO2 captured, at least some known carbon capture systems use water to improve CO2 capture efficiency. For example, a carbon capture system can use wet conditions to improve CO2 adsorption performance. However, if too much H2O is adsorbed, the interference from H2O molecules may reduce the CO2 adsorption capacity of the chemical adsorbent materials used in the adsorption bed. Therefore, there is a need for a capture system that uses functionalized chemical adsorbents in the presence of water to optimize the efficiency and productivity of carbon dioxide adsorption and desorption.

[0010] Correspondingly, aminoalkyl-substituted disiloxanes can be used for a variety of purposes. For example, they are particularly useful in carbon capture systems or aminoorganosilicon-based products.

[0011] Substituted disiloxanes are generally produced by known reactions. However, the known reactions may be limited in scope and may be ineffective for producing aminoalkyl-substituted disiloxanes. For example, the method described in CN102675596 involves a reaction pathway that is not suitable for aminoalkyl-substituted disiloxanes due to side reactions that preferentially form cyclic products. Similarly, the method described in CN102351893 starts from materials that can only be hydrolyzed into one compound. In addition, some methods, such as those described in Li et al., Thermochimica Acta, 2012, 545, 75, require multi-step reaction pathways and intermediate purification steps, which may require a relatively large number of reaction steps, and / or which may reduce the overall yield and increase the cost and complexity of the method.

[0012] Accordingly, the opportunities for preparing aminoalkyl-substituted disiloxanes are limited. Thus, there is a need for a simplified method for preparing aminoalkyl-substituted disiloxanes.

[0013] Correspondingly, some power plant systems may include a post-combustion carbon capture system configured to capture carbon dioxide (CO2) from the exhaust gas (flue gas) produced. PCC systems can be used to capture CO2 from the exhaust gas produced by power plants, which include, for example, coal-fired systems, gas turbines, and / or boilers. Some types of PCC systems use metal-organic frameworks to facilitate carbon capture. Metal-organic frameworks generally include two main components: an inorganic metal component (commonly referred to as a secondary building unit or SBU) and an organic component (commonly referred to as a linker). A variety of different MOFs have been developed and their capture capacities (e.g., a measure of the effectiveness with which a particular MOF performs in capturing CO2) have been tested. However, there may be millions of combinations of metals, linkers, and other functional groups available for use in MOFs, some of which may produce a greater capture capacity and productivity than existing MOFs, while it is economically infeasible to actually create and study every possible combination of components.

[0014] There is a need for systems and methods for modeling MOF performance using known MOFs in order to predict how other proposed MOFs will perform and to adjust the operation of carbon capture systems using MOFs based on the predicted carbon capture performance.

[0015] The present disclosure addresses these related needs, both individually and jointly. SUMMARY OF THE INVENTION

[0016] In one aspect, a functionalized adsorbent is provided. The functionalized adsorbent comprises an adsorbent and at least one functionalized ligand, the functionalized ligand comprising a polyamine comprising at least one cyclic unit.

[0017] 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 having at least one cyclic unit; optionally at least one functionalized ligand not comprising a polyamine having at least one cyclic unit; optionally a solvent; and optionally a non-solvent; and (II) functionalizing the adsorbent.

[0018] In another aspect, a method for trapping 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 having at least one cyclic unit; and (II) trapping an amount of the at least one gas with the functionalized adsorbent.

[0019] In another aspect, a method for collecting at least one gas is provided. The method comprises: (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising a polyamine having at least one cyclic unit; (II) trapping an amount of the at least one gas with the functionalized adsorbent; and (III) releasing the at least one gas from the functionalized adsorbent. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] 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 drawings, wherein:

[0021] Figure 1 is a schematic diagram of an exemplary capture system according to the present disclosure that can be used to capture CO2;

[0022] Figure 2 is a schematic diagram of an alternative capture system according to the present disclosure that can be used to capture CO2;

[0023] Figure 3 shows an exemplary type of Figure 2 water adsorption isotherm that the capture system according to the present disclosure can have;

[0024] Figure 4 is an exemplary control system schematic according to the present disclosure that can be used with Figure 1 and Figure 2 the capture system of;

[0025] Figure 5Shows the exemplary potential H2O adsorption capacity of adsorbents functionalized with AEAM, spermidine, a first amine hybrid (hybrid compound 1, spermine:AEAM = 0.65:0.35), or a second amine hybrid (hybrid compound 2, spermine:AEAM = 0.32:0.46) measured at 25 °C using dynamic vapor sorption (DVS) gravimetry in accordance with the present disclosure;

[0026] Figure 6 Shows the variation of the exemplary potential H2O adsorption capacity of an adsorbent functionalized with a first amine hybrid (hybrid compound 1, spermine:AEAM = 0.65:0.35) measured at different temperatures using dynamic vapor sorption (DVS) gravimetry with respect to the H2O partial pressure in accordance with the present disclosure;

[0027] Figure 7 Shows the variation of the exemplary potential H2O adsorption capacity of an adsorbent functionalized with a first amine hybrid (hybrid compound 1, spermine:AEAM = 0.65:0.35) measured at different temperatures using dynamic vapor sorption (DVS) gravimetry with respect to the relative humidity in accordance with the present disclosure;

[0028] Figure 8 Shows the variation of the exemplary potential CO2 and H2O adsorption capacities of an adsorbent functionalized with a first amine hybrid (hybrid compound 1, spermine:AEAM = 0.65:0.35) measured at 40 °C using dynamic vapor sorption (DVS) gravimetry with respect to the relative humidity in accordance with the present disclosure;

[0029] Figure 9 Shows the variation of the exemplary potential CO2 adsorption capacity of an adsorbent functionalized with a first amine hybrid (hybrid compound 1, spermine:AEAM = 0.65:0.35) measured at different temperatures using dynamic vapor sorption (DVS) gravimetry with respect to the water pressure in accordance with the present disclosure;

[0030] Figure 10 Shows the variation of the exemplary potential H2O adsorption capacity of an adsorbent functionalized with a first amine hybrid (hybrid compound 1, spermine:AEAM = 0.65:0.35) measured at different temperatures using dynamic vapor sorption (DVS) gravimetry with respect to the water pressure in accordance with the present disclosure;

[0031] Figure 11 Shows the variation of the exemplary potential CO2 adsorption capacity of an adsorbent functionalized with a first amine hybrid (hybrid compound 1, spermine:AEAM = 0.65:0.35) measured at different temperatures using dynamic vapor sorption (DVS) gravimetry with respect to the relative humidity in accordance with the present disclosure;

[0032] Figure 12AShows exemplary potential CO2 adsorption isotherms for an adsorbent functionalized with a first amine hybrid (hybrid compound 1, spermine:AEAM = 0.65:0.35) measured at 40 °C using dynamic vapor sorption (DVS) gravimetry for dry CO2 and wet CO2 with a relative humidity of 30%;

[0033] Figure 12B Shows exemplary CO2 adsorption and H2O isotherms for an adsorbent functionalized with hybrid compound 3 (spermine:AEAM = 0.69:0.23) measured using a breakthrough test apparatus with separate CO2 and H2O sensors for dry CO2 and wet CO2 with different relative humidities at 25 °C and a CO2 concentration of 400 ppmv;

[0034] Figure 13 Is an exemplary method flow chart according to the present disclosure;

[0035] Figure 14 Shows an exemplary PCC modeling system according to the present disclosure, which can be used to predict how a specific MOF will perform when capturing carbon dioxide (CO2) from the exhaust gas of a coal-fired power plant;

[0036] Figure 15 Is a chart showing the decline in CO2 adsorption productivity of an exemplary adsorbent (e.g., an exemplary MOF) from a synthetic powder measured under equilibrium conditions to a final film coating on a substrate measured under dynamic conditions according to the present disclosure;

[0037] Figures 16A to 16C Is a flow chart showing an exemplary method according to the present disclosure for analyzing the expected performance of an expected adsorbent in a post-combustion carbon capture system;

[0038] Figure 17 Shows an exemplary correlation matrix according to the present disclosure;

[0039] Figure 18 Shows the 1H NMR analysis of Mg2(dobpdc)1(IPA) according to the present disclosure 1.92 ;

[0040] Figure 19 Is a scanning electron microscope (SEM) image of an exemplary MOF-274 (sample ID#A2111) prepared according to the present disclosure;

[0041] Figure 20 Depicts SEM images of an exemplary MOF-274 prepared using salicylic acid (left) and fluorosalicylic acid (right) as crystal growth inhibitors according to the present disclosure;

[0042] Figure 21Depicts the powder X-ray diffraction (XRD) spectrum of MOF-274 synthesized using 4,4'-biphenol as a crystal growth inhibitor according to the present disclosure, where the input molar ratio of 4,4'-biphenol:H4dobpdc is indicated by an arrow;

[0043] Figure 22 Depicts SEM images of exemplary MOF-274 prepared according to the present disclosure without incorporation (left) and with incorporation of 9.24 wt% 4,4'-biphenyldiol (right);

[0044] Figure 23 Depicts the powder XRD patterns of the crystal growth inhibitor 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC) and MOF-274 synthesized using BPYDC according to the present disclosure, with the input molar ratio of BPYDC:H4dobpdc shown above each line;

[0045] Figure 24 Depicts SEM images of exemplary MOF-274 prepared according to the present disclosure using BPYDC as a crystal growth inhibitor (incorporation amounts of 0.13 wt%, 2.29 wt%, and 24.78 wt%);

[0046] Figure 25 Depicts the powder XRD patterns of the crystal growth inhibitor 2,2'-bipyridine-5,5'-dimethanol (BPYDM) and MOF-274 synthesized using BPYDM according to the present disclosure, with the input molar ratio of BPYDM:H4dobpdc shown above each line;

[0047] Figure 26 Depicts SEM images of exemplary MOF-274 prepared according to the present disclosure using BPYDM as a crystal growth inhibitor (incorporation amounts of 1.17 wt%, 3.43 wt%, and 6.80 wt%);

[0048] Figure 27 Depicts the chemical structures of spermine and exemplary aminoorganosilanes according to the present disclosure;

[0049] Figure 28 Depicts SEM images of a comparative example (Comparative - 3) of an adsorbent (GE115 - A259) of MOF-274 (ID#: A21) synthesized according to a conventional procedure;

[0050] Figure 29 Depicts SEM images of an inventive example of an adsorbent (GE115 - A272) (Inventive - 4) according to the present disclosure comprising mortar and ground MOF-274 (ID# A21);

[0051] Figure 30Depicts a SEM image of an inventive embodiment of an adsorbent (GE115 - A279) (invention - 5) including mechanically ground MOF - 274 according to the present disclosure;

[0052] Figure 31 Is a graph depicting the variation of CO₂ absorption of adsorbents including pure spermine, pure APAP, and mixtures of different ratios with spermine loading measured using a breakthrough test apparatus at 25 °C, 50% RH, and 400 ppmv CO₂ according to the present disclosure;

[0053] Figure 32 Is a graph depicting the variation of CO₂ absorption of adsorbents including pure spermine, pure APAP, and mixtures of different ratios with spermine loading measured using dynamic vapor sorption (DVS) gravimetry at 120 °C and 100 mBar CO₂ partial pressure according to the present disclosure;

[0054] Figure 33 A graph depicting the variation of CO₂ adsorption working capacity of adsorbents including pure spermine, pure APAP, and mixtures of different ratios with spermine loading according to the present disclosure.

[0055] Figure 34 Is an exemplary method flowchart according to the present disclosure;

[0056] Figure 35 Is an exemplary method flowchart according to the present disclosure;

[0057] Figure 36 Is an exemplary method flowchart according to the present disclosure;

[0058] Figure 37 Is an exemplary method flowchart according to the present disclosure;

[0059] Figure 38 Shows 1 ¹H NMR analysis of GE181 - A224 according to the present disclosure;

[0060] Figure 39 Shows 1 ¹H NMR analysis of GE182 - A225 according to the present disclosure;

[0061] Figure 40 Shows 1 ¹H NMR analysis of BEDCH in 600 μL of MeOD according to the present disclosure. 1 ¹H NMR (MeOD) δ 2.76 (t, 4H), 2.65 (t, 4H), 2.46 (d, 4H), 1.88 (d, 4H), 1.49 (broad m, 2H), 0.99 (m, 4H);

[0062] Figure 41 Shows the 1 1H NMR analysis (DMSO-d6, D2O) δ 7.85 (dd, 2H), 7.69 (m, 5H), 6.98 (dd, 2H), 1.74 - 1.59 (m, 6H), 0.91 (m, 4H);

[0063] Figure 42 Depicts the SEM image of an exemplary mechanically ground MOF-274 according to the present disclosure;

[0064] Figure 43 Shows the 1 1H NMR analysis;

[0065] Figure 44 Shows the 1 1H NMR analysis of Ph-3-ED in 600 μL of D2O according to the present disclosure, 1 1H NMR (D2O) δ 7.25 (s, 1H), 3.78 (s, 6H), 2.76 (t, 6H), 2.66 (t, 6H);

[0066] Figure 45 Shows the 1 1H NMR analysis performed on GE223-67A after digestion with 20 μL of 20% DCl / D2O, 200 μL of D2O, and 600 μL of DMSO-d6 according to the present disclosure, 1 1H NMR (DMSO-d 6, D2O) δ 7.85 (dd, 2H), 7.69 (m, 5H), 6.98 (dd, 2H), 4.22 (s, 6H), 3.29 (t, 6H), 3.20 (t, 6H);

[0067] Figure 46 Shows the H2O isotherm of GE181 (1,3-cyclohexanediamine) at 25 °C measured using DVS gravimetry according to the present disclosure;

[0068] Figure 47 Shows the H2O isotherm of GE182 (trans-1,4-cyclohexanediamine) at 25 °C measured using DVS gravimetry according to the present disclosure;

[0069] Figure 48 Shows the H2O isotherm of GE183 (1,3-benzenedimethanamine) at 25 °C measured using DVS gravimetry according to the present disclosure;

[0070] Figure 49Shows the H2O isotherm of GE186 (1,4-benzenedimethanamine) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0071] Figure 50 Shows the H2O isotherm of GE195 (furan-2,5-diamine) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0072] Figure 51 Shows the H2O isotherm of GE193 (1,4-bis(aminomethyl)cyclohexane) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0073] Figure 52 Shows the H2O isotherm of GE205 (4-(aminomethyl)cyclohexanamine) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0074] Figure 53 Shows the H2O isotherm of GE206 (1,3-bis(aminomethyl)cyclohexane) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0075] Figure 54 Shows the H2O isotherm of GE214 (bis(aminomethyl)norbornane) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0076] Figure 55 Shows the H2O isotherm of GE216 (4,4'-methylenebis(2-methylcyclohexylamine)) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0077] Figure 56 Shows the H2O isotherm of GE217 (tetrafluoroterephthalamide) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0078] Figure 57 Shows the H2O isotherm of GE218 (racemic-(1r,4r)-N1,N4-dimethylcyclohexane-1,4-diamine) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0079] Figure 58 Shows the H2O isotherm of GE220 (1,3,5-benzenetricamine) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0080] Figure 59Shows the H2O isotherm of GE221 (1,3,5-cyclohexanetriyltrimethylamine) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0081] Figure 60 Shows the H2O isotherm of GE223 (Ph-3-ED) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0082] Figure 61 Shows the H2O isotherm of GE225 (methyl({4-[(methylamino)methyl]phenyl}methyl)amine) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0083] Figure 62 Shows the H2O isotherm of GE226 (a mixture of 1,4-benzenedimethanamine and 1,3,5-benzenetriclamine) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0084] Figure 63 Shows the H2O isotherm of GE227 (a mixture of 1,4-benzenedimethanamine and 1,3,5-benzenetriclamine) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0085] Figure 64 Shows the H2O isotherm of GE230 (4-(2-aminoethyl)aniline) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0086] Figure 65 Shows the H2O isotherm of GE234 (a mixture of spermine and 1,4-bis-(aminomethyl)-cyclohexane) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0087] Figure 66 Shows the H2O isotherm of GE235 (a mixture of spermine and 1,4-bis-(aminomethyl)-cyclohexane) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0088] Figure 67 Shows the H2O isotherm of GE238 (1,4-bis-(aminomethyl)-cyclohexane) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0089] Figure 68 Shows the H2O isotherm of GE240 (4-(2-aminoethyl)cyclohexanamine) measured at 25 °C using DVS gravimetry according to the present disclosure;

[0090] Figure 69Shows the H2O isotherm of GE241 (1,3-bis-(aminomethyl)cyclohexane) measured using DVS gravimetry at 25 °C according to the present disclosure;

[0091] Figure 70 Shows the H2O isotherm of GE248 (N1,N4-bis(2-aminoethyl)-1,4-cyclohexanedimethanamine, BEDCH) measured using DVS gravimetry at 25 °C according to the present disclosure;

[0092] Figure 71 Shows the CO2 isotherm of GE181 (1,3-cyclohexanediamine) measured using DVS gravimetry at 25 °C according to the present disclosure;

[0093] Figure 72 Shows the CO2 isotherm of GE182 (trans-1,4-cyclohexanediamine) measured using DVS gravimetry at 25 °C according to the present disclosure;

[0094] Figure 73 Shows the CO2 isotherm of GE183 (1,3-benzenedimethanamine) measured using DVS gravimetry at 25 °C according to the present disclosure;

[0095] Figure 74 Shows the CO2 isotherm of GE186 (1,4-benzenedimethanamine) measured using DVS gravimetry at 25 °C according to the present disclosure;

[0096] Figure 75 Shows the CO2 isotherm of GE193 (1,4-bis-(aminomethyl)-cyclohexane) measured using DVS gravimetry at 25 °C according to the present disclosure;

[0097] Figure 76 Shows the CO2 isotherm of GE206 (1,3-bis-(aminomethyl)-cyclohexane) measured using DVS gravimetry at 25 °C according to the present disclosure;

[0098] Figure 77 Shows the CO2 isotherm of GE214 (bis(aminomethyl)norbornane) measured using DVS gravimetry at 25 °C according to the present disclosure;

[0099] Figure 78 Shows the CO2 isotherm of GE205 (4-(aminomethyl)cyclohexanamine (AMCHA)) measured using DVS gravimetry at 25 °C according to the present disclosure; °

[0100] Figure 79Shows the CO2 isotherm of GE222 (Ph-3-ED) measured by DVS gravimetry at 25 °C; °

[0101] Figure 80 Shows the CO2 isotherm of GE225 (N-methyl-1-[4-(methylaminomethyl)phenyl]methanamine) measured by DVS gravimetry at 25 °C; °

[0102] Figure 81 Shows the CO2 isotherm of GE226 (1,4-benzenedimethanamine and 1,3,5-benzenetriyltrimethanamine) measured by DVS gravimetry at 25 °C; °

[0103] Figure 82 Shows the CO2 isotherm of GE227 (1,4-benzenedimethanamine and 1,3,5-benzenetriyltrimethanamine) measured by DVS gravimetry at 25 °C; °

[0104] Figure 83 Shows the CO2 isotherm of GE303-169 (N1,N1'-(cyclohexane-1,4-diyl)bis(propane-1,3-diamine)) measured by DVS gravimetry at 25 °C; °

[0105] Figure 84 Shows the variation of CO2 uptake with spermine loading of adsorbents including pure spermine, pure BEDCH, and mixtures at different ratios measured using a breakthrough test rig at 22 °C, 50% RH, and 400 vppm CO2 according to the present disclosure;

[0106] Figure 85 Shows the variation of CO2 uptake with spermine loading of adsorbents including pure spermine, pure BEDCH, and mixtures at different ratios measured by DVS gravimetry at 120 °C and 100 mBar CO2 partial pressure according to the present disclosure;

[0107] Figure 86 Shows the variation of CO2 adsorption working capacity with spermine loading of adsorbents including pure spermine, pure BEDCH, and mixtures at different ratios according to the present disclosure;

[0108] Figure 87 Is an exemplary method flowchart according to the present disclosure;

[0109] Figure 88 Is an exemplary method flowchart according to the present disclosure;

[0110] Figure 89 Is an exemplary method flowchart according to the present disclosure; and

[0111] Figure 90 is an exemplary method flow chart according to the present disclosure.

[0112] Unless otherwise specified, the drawings provided herein are intended to illustrate the features of the embodiments of the present disclosure. It is believed that these features are applicable to a variety of systems including one or more embodiments of the present disclosure. Accordingly, the drawings are not intended to include all conventional features known to those of ordinary skill in the art that are required to practice the embodiments disclosed herein. Detailed Description

[0113] The embodiments of the present disclosure can be combined in any way, including various combinations of composition embodiments, system embodiments, and method embodiments. The subject headings are provided for convenience and do not separate or limit the embodiments of the present disclosure. Accordingly, the following embodiments are to be construed as illustrative only and do not limit the present disclosure in any way.

[0114] Carbon Dioxide Capture System Using Functionalized Adsorbents and Water Management

[0115] In one aspect, a capture system for capturing carbon dioxide is provided. The capture system includes an adsorption bed that contains at least one adsorption module and a functionalized adsorbent, the at least one adsorption module being oriented to receive an air stream, adsorb carbon dioxide in the air stream through the functionalized adsorbent, and discharge an exhaust air stream. The capture system further includes: a contactor for dynamically controlling the temperature and relative humidity of the at least one adsorption module; and a controller configured to adjust the temperature and relative humidity based on the functionalized adsorbent to promote an increase in the amount of carbon dioxide captured by the adsorption bed.

[0116] The embodiments described herein relate to systems that use functionalized chemisorbents in the presence of water to facilitate optimizing the adsorption and desorption of carbon dioxide by an adsorption bed. The advantages of the systems described herein include at least: (i) improved efficiency and performance of carbon dioxide adsorption and desorption due to the use of temperature variations in the adsorption bed; (ii) improved efficiency and performance of carbon dioxide adsorption and desorption due to the use of functionalized adsorbents within the adsorption bed; (iii) improved efficiency and performance of carbon dioxide adsorption and desorption due to the use of variations in the relative humidity of water within the adsorption bed; and (iv) improved performance of the capture system due to adjusting the temperature and relative humidity of water within one or more adsorption modules within the adsorption bed based on the functionalized adsorbent within one or more adsorption modules.

[0117] Figure 1FIG. 0 is a schematic diagram of an exemplary capture system 100 that can be used to capture CO2 using an adsorption bed 102. In this exemplary embodiment, the adsorption bed 102 includes at least one adsorption module 104. More specifically, in this exemplary embodiment, the adsorption bed 102 includes four adsorption modules 104a-d. In some embodiments, the capture system 100 may include more or fewer than four adsorption modules 104. Additionally, in this exemplary embodiment, the adsorption bed 102 includes an inlet 106 and an outlet 108. The inlet 106 and the outlet 108 are oriented such that during operation, the gas stream 110 received through the inlet 106 is directed to flow through each adsorption module 104 in series towards the outlet 108. As the gas stream 110 is directed through each adsorption module 104, the adsorption bed 102 captures CO2 from the gas stream 110, and the exhaust gas stream 112 is discharged through the outlet 108.

[0118] The adsorption module 104 may include a solid adsorbent to preferentially capture specific components of the gas stream 110, such as CO2 and H2O. In an exemplary embodiment, the adsorption module 104 includes a functionalized adsorbent 114, which includes an adsorbent and a functionalized ligand that includes at least one amine group, such as, but not limited to, an aminoorganosilane group, to facilitate an increased CO2 capture capacity and productivity of the adsorption bed 102. Generally, the functionalized adsorbent 114 can be any form known in the art to facilitate the systems described herein. For example, the functionalized adsorbent 114 can be in the form of a powder, a composite mixed with a binder, a membrane or coating, a packed bed, and / or a column.

[0119] In this exemplary embodiment, after being received by the inlet 106, the gas stream 110 is directed through the first module 104a of the adsorption module 104. Each adsorption module 104 includes a functionalized adsorbent 114 to adsorb CO2 contained in the gas stream 110. In some embodiments, the functionalized adsorbent 114 of each adsorption module 104 may be the same. In other embodiments, the functionalized adsorbent 114 within at least one adsorption module 104 may be different.

[0120] Typically, the gas stream 110 can be any suitable gas known in the art to facilitate the systems described herein. For example, the gas stream 110 can be air, flue gas, post-combustion gas, natural gas, and / or combinations thereof. In this exemplary embodiment, the gas stream 110 includes CO2 and H2O. In some embodiments, CO2 can be present in the gas stream 110 in the range of about 1 v% to about 10 v%. In other embodiments, CO2 can be present in the gas stream 110 in an amount less than 1 v%, such as in a volume of about or less than 300 ppm to 500 ppm. In other embodiments, CO2 can be present in the gas stream 110 in an amount greater than 10 v%. In some embodiments, H2O can be present in the gas stream 110 in the range of about 0.01 v% to about 20 v%. In other embodiments, H2O can be present in the gas stream 110 in an amount less than 7 v%, such as about 2 v% to 7 v% in air during hot and humid summer months, or less than 2 v% in air during cold winter months. In other embodiments, H2O can be present in the gas stream 110 in an amount greater than 5 v%, such as in post-combustion gas.

[0121] In this exemplary embodiment, when the gas stream 110 enters the inlet 106, the CO2 concentration of the gas stream 110 is typically the highest. As CO2 is adsorbed by the functionalized adsorbent 114 of each subsequent adsorption module 104, the concentration of CO2 in the gas stream 110 decreases as the gas stream 110 is directed through the adsorption modules 104a-d towards the outlet 108. In this exemplary embodiment, during a specified adsorption cycle, the CO2 concentration in the gas stream 110 flowing through the adsorption modules 104a-d is the lowest at the outlet 108.

[0122] In this exemplary embodiment, the capture system 100 further includes a controller 116 that dynamically adjusts the operation of the capture system 100. For example, as further described herein, the controller 116 can promote maximizing CO2 capture by changing the temperature of one or more of the adsorption modules 104 and / or by changing the H2O content within one or more of the adsorption modules 104.

[0123] The controller 116 regulates the operating conditions of the capture system 100 by dynamically adjusting the temperature of each adsorption module 104a-d. In this exemplary embodiment, the adsorption module 104 includes a contactor 118. The contactor 118 includes a contactor inlet 120 and a contactor outlet 121. In this exemplary embodiment, the temperature of the adsorption module 104 is regulated by heat transfer of the first stream 122 received through the contactor inlet 118. The contactor 118 can regulate the temperature of the adsorption module 104 using indirect or direct heat transfer. For example, the contactor 118 can include a fluid circuit (not shown) defined between the contactor inlet 120 and the contactor outlet 121 and extending from the contactor inlet 120 to the contactor outlet 121 such that indirect heat transfer occurs between the first stream 122 flowing within the fluid circuit (not shown) and the functionalized adsorbent 114 within the adsorption module 104. Additionally, for example, the contactor 118 can be in direct fluid communication with the adsorption module 104, where direct heat transfer occurs between the first stream 122 and the functionalized adsorbent 114 within the adsorption module 104. In some embodiments, the contactors 118 of one or more adsorption modules 104a-d can be coupled in series and / or in parallel.

[0124] The controller 116 can adjust the temperature of one or more adsorption modules 104 while monitoring the regulated temperature T of the first stream 122 reg . In some embodiments, the first stream 122 can be in liquid form. In other embodiments, the first stream 122 can be in gaseous form. The direct or indirect heat transfer between the first stream 122 and the functionalized adsorbent 114 within one or more adsorption modules 104 helps control the temperature of the functionalized adsorbent 114. The controller 116 can use the contactor sensor 130 ( Figure 4 shown) to monitor the regulated temperature T of the first stream 122 reg . Additionally, the controller 116 can use the module sensor 134 ( Figure 4 shown) to monitor the controlled temperature T of at least one adsorption module 104 cntl . Under operating conditions where the controlled temperature T of at least one adsorption module 104 cntl is lower than the desired value, the controller 124 can selectively increase the regulated temperature T of the first stream 122 reg , thereby increasing the temperature of at least one adsorption module 104. Alternatively, under operating conditions where the controlled temperature T of at least one adsorption module 104 cntl is higher than the desired value, the controller 124 can selectively decrease the regulated temperature T of the first stream 122 reg , thereby decreasing the temperature of at least one adsorption module 104.

[0125] Generally, the regulated temperature T of the first stream 122 regAnd the temperature of the adsorption module 104 therefrom can be any suitable temperature known in the art that is conducive to CO2 capture by the systems described herein. In some embodiments, the regulated temperature T of the first stream 122 reg can be in the range of about 0 °C to about 150 °C. In other embodiments, the regulated temperature T of the first stream 122 reg can be in the range of about 60 °C to about 250 °C. In an exemplary embodiment, the regulated temperature T of the first stream 122 is monitored within each adsorption module 104a-d reg . In some embodiments, the regulated temperature T of the first stream 122 reg can be substantially consistent within each adsorption module 104. In other embodiments, the regulated temperature T of the first stream 122 reg can vary among the different adsorption modules 104a-d.

[0126] Additionally, the controller 116 can change the regulated temperature T of the first stream 122 within any one of the adsorption modules 104a-d reg . For example, one or more of the adsorption modules 104a-d can include more than one module sensor 134 ( Figure 4 shown). Thus, the controller 116 can generate a temperature profile that includes varying values of the regulated temperature T of the first stream 122 within any or all of the adsorption modules 104a-d reg . In some embodiments, the varying values of the regulated temperature T of the first stream 122 reg can form a gradient temperature profile within any or all of the adsorption modules 104a-d. In other embodiments, the varying values of the regulated temperature T of the first stream 122 reg can form a discrete temperature profile within any or all of the adsorption modules 104a-d.

[0127] Figure 2 is a schematic diagram of an exemplary capture system 200 that can be used to capture CO2 using the adsorption bed 102. Figure 2 The embodiment shown in Figure 1 is similar to the embodiment shown in Figure 2 , with the differences noted herein. Thus, Figure 1The same reference numerals are used in the figures. The controller 116 dynamically adjusts the H2O relative humidity by adjusting the H2O content within each adsorption module 104a-d, thereby assisting in regulating the operating conditions of the capture system 200. In this exemplary embodiment, the adsorption module 104 includes an injector 202 that includes an injector inlet 204. A second stream 206 received through the injector inlet 204 assists in regulating the H2O relative humidity by adjusting the H2O content within the adsorption module 104. In this exemplary embodiment, the second stream 206 includes H2O. The second stream 206 may include H2O in liquid form (e.g., water) or gas form (e.g., water vapor). In some embodiments, H2O may be present in the second stream 206 in the range of from about 0.1 v% to about 20 v%. In other embodiments, H2O may be present in the second stream 206 in the range of from about 4 v% to about 15 v%. In other embodiments, H2O may be present in the second stream 206 in the range of from about 0.5 v% to about 4 v%, such as typically occurs in ambient air.

[0128] The controller 116 may adjust the H2O content within one or more adsorption modules 104 by regulating the flow rate of the second stream 206 into the one or more adsorption modules 104. For example, the controller 116 may use the module sensor 134 ( Figure 4 as shown) to monitor the relative humidity level of the H2O concentration C of the adsorption module 104. Under operating conditions where the H2O relative humidity level of the H2O concentration C is below the desired level in at least one adsorption module 104, the controller 116 may selectively increase the flow rate of the second stream 206, thereby injecting additional H2O into the at least one adsorption module 104. Under operating conditions where the H2O relative humidity level is above the desired level in at least one adsorption module 104, the controller 116 may selectively decrease the flow rate of the second stream 206, thereby reducing the amount of additional H2O injected into the at least one adsorption module 104. In another embodiment, at the start of the adsorption cycle, the controller 116 may selectively increase the flow rate of the second stream 206, thereby injecting additional H2O into the at least one adsorption module 104 to raise the relative humidity above the desired relative humidity level, thereby allowing for rapid H2O adsorption. Then, at a later stage of the adsorption cycle, the controller 116 may selectively decrease or stop the flow of the second stream 206 to reduce the relative humidity level of the at least one adsorption module 104.

[0129] The controller 116 may also regulate the temperature T of the first stream 122 of one or more absorption modules 104 by monitoring regto adjust the relative humidity of H2O within one or more adsorption modules 104. Under operating conditions where the relative humidity level of H2O is higher than the desired level in at least one adsorption module 104, the controller 116 can selectively increase the regulated temperature T of the first stream 122 reg , thereby increasing the temperature of at least one adsorption module 104. Since the saturation vapor pressure increases at elevated temperatures, the relative humidity of H2O is reduced. Under operating conditions where the relative humidity of H2O is lower than the desired value in at least one adsorption module 104, the controller 116 can selectively decrease the regulated temperature T of the first stream 122 reg , thereby decreasing the temperature of at least one adsorption module 104 and causing the relative humidity of H2O to increase. The regulated temperature T of the first stream 122 reg can be increased or decreased using any of the systems described herein.

[0130] The controller 116 adjusts the operating conditions of the capture system 200 to promote optimized CO2 adsorption and desorption by maintaining the relative humidity of each adsorption module 104a - d. The relative humidity of each adsorption module 104a - d can be based on the regulated temperature T of the first stream 122 reg and the H2O concentration C of the adsorption module 104. In this exemplary embodiment, the controller 116 adjusts the regulated temperature T of the first stream 122 reg and the H2O concentration C of the adsorption module 104 based on the H2O adsorption isotherm of the functionalized adsorbent 114 within the adsorption module 104 to promote optimized CO2 adsorption and desorption through monolayer adsorption of H2O.

[0131] Generally, the capture system 200 can have any suitable adsorption isotherm that promotes CO2 capture by the systems described herein. There are six types of moisture adsorption isotherms defined by IUPAC, and their shapes depend on relative humidity and temperature ( Figure 3 shown). Among these six types, types II, IV, and VI each show a flat region (e.g., a "turning point") up to the inflection point, typically corresponding to monolayer coverage and adsorption of H2O ( Figure 3 shown). In this exemplary embodiment, the controller 116 adjusts the operating conditions of the capture system 200 for monolayer coverage and H2O adsorption of the functionalized adsorbent 114, thereby promoting optimized CO2 adsorption and desorption. For example, the capture system 200 can have a type II, IV, or VI adsorption isotherm ( Figure 3 shown), which is particularly beneficial for ensuring monolayer coverage and H2O adsorption, thereby increasing the CO2 adsorption capacity of the functionalized adsorbent 114.

[0132] In addition to depending on relative humidity and temperature, the adsorption isotherm also depends on the adsorbent material. In many embodiments, the functionalized adsorbent 114 can be any functionalized adsorbent material that promotes the capture of CO2 in the systems described herein. In an exemplary embodiment, the functionalized adsorbent 114 includes an adsorbent and at least one functionalized ligand that includes an aminoorganosilane group to optimize the CO2 capture capacity and productivity with respect to the adsorption of H2O.

[0133] Generally, the functionalized adsorbents according to the present disclosure can be used in conjunction with the compositions, systems, and methods according to the present disclosure. The functionalized adsorbents are not limited to any particular embodiment disclosed herein.

[0134] In some embodiments, the functionalized adsorbent includes a first type of functionalized ligand, wherein the first type of functionalized ligand includes at least one functionalized ligand that includes an aminoorganosilane group. Generally, the at least one functionalized ligand that includes an aminoorganosilane group can include any such suitable ligand that promotes the functionalized adsorbent described herein. The at least one functionalized ligand that includes an aminoorganosilane group can include only one functionalized ligand that includes an aminoorganosilane group, or can include two or more functionalized ligands each including an aminoorganosilane group.

[0135] Generally, the adsorbent can be any suitable adsorbent known in the art that promotes the functionalized adsorbent described herein. In some embodiments, the adsorbent is selected from the group consisting of coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCP), covalent organic framework (COF) compounds, zeolitic imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open frameworks, reticular chemical compositions, silica particles, zeolites, silicon-aluminum-phosphate (SAPO), aluminum-phosphate (AlPO), polyaromatic frameworks (PAF), activated carbon, molecular organic solids, and combinations thereof.

[0136] As used herein, an MOF compound is a class of compounds that includes metal ions or clusters coordinated to organic ligands to form one-dimensional, two-dimensional, or three-dimensional structures. The metal ions or clusters act as linkers and bind through polyvalent organic ligands that act as connectors in the network structure. MOF compounds have modular properties that allow for synthetic tunability, which provides fine chemical and structural control. Properties such as porosity, stability, particle morphology, and conductivity can be tailored for specific applications.

[0137] In many embodiments, the adsorbent is an MOF compound that includes an MOF metal or metal-containing cluster and an MOF linker.

[0138] 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.

[0139] In some embodiments, the MOF-metal-containing cluster can be any suitable MOF-metal-containing cluster known in the art to promote the functionalized adsorbents described herein. In some embodiments, the MOF-metal-containing cluster includes MOF metal nodes and linker struts, where the definitions of the MOF metal and the linker are as described herein. In other embodiments, the MOF-metal-containing cluster includes MOF metal-oxygen clusters.

[0140] In some embodiments, the MOF linker can be any suitable MOF linker known in the art to promote the functionalized adsorbents described herein. Generally, the geometry and connectivity of the linker contribute to the structure of the resulting MOF compound. Adjusting the linker geometry, length, ratio, and functional groups can regulate the size, shape, and inner surface properties of the MOF compound for target applications.

[0141] In at least some embodiments, the MOF linker is a linker selected from the group consisting of: polytopic linker, ditopic linker, tritopic linker, tetratopic linker, pentatopic linker, hexatopic linker, heptatopic linker, octatopic linker, mixed linker, asymmetric linker, metal linker, N-heterocyclic linker, and combinations thereof.

[0142] In at least some embodiments, the MOF linker is a linker selected from the group consisting of: polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxobiphenyl-3,3'-dicarboxylate (dobpdc 4- )、4,4"-dioxo-[1,1':4',1"-terphenyl]-3,3"-dicarboxylate (dotpdc 4- )、2,5-dioxobenzene-1,4-dicarboxylate (dobdc 4- )、4,6-dihydroxyisophthalic acid (m-dobdc 4-) 3,3'-Dioxo-biphenyl-4,4'-dicarboxylate (carboxylate-dobpdc 4- ) 4,4'-[Oxalyldiimino]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, partial, and fully deprotonated forms, and combinations thereof. As another example, in at least some embodiments, the MOF linker is a linker selected from the group consisting of: dicarboxylates (e.g., terephthalic acid), tricarboxylates (e.g., 1,3,5-benzenetricarboxylic acid), azolates, tetrazolates, and combinations thereof.

[0143] As another example, in at least some embodiments, the MOF linker is a dicarboxylic acid linker selected from the group consisting of: 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, terephthalic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, PluriolE 200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-dicarboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxyphenyl)-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindane dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenone dicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diaminodiphenyl ether diimide dicarboxylic acid, 4,4'-diaminodiphenylmethane diimide dicarboxylic acid, 4,4'-diaminodiphenyl sulfone diimide dicarboxylic acid, 2,6-Naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2'-3'-diphenyl-p-terphenyl-4,4"-dicarboxylic acid, 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, icosenedicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorescein ring-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, and combinations thereof.

[0144] As another example, in at least some embodiments, the MOF linker is a tricarboxylic acid linker selected from the group consisting of: 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-f]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurintricarboxylic acid, and combinations thereof.

[0145] As another example, in at least some embodiments, the MOF linker is a tetracarboxylic acid linker selected from the group consisting of: 1,1-dioxide-perylene[1,12-bcd]thiophene-3,4,9,10-tetracarboxylic acid, perylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, meso-1,2,3,4-butane tetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenone tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, tetrahydrofuran tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, and combinations thereof.

[0146] In this exemplary embodiment, the MOF linker is 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc) and / or 4,4'-dioxobiphenyl-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.

[0147] In some embodiments, the MOF linker is one or more of the following linkers:

[0148]

[0149]

[0150]

[0151] And / or

[0152]

[0153] In some embodiments, the MOF linker is one or more of the following linkers:

[0154] 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).

[0155] In some embodiments, the functionalized adsorbent is a functionalized MOF compound of formula (A-I)

[0156]

[0157] wherein:

[0158] M is a MOF metal or a metal-containing cluster;

[0159] L is a MOF linker;

[0160] F A is at least one functionalized ligand comprising an aminoorganosilane group;

[0161] F B is at least one functionalized ligand that does not comprise an aminoorganosilane group;

[0162] x is a value in the range of 1 to 6;

[0163] y is a value in the range of 1 to 6;

[0164] a is a value greater than 0 and less than or equal to 2; and

[0165] b is a value in the range of 0 to 2.

[0166] In some embodiments, the functionalized adsorbent comprises a second type of functionalized ligand, wherein the second type of functionalized ligand comprises at least one functionalized ligand that does not comprise an aminoorganosilane group. In some embodiments, the functionalized adsorbent further comprises at least one functionalized ligand that does not comprise an aminoorganosilane group. Generally, the at least one functionalized ligand that does not comprise an aminoorganosilane group may comprise any such suitable ligand that promotes the functionalized adsorbent described herein. The at least one functionalized ligand that does not comprise an aminoorganosilane group may comprise only one functionalized ligand that does not comprise an aminoorganosilane group, or may comprise two or more functionalized ligands each of which does not comprise an aminoorganosilane group.

[0167] In some embodiments, the at least one functionalized ligand that does not contain an amino organosilicon group is selected from the group consisting of: amine ligands, monoamine ligands, diamine ligands, triamine ligands, tetraamine ligands, pentamine ligands, hexamine ligands, polyamine ligands, alkylamine ligands, and amino alcohol ligands. Exemplary ligands include, but are not limited to, ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, bis(N-methyl)ethylenediamine, N-isopropylethylenediamine, N,N-dimethyl-N-methylethylenediamine, bis(N,N-dimethyl)ethylenediamine, N,N-diisopropylethylenediamine, 2,2-dimethyl-1,3-diaminopropane, 1,3-diaminopentane, diethylenetriamine, N-(2-aminoethyl)-1,3-propanediamine, bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane (spermidine), triethylenetetramine, N,N'-bis(2-aminoethyl)-1,3-propanediamine, 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, N,N'-bis(3-aminopropyl)-1,4-diaminobutane (spermine), tetraethylenepentamine, and / or combinations thereof.

[0168] Typically, the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand not comprising an aminoorganosilane group can be present in any suitable ratio known in the art to facilitate the functionalized adsorbents described herein. In some embodiments, the ratio is selected from the group consisting of molar ratio, weight ratio, and volume ratio. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand not comprising an aminoorganosilane group are present in a ratio in the range of about 10:1 to about 1:10. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand not comprising an aminoorganosilane group are present in a ratio in the range of about 9:1 to about 1:9. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand not comprising an aminoorganosilane group are present in a ratio in the range of about 8:1 to about 1:8. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand not comprising an aminoorganosilane group are present in a ratio in the range of about 7:1 to about 1:7. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand not comprising an aminoorganosilane group are present in a ratio in the range of about 6:1 to about 1:6. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand not comprising an aminoorganosilane group are present in a ratio in the range of about 5:1 to about 1:5. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand not comprising an aminoorganosilane group are present in a ratio in the range of about 4:1 to about 1:4. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand not comprising an aminoorganosilane group are present in a ratio in the range of about 3:1 to about 1:3. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand not comprising an aminoorganosilane group are present in a ratio in the range of about 2:1 to about 1:2. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand not comprising an aminoorganosilane group are present in a ratio of about 1:1.

[0169] In some embodiments, the amount of the at least one functionalized ligand comprising an aminoorganosilane group is lower than the amount of the at least one functionalized ligand not comprising an aminoorganosilane group.

[0170] In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand not comprising an aminoorganosilane group are present in a ratio of about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, or about 1:10.

[0171] In many embodiments, the at least one functionalized ligand comprising an aminoorganosilane group can be any suitable at least one functionalized ligand comprising an aminoorganosilane group known in the art that promotes the functionalized adsorbents described herein.

[0172] In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group includes at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group includes at least one primary amine or at least one secondary amine.

[0173] In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group includes at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentamines, hexamines, polyamines, and combinations thereof.

[0174] In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group includes at least one aminoorganosilane selected from the group consisting of linear aminoorganosilanes, cyclic aminoorganosilanes, branched aminoorganosilanes, amino-substituted siloxanes, linear amino-substituted disiloxanes, cyclic amino-substituted disiloxanes, linear amino-substituted trisiloxanes, cyclic amino-substituted trisiloxanes, linear amino-substituted tetrasiloxanes, cyclic amino-substituted tetrasiloxanes, linear amino-substituted polysiloxanes, cyclic amino-substituted polysiloxanes, silsesquioxanes, polyoctahedral silsesquioxanes, and combinations thereof.

[0175] In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group includes a symmetric structure. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group includes an asymmetric structure.

[0176] In some embodiments, when the at least one functionalized ligand comprising an aminoorganosilane group contains a disiloxane group, the at least one functionalized ligand comprising an aminoorganosilane group contains the same amine on both sides of the disiloxane group. In some embodiments, when the at least one functionalized ligand comprising an aminoorganosilane group contains a disiloxane group, the at least one functionalized ligand comprising an aminoorganosilane group contains different amines on either side of the disiloxane group.

[0177] In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group is an amino-substituted siloxane of formula (A-II), formula (A-III), formula (A-IV), formula (A-V), formula (A-VI), or formula (A-VII)

[0178]

[0179]

[0180]

[0181] wherein:

[0182] R1, R2, R3, R4, R9, R 10 , R 13 , R 14 and R 18 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted straight-chain alkyl, a substituted or unsubstituted C1-C6 straight-chain alkyl, a substituted or unsubstituted branched-chain alkyl, a substituted or unsubstituted C3-C6 branched-chain alkyl, a substituted or unsubstituted straight-chain heteroalkyl, a substituted or unsubstituted branched-chain heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0183] 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, a substituted or unsubstituted C3-C6 branched-chain alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl,

[0184] R7, R8, R 12 and R 16 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C1-C6 straight-chain alkyl, a substituted or unsubstituted C3-C6 branched-chain alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, and a substituent of formula (A-VIII)

[0185]

[0186] wherein:

[0187] The wavy bond represents the bonding position to formula (A-II) or formula (A-III) or formula (A-IV) or formula (A-V) or formula (A-VI) or formula (A-VII);

[0188] R 19 , R 20 , R21 , R 22 , R 23 and R 24 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 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;

[0189] 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 form a monocyclic ring selected from the group consisting of heterocycloalkyl and heteroaryl;

[0190] R 27 , R 28 and R 29 are each independently selected from the group consisting of: a direct bond, 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, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-;

[0191] R 30 is 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, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl;

[0192] j is an integer in the range of 0 to 20;

[0193] k is an integer in the range of 0 to 20;

[0194] m is an integer in the range of 0 to 20; and

[0195] n is an integer in the range of 0 to 20.

[0196] In some embodiments, the at least one functionalized ligand comprising an aminoorganosilane group is selected from the group consisting of:

[0197]

[0198]

[0199]

[0200]

[0201] and

[0202]

[0203] Figure 4 is a schematic diagram of an exemplary control system 400 that can be used to capture CO2 with a capture system, such as capture system 100 ( Figure 1 shown) and / or capture system 200 ( Figure 2 shown). In this exemplary embodiment, the controller 116 includes a memory 402 and a processor 404. The controller 116 can adjust the temperature of one or more adsorption modules 104a-d based on data received by the control system 400 from the contact sensor 130, such as but not limited to the regulated temperature T reg of the first stream 122. The controller 116 can adjust the temperature of one or more adsorption modules 104a-d based on a comparison with data stored in the memory 402, such as the desired range of the regulated temperature T reg , instructions stored in the memory 402, and / or data analyzed by the processor 404.

[0204] Additionally, the controller 116 can adjust the temperature of one or more adsorption modules 104a-d based on data received by the control system 400 from the module sensor 134, such as but not limited to the control temperature T cntl within one or more adsorption modules 104a-d and / or the H2O relative humidity. The controller 116 can adjust the temperature of one or more adsorption modules 104a-d based on a comparison with data stored in the memory 402, such as the desired range of the control temperature T cntl and / or the H2O relative humidity, instructions stored in the memory 402, and / or data analyzed by the processor 404.

[0205] This document describes exemplary systems that use functionalized chemisorbents in the presence of water to facilitate optimized adsorption and desorption of carbon dioxide in an adsorption bed. The exemplary systems described herein offer several advantages over conventional designs and methods, including at least: increased efficiency and performance of carbon dioxide adsorption and desorption due to temperature variations in the adsorbent bed; increased efficiency and performance of carbon dioxide adsorption and desorption due to the use of functionalized adsorbents within the adsorbent bed; increased efficiency and performance of carbon dioxide adsorption and desorption due to variations in the relative humidity of water within the adsorbent bed; and increased performance of the capture system due to regulating the temperature and relative humidity of water within one or more adsorption modules within the adsorbent bed based on the functionalized adsorbent.

[0206] Other aspects of the invention are provided by the subject matter of the following clauses:

[0207] 1. A capture system for capturing carbon dioxide, the capture system comprising: an adsorption bed comprising at least one adsorption module and a functionalized adsorbent, the at least one adsorption module being oriented to: receive an air stream; adsorb carbon dioxide from the air stream through the functionalized adsorbent; and discharge an exhaust air stream; a contactor for dynamically controlling the temperature and relative humidity of the at least one adsorption module; and a controller configured to regulate the temperature and the relative humidity based on the functionalized adsorbent to facilitate an increase in the amount of carbon dioxide captured by the adsorption bed.

[0208] 2. The capture system according to any of the preceding clauses, wherein the contactor is oriented to receive a regulating fluid for dynamically controlling the temperature of the at least one adsorption module.

[0209] 3. The capture system according to any of the preceding clauses, further comprising at least one ejector oriented to discharge a water stream to control the relative humidity of water of the at least one adsorption module.

[0210] 4. The capture system according to any of the preceding clauses, wherein the controller is further configured to reduce the fluid temperature of the regulating fluid received by the contactor to facilitate an increase in the relative humidity of water.

[0211] 5. The capture system according to any of the preceding clauses, wherein the controller is further configured to regulate the relative humidity of water of the at least one adsorption module to facilitate an increase in the amount of carbon dioxide captured by the adsorption bed.

[0212] 6. The capture system according to any of the preceding clauses, wherein the controller is further configured to increase the relative humidity of water of the at least one adsorption module to facilitate an increase in the amount of carbon dioxide adsorbed by the functionalized adsorbent.

[0213] 7. The capture system according to any one of the preceding clauses, wherein the controller is further configured to increase the pressure of the water stream discharged from the ejector to facilitate an increase in the relative humidity of water in the at least one adsorption module.

[0214] 8. The capture system according to any one of the preceding clauses, wherein the controller is further configured to adjust the temperature and relative humidity of water in the at least one adsorption module to achieve a desired relative humidity based on the water adsorption isotherm of the functionalized adsorbent.

[0215] 9. The capture system according to any one of the preceding clauses, wherein the temperature and relative humidity of water in the at least one adsorption module are based on the relative humidity at the inflection point of the water adsorption isotherm of the functionalized adsorbent.

[0216] 10. The capture system according to any one of the preceding clauses, wherein the at least one adsorption module includes a plurality of adsorption modules connected in a series flow arrangement.

[0217] 11. The capture system according to any one of the preceding clauses, wherein the at least one ejector includes an ejector connected to each of the plurality of adsorption modules.

[0218] 12. The capture system according to any one of the preceding clauses, wherein the controller is further configured to adjust the temperature and relative humidity of water in each of the plurality of adsorption modules.

[0219] 13. The capture system according to any one of the preceding clauses, wherein the functionalized adsorbent includes an adsorbent and at least one functionalized ligand containing an amine group.

[0220] 14. The capture system according to any one of the preceding clauses, wherein the at least one functionalized ligand containing an amine group includes at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof.

[0221] 15. The capture system according to any one of the preceding clauses, wherein the at least one functionalized ligand containing an amine group includes at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentamines, hexamines, polyamines, and combinations thereof.

[0222] 16. The capture system according to any one of the preceding clauses, wherein the functionalized adsorbent includes an adsorbent and at least one functionalized ligand containing an aminoorganosilane group.

[0223] 17. The capture system according to any one of the preceding clauses, wherein the functionalized adsorbent is a functionalized MOF compound of formula (A-I)

[0224]

[0225] Wherein:

[0226] M is a MOF metal or a metal-containing cluster;

[0227] L is a MOF linker;

[0228] F A is the at least one functionalized ligand containing an aminoorganosilicon group;

[0229] F B is at least one functionalized ligand not containing an aminoorganosilicon group;

[0230] x is a value in the range of 1 to 6;

[0231] y is a value in the range of 1 to 6;

[0232] a is a value greater than 0 and less than or equal to 2; and

[0233] b is a value in the range of 0 to 2.

[0234] 18. The capture system according to any one of the preceding clauses, wherein the MOF metal or metal-containing cluster comprises a metal selected from the group consisting of: alkali metals, alkaline earth metals, transition metals, Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, their ions, their hydrates, their salts, their halides, their fluorides, their chlorides, their bromides, their iodides, their nitrates, their acetates, their sulfates, their phosphates, their carbonates, their oxides, their formates, their carboxylates, and combinations thereof.

[0235] 19. The capture system according to any one of the preceding clauses, wherein the MOF linker comprises a linker selected from the group consisting of: polyhedral linkers, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4"-dioxo-[1,1':4',1"-terphenyl]-3,3"-dicarboxylate (dotpdc 4- ), 2,5-dioxobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-dobdc 4- ), 3,3'-dioxo-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4-), 4,4'-[oxybis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), dicarboxylates, terephthalic acid, tricarboxylates, 1,3,5-benzenetricarboxylic acid, azoles, tetrazoles, 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, terephthalic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxyl)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindane dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9 - Trioxaundecanedicarboxylic acid, o - Hydroxybenzophenone dicarboxylic acid, Pluriol E 300 - dicarboxylic acid, Pluriol E 400 - dicarboxylic acid, Pluriol E 600 - dicarboxylic acid, Pyrazole - 3,4 - dicarboxylic acid, 2,3 - Pyrazinedicarboxylic acid, 5,6 - Dimethyl - 2,3 - pyrazinedicarboxylic acid, 4,4'-Diaminodiphenyl ether diimide dicarboxylic acid, 4,4'-Diaminodiphenylmethane diimide dicarboxylic acid, 4,4'-Diaminodiphenylsulfone diimide dicarboxylic acid, 2,6 - Naphthalenedicarboxylic acid, 1,3 - Adamantanedicarboxylic acid, 1,8 - Naphthalenedicarboxylic acid, 2,3 - Naphthalenedicarboxylic acid, 8 - Methoxy - 2,3 - naphthalenedicarboxylic acid, 8 - Nitro - 2,3 - naphthalenedicarboxylic acid, 8 - Sulfonyl - 2,3 - naphthalenedicarboxylic acid, 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, Eicosenedicarboxylic acid, 4,4'-Dihydroxydiphenylmethane - 3,3'-dicarboxylic acid, 1 - Amino - 4 - methyl - 9,10 - dioxo - 9,10 - dihydroanthracene - 2,3 - dicarboxylic acid, 2,5 - Pyridinedicarboxylic acid, Cyclohexene - 2,3 - dicarboxylic acid, 2,9 - Dichlorofluorescein ring - 4,11 - dicarboxylic acid, 7 - Chloro - 3 - methylquinoline - 6,8 - dicarboxylic acid, 2,4 - Dichlorobenzophenone - 2',5'-dicarboxylic acid, 1,3 - Benzenedicarboxylic acid, 2,6 - Pyridinedicarboxylic acid, 1 - Methylpyrrole - 3,4 - dicarboxylic acid, 1 - Benzyl - 1H - pyrrole - 3,4 - dicarboxylic acid, Anthraquinone - 1,5 - dicarboxylic acid, 3,5 - Pyrazoledicarboxylic acid, 2 - Nitrobenzene - 1,4 - dicarboxylic acid, Heptane - 1,7 - dicarboxylic acid, Cyclobutane - 1,1 - dicarboxylic acid, 1,14 - Tetradecanedicarboxylic acid, 5,6 - Dehydro - norbornane - 2,3 - dicarboxylic acid, 5 - Ethyl - 2,3 - pyridinedicarboxylic acid, 2 - Hydroxy - 1,2,3 - propanetricarboxylic acid, 7 - Chloro - 2,3,8 - quinolinetricarboxylic acid, 1,2,4 - Benzenetricarboxylic acid, 1,2,4 - Butanetricarboxylic acid, 2 - Phosphono - 1,2,4 - butanetricarboxylic acid, 1,3,5 - Benzenetricarboxylic acid, 1 - Hydroxy - 1,2,3 - propanetricarboxylic acid, 4,5 - Dihydro - 4,5 - dioxo - 1H - pyrrolo[2,3 - f]quinoline - 2,7,9 - tricarboxylic acid, 5 - Acetyl - 3 - amino - 6 - methylbenzene - 1,2,4 - tricarboxylic acid, 3 - Amino - 5 - benzoyl - 6 - methylbenzene - 1,2,4 - tricarboxylic acid, 1,2,3 - Propanetricarboxylic acid, Aurintricarboxylic acid, 1,1 - Dioxide - perylene[1,12 - bcd]thiophene - 3,4,9,10-Pyromellitic acid, perylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenone tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, tetrahydrofuran tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, polyhedral linkers, double-sided linkers, triple-sided linkers, four-sided linkers, five-sided linkers, six-sided linkers, seven-sided linkers, eight-sided linkers, mixed linkers, asymmetric linkers, metal linkers, N-heterocyclic linkers, their protonated, partially or fully deprotonated forms, and combinations thereof.,

[0236] 20. The trapping system according to any one of the preceding clauses, wherein the at least one functionalized ligand comprising an aminoorganosilane group comprises at least one aminoorganosilane selected from the group consisting of: linear aminoorganosilanes, cyclic aminoorganosilanes, branched aminoorganosilanes, amino-substituted siloxanes, linear amino-substituted disiloxanes, cyclic amino-substituted disiloxanes, linear amino-substituted trisiloxanes, cyclic amino-substituted trisiloxanes, linear amino-substituted tetrasiloxanes, cyclic amino-substituted tetrasiloxanes, linear amino-substituted polysiloxanes, cyclic amino-substituted polysiloxanes, silsesquioxanes, polyoctahedral silsesquioxanes, and combinations thereof.

[0237] Synthesis of aminoalkyl-substituted disiloxanes.

[0238] In one aspect, a method for preparing an aminoalkyl-substituted disiloxane is provided. The method comprises: I) forming a mixture comprising: a diamine or polyamine containing at least one primary amine group; and a silane; II) reacting the mixture in a first reaction; III) adding a hydrolyzing agent to the mixture; and IV) reacting the mixture in a second reaction to form the aminoalkyl-substituted disiloxane.

[0239] In another aspect, an aminoalkyl-substituted disiloxane of formula (B-I) is provided. The formula is:

[0240]

[0241] Wherein:

[0242] R12 and R 13 and R 14 and R 15 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 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;

[0243] R 16 and R 17 are each independently selected from the group consisting of: a direct bond, 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; and

[0244] R 18 and R 19 are each independently selected from the substituents of formula (B-IV)

[0245]

[0246] wherein:

[0247] The wavy bond represents the bonding position to formula (B-I);

[0248] R 25 and R 26 and R -27 and R 28 and R 29 and R 30 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 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;

[0249] R 31 and R 32Each independently is selected from the group consisting of: hydrogen, a substituted or unsubstituted straight-chain alkyl group, a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C1-C3 straight-chain alkyl group, a substituted or unsubstituted branched-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, methyl, ethyl, propyl, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, and a substituted or unsubstituted C4-C6 cycloalkyl group, or when taken together, R 31 and R 32 form a monocyclic ring selected from the group consisting of a heterocycloalkyl group or a heteroaryl group;

[0250] R 33 、R 34 and R 35 Each independently is 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 -NHCH2CH2CH2CH2-;

[0251] R 36 is selected from the group consisting of: hydrogen, a substituted or unsubstituted straight-chain alkyl group, a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C1-C3 straight-chain alkyl group, a substituted or unsubstituted branched-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, methyl, ethyl, propyl, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C4-C6 cycloalkyl group, a heterocycloalkyl group, and a heteroaryl group; and

[0252] m is an integer in the range of 0 to 20;

[0253] provided that the aminoalkyl-substituted disiloxane is not

[0254] The embodiments described herein overcome at least some of the disadvantages of known methods for preparing aminoalkyl-substituted disiloxanes and known aminoalkyl-substituted disiloxanes. Exemplary embodiments described herein include a method for preparing an aminoalkyl-substituted disiloxane, the method comprising: I) forming a mixture comprising: a diamine or polyamine containing at least one primary amine group; and a silane; II) reacting the mixture in a first reaction; III) adding a hydrolyzing agent to the mixture; and IV) reacting the mixture in a second reaction to form the aminoalkyl-substituted disiloxane. Compared with known methods for preparing aminoalkyl-substituted disiloxanes, the exemplary embodiments described herein avoid side reactions and / or produce the desired product with higher yield and purity in fewer steps.

[0255] In many embodiments, the method is a one-pot synthesis. As used herein, a one-pot synthesis is a synthesis that is carried out in a single reaction vessel. There is no need to remove intermediates from the reaction vessel for separation and / or purification. A one-pot synthesis may include one reaction or more than one reaction. A one-pot synthesis is particularly advantageous in reducing reaction complexity and avoiding lengthy and expensive separations and purifications.

[0256] In many embodiments, the aminoalkyl-substituted disiloxane is an amino-C1-C6-alkyl-substituted disiloxane. Embodiments comprising C1-C6 alkyl groups are thermodynamically more favorable for formation compared to other compounds comprising larger aminoalkyl substituents or alternative substituents. In some embodiments, the aminoalkyl-substituted disiloxane is an aminomethyl-substituted disiloxane.

[0257] Figure 13 is Exemplary Method Flowchart 1310. In this exemplary embodiment, Method Flowchart 1310 depicts the basic method steps of the exemplary embodiments described herein and is not intended to limit method embodiments. First, a mixture 1312 is formed, which includes: a diamine or polyamine containing at least one primary amine group; and a silane. The mixture is reacted 1314 in a first reaction, and a hydrolyzing agent 1316 is added to the mixture. Then the mixture is reacted 118 in a second reaction to form the aminoalkyl-substituted disiloxane.

[0258] In some embodiments, the aminoalkyl-substituted disiloxanes according to the present disclosure are selected from the group consisting of aminoalkyl-substituted disiloxanes of formula (B-I)

[0259]

[0260] wherein:

[0261] R 12 、R 13 、R 14 、R15 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-chain heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0262] R 16 and R 17 Each independently selected from a direct bond, 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, preferably C1-C6 straight-chain alkyl, even more preferably C1 alkyl;

[0263] R 18 and R 19 Each independently selected from substituents of formula (B-IV)

[0264]

[0265] wherein:

[0266] The wavy bond represents the bonding position to formula (B-I);

[0267] R 25 、R 26 、R -27 、R 28 、R 29 and R 30 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;

[0268] R 31 and R 32 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 31 and R 32Form a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl;

[0269] R 33 、R 34 and R 35 are each independently selected from the group consisting of: a direct bond, 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, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-;

[0270] R 36 is 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, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl; and

[0271] m is an integer in the range of 0 to 20, preferably an integer in the range of 0 to 10, and even more preferably an integer in the range of 0 to 3;

[0272] provided that the aminoalkyl-substituted disiloxane is not

[0273] In some embodiments, the aminoalkyl-substituted disiloxane is selected from the group consisting of:

[0274]

[0275]

[0276] and

[0277]

[0278] In some embodiments, the diamine or polyamine containing at least one primary amine group can be any suitable diamine or polyamine containing at least one primary amine group known in the art that promotes the methods described herein. In other embodiments, the diamine or polyamine containing at least one primary amine group is a compound of formula (B-II)

[0279]

[0280] wherein:

[0281] R1, R2, R3, R4, R5, and R6 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 branched-chain alkyl, substituted or unsubstituted C3-C6 branched-chain alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched-chain heteroalkyl, substituted or unsubstituted C3-C6 branched-chain heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0282] R7 and R8 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, R7 and R8 form a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl;

[0283] R9, R 10 and R 11 are each independently selected from the group consisting of a direct bond, 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, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-; and

[0284] n is an integer in the range of 0 to 20, preferably an integer in the range of 0 to 10, and even more preferably an integer in the range of 0 to 3.

[0285] In some embodiments, the silane can be any suitable silane known in the art that promotes the methods described herein. In some embodiments, the silane is an alkoxysilane. In at least some embodiments, the silane is a compound of formula (B-III)

[0286]

[0287] wherein:

[0288] R 20 is selected from the group consisting of halide ions, fluoride ion, chloride ion, bromide ion, and iodide ion;

[0289] R 21 and R 22Each independently is selected from the group consisting of: hydrogen, a substituted or unsubstituted straight-chain alkyl group, a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted branched alkyl group, a substituted or unsubstituted C3-C6 branched alkyl group, a substituted or unsubstituted straight-chain heteroalkyl group, a substituted or unsubstituted branched heteroalkyl group, an aryl group, a phenyl group, a heteroaryl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group;

[0290] R 23 and R 24 Each independently is selected from the group consisting of: a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C3-C6 branched 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 aryl group, and a phenyl group.

[0291] In some embodiments, R 23 and R 24 Each independently is selected from the group consisting of: a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C3-C6 branched 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, preferably a C1-C6 straight-chain alkyl group.

[0292] In some embodiments, R 23 is a C1 alkyl group.

[0293] In some embodiments, R 24 is 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 aryl group, or a phenyl group.

[0294] In some embodiments, the silane is In some embodiments, the silane is

[0295] In many embodiments, reacting the mixture in the first reaction 1314 can be carried out under any suitable reaction conditions known in the art that facilitate the methods described herein. In some embodiments, reacting the mixture in the first reaction 1314 includes stirring the mixture.

[0296] In many embodiments, reacting the mixture in the first reaction 1314 can be carried out for any suitable amount of time known in the art to facilitate the methods described herein. In some embodiments, the elapsed time for the mixture to react in the first reaction 1314 ranges from about 1 second to about 12 hours. In some embodiments, the elapsed time for the mixture to react in the first reaction 1314 ranges from about 1 second to about 6 hours. In some embodiments, the elapsed time for the mixture to react in the first reaction 1314 ranges from about 1 second to about 3 hours. In some embodiments, the elapsed time for the mixture to react in the first reaction 1314 ranges from about 1 hour to about 3 hours. In some embodiments, the elapsed time for the mixture to react in the first reaction 1314 ranges from about 2 hours to about 3 hours.

[0297] In some embodiments, reacting the mixture in the first reaction 1314 includes dropwise adding a silane (such as chloromethyldimethyl ethoxysilane) to a pure diamine or polyamine containing at least one primary amine group within about 1 hour. Allow the reaction temperature to rise to about 90 °C due to the exothermic reaction and maintain this temperature during the reaction duration (a total of about 2 - 3 hours). During this period, the HCl salt of the amine is formed and may precipitate to varying degrees depending on the amine.

[0298] In some embodiments, the hydrolyzing agent is added dropwise 1316 to the mixture. In some embodiments, the hydrolyzing agent is added to the mixture over a period of time. In some embodiments, the hydrolyzing agent is added to the mixture 1316 over a period of time ranging from about 1 second to about 12 hours. In some embodiments, the hydrolyzing agent 1316 is added within 30 minutes and under exothermic conditions and then cooled to room temperature, and then the mixture is reacted in the second reaction 118.

[0299] In some embodiments, the hydrolyzing agent 1316 is added within 30 minutes and under exothermic conditions before reacting the mixture in the second reaction 1318. In these embodiments, the reaction 1318 is completed before cooling the reaction mixture to room temperature.

[0300] In many embodiments, the hydrolyzing agent can be any suitable hydrolyzing agent known in the art to facilitate the methods described herein. In some embodiments, the hydrolyzing agent is an aqueous solution. In some embodiments, the hydrolyzing agent is water.

[0301] In many embodiments, reacting the mixture in the second reaction 1318 can be carried out under any suitable reaction conditions known in the art to facilitate the methods described herein. In some embodiments, reacting the mixture in the second reaction 1318 includes adjusting the temperature of the mixture. In some embodiments, reacting the mixture in the second reaction 1318 includes cooling the mixture.

[0302] In some embodiments, the aminoalkyl-substituted disiloxane is further extracted from the reaction mixture. In some embodiments, the aminoalkyl-substituted disiloxane is further extracted from the reaction mixture with an organic solvent.

[0303] In some embodiments, extracting the aminoalkyl-substituted disiloxane from the reaction mixture comprises dropwise adding an organic solvent (e.g., chloroform and / or toluene) to the reaction mixture over 30 minutes and vigorously stirring the reaction mixture for about 1 hour or until cooled to room temperature. Once cooled, the organic layer is separated, the aqueous layer is back-extracted with a minimal amount of organic solvent, and the combined organic layers are concentrated under vacuum, triturated once with an organic solvent, and then dried under vacuum.

[0304] In some embodiments, the aminoalkyl-substituted disiloxane is further purified. In some embodiments, further purification comprises using distillation, vacuum distillation, and / or heating. In some embodiments, further purification comprises using vacuum distillation to remove impurities and by-products. In these embodiments, the remaining material in the distillation flask is a higher purity product relative to the product before purification.

[0305] In many embodiments, the mixture is reacted in a second reaction 1318 for any suitable amount of time known in the art to facilitate the methods described herein. In some embodiments, the elapsed time for the mixture to react in the second reaction 1318 ranges from about 1 second to about 12 hours. In some embodiments, the elapsed time for the mixture to react in the second reaction 1318 ranges from about 1 second to about 6 hours. In some embodiments, the elapsed time for the mixture to react in the second reaction 1318 ranges from about 1 second to about 3 hours. In some embodiments, the elapsed time for the mixture to react in the second reaction 1318 ranges from about 1 hour to about 3 hours. In some embodiments, the elapsed time for the mixture to react in the second reaction 1318 ranges from about 2 hours to about 3 hours.

[0306] In many embodiments, the method may further comprise any other suitable processing steps known in the art to facilitate the success of the methods described herein. Such processing steps may include, but are not limited to, only washing, drying, filtering, purifying, separating, centrifuging, and any combination thereof. In some embodiments, the method further comprises washing the aminoalkyl-substituted disiloxane compound. In some embodiments, the method further comprises purifying the aminoalkyl-substituted disiloxane compound. In some embodiments, purification comprises using distillation, vacuum distillation, and / or heating. In some embodiments, the method further comprises removing volatile reaction by-products.

[0307] In some embodiments, the method comprises: I) forming a mixture comprising: a diamine or polyamine containing at least one primary amine group; and a chloromethyldimethylalkoxysilane; II) reacting the mixture in a first reaction by a controlled exothermic nature; III) adding a hydrolyzing agent to the mixture; IV) reacting the mixture in a second reaction to form an aminoalkyl-substituted disiloxane; (V) extracting the aminoalkyl-substituted disiloxane; and (VI) purifying the aminoalkyl-substituted disiloxane.

[0308] In many embodiments, the aminoalkyl-substituted disiloxane can be used for any suitable purpose known in the art. In some embodiments, the aminoalkyl-substituted disiloxane is used in a carbon capture system. In some embodiments, the aminoalkyl-substituted disiloxane is used in amino-organosilicon-based products.

[0309] Other aspects of the present disclosure are provided by the subject matter of the following clauses:

[0310] 1. A method for preparing an aminoalkyl-substituted disiloxane, the method comprising: I) forming a mixture comprising: a diamine or polyamine containing at least one primary amine group; and a silane; II) reacting the mixture in a first reaction; III) adding a hydrolyzing agent to the mixture; and IV) reacting the mixture in a second reaction to form the aminoalkyl-substituted disiloxane.

[0311] 2. The method according to the previous clause, wherein the aminoalkyl-substituted disiloxane is a compound of formula (B-I)

[0312]

[0313] wherein:

[0314] R 12 、R 13 、R 14 、R 15 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 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;

[0315] R 16 and R 17 are each independently selected from the group consisting of: a direct bond, 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;

[0316] R 18 and R 19 are each independently selected from the substituents of formula (B-IV)

[0317]

[0318] wherein:

[0319] The wavy bond represents the bonding position to formula (B-I);

[0320] R 25 、R 26 、R -27 、R 28 、R 29 and R 30 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 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;

[0321] R 31 and R 32 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 31 and R 32 form a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl;

[0322] R 33 、R 34 and R 35 are each independently selected from the group consisting of: a direct bond, 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, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-;

[0323] R 36selected 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; and

[0324] m is an integer in the range of 0 to 20.

[0325] 3. The method according to any one of the preceding clauses, wherein the aminoalkyl-substituted disiloxane is a compound selected from the group consisting of:

[0326]

[0327]

[0328] and

[0329]

[0330] 4. The method according to any one of the preceding clauses, wherein the diamine or polyamine containing at least one primary amine group is a compound of formula (B-II)

[0331]

[0332] wherein:

[0333] R1, R2, R3, R4, R5 and R6 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 branched-chain alkyl, substituted or unsubstituted C3-C6 branched-chain alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched-chain heteroalkyl, substituted or unsubstituted C3-C6 branched-chain heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0334] R7 and R8 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, R7 and R8 form a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl;

[0335] R9, R10 and R 11 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 -NHCH2CH2CH2CH2-; and

[0336] n is an integer in the range of 0 to 20.

[0337] 5. The method according to any one of the preceding clauses, wherein the silane is a compound of formula (B-III)

[0338]

[0339] wherein:

[0340] R 20 is selected from the group consisting of a halide ion, a fluoride ion, a chloride ion, a bromide ion, and an iodide ion;

[0341] R 21 and R 22 each independently selected from the group consisting of hydrogen, a substituted or unsubstituted straight-chain alkyl group, a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted branched-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, a substituted or unsubstituted straight-chain heteroalkyl group, a substituted or unsubstituted branched-chain heteroalkyl group, an aryl group, a phenyl group, a heteroaryl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group;

[0342] R 23 and R 24 each independently selected from the group consisting of 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 aryl group, and a phenyl group.

[0343] 6. The method according to any one of the preceding clauses, wherein the silane is

[0344] 7. The method according to any one of the preceding clauses, wherein reacting the mixture in the first reaction comprises stirring the mixture.

[0345] 8. The method according to any one of the preceding clauses, wherein reacting the mixture in the first reaction comprises reacting the mixture for a first period of time.

[0346] 9. The method according to any one of the preceding clauses, wherein the first time period is a time in the range of from about 1 second to about 12 hours.

[0347] 10. The method according to any one of the preceding clauses, wherein the hydrolyzing agent is an aqueous solution.

[0348] 11. The method according to any one of the preceding clauses, wherein the hydrolyzing agent is water.

[0349] 12. The method according to any one of the preceding clauses, wherein the hydrolyzing agent is added to the mixture during a second time period.

[0350] 13. The method according to any one of the preceding clauses, wherein the second time period is a time in the range of from about 1 second to about 12 hours.

[0351] 14. The method according to any one of the preceding clauses, wherein the hydrolyzing agent is added dropwise to the mixture.

[0352] 15. The method according to any one of the preceding clauses, wherein the method further comprises purifying the aminoalkyl-substituted disiloxane.

[0353] 16. The method according to any one of the preceding clauses, wherein at least one method step comprises adjusting the temperature of the mixture.

[0354] 17. The method according to any one of the preceding clauses, wherein reacting the mixture in a second reaction comprises adjusting the temperature of the mixture.

[0355] 18. The method according to any one of the preceding clauses, wherein reacting the mixture in a second reaction comprises cooling the mixture.

[0356] 19. The method according to any one of the preceding clauses, wherein the method is a one-pot synthesis.

[0357] 20. An aminoalkyl-substituted disiloxane prepared by the method according to any one of the preceding clauses.

[0358] 21. An aminoalkyl-substituted disiloxane of formula (B-I)

[0359]

[0360] Wherein:

[0361] R 12 、R 13 、R 14 、R 15Each 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-chain heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0362] R 16 and R 17 Each independently selected from the group consisting of: a direct bond, 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;

[0363] R 18 and R 19 Each independently selected from the substituents of formula (B-IV)

[0364]

[0365] wherein:

[0366] The wavy bond represents the bonding position to formula (B-I);

[0367] R 25 、R 26 、R -27 、R 28 、R 29 and R 30 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;

[0368] R 31 and R 32 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 31 and R 32 form a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl;

[0369] R 33 、R 34 and R 35 each independently is 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 -NHCH2CH2CH2CH2-;

[0370] R 36 is selected from the group consisting of: hydrogen, a substituted or unsubstituted straight-chain alkyl group, a substituted or unsubstituted C1-C6 straight-chain alkyl group, a substituted or unsubstituted C1-C3 straight-chain alkyl group, a substituted or unsubstituted branched-chain alkyl group, a substituted or unsubstituted C3-C6 branched-chain alkyl group, methyl, ethyl, propyl, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C4-C6 cycloalkyl group, a heterocycloalkyl group, and a heteroaryl group; and

[0371] m is an integer in the range of 0 to 20;

[0372] provided that the aminoalkyl-substituted disiloxane is not

[0373] 22. The aminoalkyl-substituted disiloxane according to the previous clause, wherein the aminoalkyl-substituted disiloxane is a compound selected from the group consisting of:

[0374]

[0375]

[0376] and

[0377]

[0378] Machine Learning Model Incorporating Physical Characteristics of Adsorbents for Post-Combustion Carbon Capture

[0379] In one aspect, a power generation system is provided. The power generation system includes a capture system for capturing carbon dioxide, a controller configured to operate the capture system, and a modeling system including a processor. The processor is configured to identify a model training data set, each instance of which identifies an adsorbent used by the capture system, a carbon capture performance value of the adsorbent, and a plurality of primary feature values associated with a plurality of primary features. The processor is further configured to generate one or more secondary features based on one or more of the plurality of primary features, each of the one or more secondary features being a combination of at least two of the plurality of primary features; and determine a plurality of correlation magnitude values, the plurality of correlation magnitude values including a correlation magnitude value between each of the plurality of primary features and each of the one or more secondary features. The processor is further configured to identify a first subset of the model training data set based on the plurality of correlation magnitude values, determine the statistical significance of each instance of the first subset of the model training data set, and identify a second subset of the model training data set based on the statistical significance, wherein the statistical significance of each instance of the second subset of the model training data set is lower than a predetermined threshold. The processor is further configured to generate a transfer function based on the second subset of the model training data set, and use the transfer function to determine one or more expected adsorbents to be used by the capture system based on the carbon capture performance value. The controller operates the capture system using the one or more expected adsorbents determined by the modeling system.

[0380] In another aspect, a method of selecting one or more expected adsorbents for operating a capture system to capture carbon dioxide is provided. The method includes identifying a model training data set, each instance of which identifies an adsorbent used by the capture system, a carbon capture performance value of the adsorbent, and a plurality of primary feature values associated with a plurality of primary features. The method further includes generating one or more secondary features based on one or more of the plurality of primary features, each of the one or more secondary features being a combination of at least two of the plurality of primary features; determining a plurality of correlation magnitude values, the plurality of correlation magnitude values including a correlation magnitude value between each of the plurality of primary features and each of the one or more secondary features; and identifying a first subset of the model training data set based on the plurality of correlation magnitude values. The method further includes determining the statistical significance of each instance of the first subset of the model training data set; identifying a second subset of the model training data set based on the statistical significance, wherein the statistical significance of each instance of the second subset of the model training data set is lower than a predetermined threshold; and generating a transfer function based on the second subset of the model training data set. The method further includes using the transfer function to determine one or more expected adsorbents to be used by the capture system based on the carbon capture performance value, wherein the controller operates the capture system using the one or more expected adsorbents determined according to the transfer function.

[0381] In one embodiment, a computer program is provided and the program is embodied on a computer-readable medium. In an exemplary embodiment, the system executes on a single computer system without the need to be connected to a server computer. In additional embodiments, the system operates in an environment (Windows is a registered trademark of Microsoft Corporation, Redmond, Washington). In another embodiment, the system operates in a mainframe environment and a server environment (UNIX is a registered trademark of X / Open Company Limited, Reading, Berkshire, United Kingdom). In another embodiment, the system operates in an environment (iOS is a registered trademark of Cisco Systems, Inc., San Jose, California). In another embodiment, the system operates on a Mac environment (Mac OS is a registered trademark of Apple Inc., Cupertino, CA). In another embodiment, the system operates in an OS (Android is a registered trademark of Google, Inc., Mountain View, CA). In another embodiment, the system operates in an OS (Linux is a registered trademark of Linus Torvalds, Boston, MA). The application is flexible and is designed to operate in a variety of different environments without affecting any of the major functions. In some embodiments, the system includes multiple components distributed among multiple computing devices. One or more components may take the form of computer-executable instructions contained in a computer-readable medium.

[0382] Embodiments of the present invention generally relate to systems and methods for analyzing the physical characteristics of sorbents for post-combustion carbon capture (PCC), and more particularly to systems and methods for modeling aspects of metal-organic frameworks (MOFs) based on their composition and their performance in terms of carbon dioxide (CO2) capture capacity. In an example embodiment, the modeling system is configured to train a model based on the performance characteristics of known metal-organic frameworks (MOFs) and their associated components. The model can then be used to evaluate the desired performance of other MOFs based on the specific composition of the other MOFs. Such modeling can help scientists and engineers evaluate different MOFs without having to perform physical tests on each candidate, thus enabling the faster development of MOFs with improved performance in terms of CO2 capture capacity.

[0383] Figure 14 An exemplary PCC modeling system 1440 is shown, which can be used to predict how a particular MOF will perform when capturing carbon dioxide (CO2) from the exhaust gas 1416 of a coal-fired power plant 1410. In this exemplary embodiment, the power plant 1410 generates electricity 1412 that is distributed via the power transmission and distribution network 1414. The power plant 1410 also includes a post-combustion carbon capture (PCC) system 1420 that is configured to remove CO2 from the exhaust gas 1416 and then release the treated exhaust gas into the environment. The exemplary PCC system 1420 includes a metal-organic framework (MOF) 1422 that performs the capture function of the PCC system 1420. The MOF 1422 is composed of three main components, namely a metal 1424, an organic linker 1426, and one or more functional groups 1428. During operation, the PCC system 1420 produces some performance results, which for the purposes of discussion are generally represented here as "capture performance" 1430 (e.g., PCC capacity). The PCC modeling system 1440 is configured to estimate how a particular MOF (e.g., a specific combination of composition and various associated physical characteristics) will perform when implemented in the PCC system 1420 (e.g., performance prediction in a "real-world" environment).

[0384] In this exemplary embodiment, the PCC modeling system 1440 includes a data collection and preparation module 1442 configured to identify and store data that will be used to train a machine learning model (e.g., a supervised prediction model). The preparation module 1442 stores historical records of various adsorbents (e.g., MOF 1422) and their associated characteristics and known performance. Each historical record may include, for example, adsorbent data such as the composition of a particular adsorbent (e.g., information about the metal 1424 used in the secondary building unit or SBU, information about the organic linker 1426, and / or information about any functional groups 1428 or amines associated with a particular MOF 1422), various physical characteristics of the adsorbent (e.g., pore size, pore volume, pore size distribution, surface area, etc.), and known performance data of the adsorbent (e.g., the isosteric heat of adsorption (Q ST 0) at a particular pressure and / or temperature, Henry's law constant, selectivity ratio, adsorption capacity in millimoles of CO2 adsorbed per gram of adsorbent, adsorbent productivity in millimoles of CO2 adsorbed per gram of adsorbent per unit time, etc.). Each of these historical records may be stored as model data 1460 (e.g., in a database) and may include other data described herein. Some of these records may be collected from published literature, where other records may include data collected from laboratory measurement data or operational performance data of the PCC system 1420 (e.g., data collected during operation).

[0385] The PCC modeling system 1440 also includes an exploratory data analysis module 1444 configured to assist analyst 1402 in performing univariate data analysis on aspects of the historical data. In an exemplary embodiment, the exploratory data analysis module 1444 is configured to generate a chart showing the individual components of known MOFs for a single feature, thereby allowing analyst 1402 to see trends in that feature for various MOFs. For example, the analysis module 1444 may generate graphs of how two types of MOFs, chemical adsorbents and physical adsorbents, perform in terms of Henry's constant, selectivity ratio, heat of adsorption, PCC capacity, and PCC productivity (e.g., as composites across the two types of MOFs). In another example, the analysis module 1444 may generate graphs of the various metal types in physical or chemical adsorbent MOFs and their respective heats of adsorption (e.g., the range of values, averages, etc. for each metal type). These graphs may be compiled and generated from the historical records identified in the model data 1460 and displayed to analyst 1402 via the display of the computing device 1404. Based on this data, analyst 1402 may further identify one or more second-order features, which may be a combination of two or more of the first-order features, as further discussed below. Such second-order features may be used for subsequent model training and analysis.

[0386] In this exemplary embodiment, the PCC modeling system 1440 further includes a correlation and bivariate analysis module 1446 configured to analyze the model data 1460 for positive or negative correlations between various pairs of features in the history. For example, the analysis module 1446 can identify a set of first-order features and possibly one or more second-order features, and perform a correlation analysis between the associated features. For each specific pair of two features, the analysis module 1446 calculates a correlation coefficient that identifies how the two features are related to each other (e.g., across all records in the model data 1460) (e.g., where a positive coefficient indicates a positive correlation between the two features, and where a negative coefficient indicates a negative correlation between the two features). These correlation coefficients can be, for example, Pearson correlation coefficients, etc. These correlation coefficients can be displayed to the analyst 1402 in matrix format, thereby allowing the analyst 1402 to view the strength of the correlations between various pairs of features. In some examples, the matrix can be a heat map that, for example, displays each correlation coefficient in the colors of a color spectrum, with one color (e.g., dark blue) at one end of the color spectrum representing a strong positive correlation, and another color (e.g., dark red) at the opposite end of the color spectrum representing a strong negative correlation, with the coloring along the color spectrum based on the magnitude of the correlation coefficient. In some examples, the analysis module 1446 can generate a paired plot for each pair of features, thereby allowing the analyst 1402 to evaluate what type of relationship (e.g., linear, non-linear, etc.) the two features have.

[0387] The PCC modeling system 1440 further includes a regression analysis module 1448 configured to perform a regression analysis using the model data 1460. In the exemplary embodiment, the regression analysis module 1448 identifies one or more features of interest for the regression analysis. In some embodiments, the analyst 1402 can examine the correlation matrix and / or paired plots described above and can select a subset of the features of interest. In some embodiments, the regression analysis module 1448 can automatically identify one or more features of interest for the regression analysis (e.g., based on the correlation coefficients of the matrix). For example, the regression analysis module 1448 can select all features that have a positive correlation coefficient (e.g., a strong positive correlation) with the PCC capacity that is higher than a specific threshold. In some embodiments, the regression analysis module 1448 can also select all features that have a negative correlation coefficient (e.g., a strong negative correlation) with the PCC capacity that is lower than a specific threshold. In some embodiments, such as features manually selected by the user to start the regression analysis.

[0388] Once the subset of features is identified, the regression analysis module 1448 performs a regression analysis process starting from the subset of features. In some embodiments, a portion of the model data 1460 may be automatically or manually identified as training data (e.g., for the regression analysis process), and the remaining portion of the model data 1460 may be reserved for evaluating the resulting model (e.g., 60% training data, 40% test data). In an exemplary embodiment, the regression analysis process is performed in one or more stages, where each stage includes performing a multiple linear regression analysis on the current set of features. Based on the results of each stage, one or more features may be removed for subsequent analysis stages, leaving another subset of the downward-selected features for the next analysis stage until a specific stopping criterion is reached. In this final stage, the regression analysis module 148 uses the last remaining downward-selected features (e.g., PCC capacity as a function of a specific downward-selected feature) to generate a transfer function. Thus, the transfer function can be applied to new MOFs and their associated eigenvalue to predict how the new MOF will perform in terms of PCC capacity, productivity, etc.

[0389] FIG. 16 and Figure 17 more particularly describe additional details and related functionality performed by the PCC modeling system 1440.

[0390] Figure 15Is Chart 1500, which shows the decline in the CO2 adsorption productivity of an exemplary adsorbent (e.g., an exemplary MOF) from a synthetic powder measured under equilibrium conditions to a final film coating on a substrate measured under dynamic conditions. In this exemplary embodiment, the Y-axis 1502 of Chart 1500 is the adsorbent productivity of the MOF in kilograms of CO2 (kgCO2) per kilogram of adsorbent (kg) per hour (h). The X-axis shows several stages 1504 of the PCC productivity: from the equilibrium powder productivity in the initial stage 1504A, to the kinetic time effect stage 1504B, the membrane mass transfer effect stage 1504C, the thermodynamic effect (working capacity between adsorption and desorption) stage 1504D, and then to the final coating working productivity stage 1504E. In this embodiment, in the initial stage 1504A, the adsorbent exhibits a productivity of approximately 0.58 kgCO2 / kg / h in the synthetic powder measured under equilibrium conditions. At each of the stages 1504A - 1504E, the adsorbent undergoes various reductions in productivity based on the various effects described above. For example, in the kinetic time effect stage 1504B, the adsorbent undergoes a production reduction 1512 of approximately 0.2, with the total dropping to approximately 0.35 kgCO2 / kg / h. Additionally, for example, in the membrane mass transfer effect stage 1504C, the adsorbent undergoes a second production reduction 1514 of approximately 0.05, with the total dropping to just below approximately 0.3 kgCO2 / kg / h. Further, for example, in the thermodynamic effect working capacity stage 1504D, the adsorbent undergoes a third production reduction 1516 of approximately 0.1, dropping to a final coating working productivity 1520 of approximately 0.2 kgCO2 / kg / h. Thus, in this example, the adsorbent undergoes a total productivity reduction 1522 of approximately 0.38 kgCO2 / kg / h, or a reduction of approximately 65% (e.g., approximately 35% utilization). This knock-down effect is specific to each adsorbent, membrane coating, and cycle time operation.

[0391] Figure 15 The decline in PCC productivity exhibited by an exemplary adsorbent typically depends on coating type and measurement type characteristics and may be due to a combination of factors such as adsorption cycle time kinetics not allowing for equilibrium to be reached, coating mass transfer resistance, and the heat of adsorption heating the adsorbent and reducing performance capacity. In the absence of Figure 14 a PCC modeling system 1440, all of these factors are typically determined experimentally in order to understand the final productivity of a given adsorbent.

[0392] For low initial adsorption concentrations, the Henry's law constant determines the equilibrium capacity of the adsorbent. The adsorbent capacity N i of adsorbent i is the Henry's law constant H i multiplied by the gas phase concentration C i of the adsorbent: N i= H i C i 。The greater the value of the Henry's constant, the steeper the initial slope of the isotherm. This means that in this low-concentration linear region of the isotherm, an adsorbent with a higher H i has a greater adsorbate capacity. Maximizing H i also increases the productivity of the adsorbent at low gas-phase adsorbate concentrations. Thus, the PCC modeling system 1440 will search for adsorbents with high Henry's law constants for CO2 adsorption by analyzing how various MOF components independently vary with the Henry's constant. Since the Henry's constant is a thermodynamic term (e.g., not a kinetic term), the kinetics of the adsorbent can also be evaluated to determine the adsorbent productivity. These measurements are not typically reported in the literature for known MOFs, so the PCC modeling system 1440 can first look at the Henry's constant to identify MOF components with the highest CO2 capacity potential at the lowest CO2 gas-phase concentrations. Where kinetic adsorption data are available, they are used as data inputs to the PCC modeling system.

[0393] Figures 16A to 16C is a flowchart showing an exemplary method 1600 for analyzing the desired performance of prospective adsorbents in a post-combustion carbon capture system. In some embodiments, the method 1600 can be performed by the PCC modeling system 1440, and the identified adsorbent can be installed in the Figure 14 PCC system 1420. In an exemplary embodiment, the method 1600 includes collecting or otherwise identifying model training data for known adsorbents (e.g., MOFs for which performance data are available) at operation 1610.

[0394] In an exemplary embodiment, the identified model training data includes instances of a single adsorbent and its specific composition, as well as known performance data (e.g., various variables of a specific known adsorbent) stored in a database such as a model database. Each adsorbent may include information about the composition of that specific adsorbent instance (e.g., specific metal elements, organic linkers, and / or functional groups or functionalities), various physical characteristics of the adsorbent instance (e.g., pore size, pore volume, isosteric heat of adsorption, Henry's law constant, selectivity ratio, Langmuir / BET area, absorption rate, etc.), known performance data of the adsorbent instance (e.g., PCC capacity and productivity), and possibly other information about the adsorbent instance, such as a unique identifier or other adsorbent data (e.g., physical adsorbent or chemical adsorbent classification). Metals may include, for example, nickel, chromium, magnesium, copper, manganese, zirconium, zinc, cobalt, indium, iron, aluminum, dysprosium, titanium, potassium, etc., or some combination or alloy. Organic linkers may include, for example, 1,4-dioxo-2,5-benzenedicarboxylate (DOBDC), 1,4-benzenedicarboxylate (BDC), 4,4'-oxybiphenyl-3,3'-dicarboxylate (DOBPDC), 1,3,5-tris(1H-1,2,3-triazol-4-yl)benzene (BTTri), 1,3,5-benzenetricarboxylate (BTC), 1H,5H-benzo(1,2-d:4,5-d')bis(triazole) (BBTA), 1,1'-biphenyl-4,4'-dicarboxylate (BPDC), 1,1'-biphenyl-3,3',5,5'-tetracarboxylate (BPTC), 1,5-dioxo-2,6-naphthalenedicarboxylate (DONDC), 1,2,4,5-benzenetetracarboxylate (BTEC), 1,4-bis(1H-pyrazol-4-ylethynyl)benzene (BPEP), 2,5-bis(1H-1,2,4-triazol-1-yl)terephthalate (BTTA), 2,4,6-tris(3,5-dicarboxyphenylamino)-1,3,5-triazine (TDPAT), 2,3,5,6-tetrachloroterephthalate (TCDC), 4,4'-sulfonyldibenzoate (SBPDC), etc. Functionalities may include, for example, open metal sites [OMS], microporosity [MP], Lewis basic sites [LBS], polar functional sites [PFS], post-synthetic modification [PSM], etc. Although exemplary metals, linkers, functional groups, and physical characteristics are provided herein, it should be understood that others are possible and within the scope of the present disclosure. In some cases, such adsorbent model training data may be manually collected and recorded in the model data database (e.g., by analyst 1402). In some embodiments, the PCC modeling system 1440 may be configured to collect such data (e.g., via other online databases, from performance or test data captured via the PCC system 1420, etc.).

[0395] In an exemplary embodiment, the adsorbent data is used by the PCC modeling system 1440 as model training data for training a machine learning model to analyze the desired performance of a prospective adsorbent (e.g., a novel combination of metals, linkers, and functionalities not yet studied and tested under real-world conditions). The model training data can be used as labeled training data in model construction (e.g., an instance of model training data with a known outcome or “label” for a particular “input”). In some embodiments, a subset of the model training data can be identified for the purpose of training the model, and another subset can be identified for the purpose of testing the model (e.g., 60% of the adsorbents are identified for training and 40% for testing, 70% for training and 30% for testing, etc.). In some embodiments, the analyst 1402 can manually identify the adsorbents for training and testing (e.g., via specific rows of a database). In some embodiments, the PCC modeling system 1440 can automatically identify the training subset and the testing subset (e.g., using pre-configured percentages, random selection, etc.).

[0396] In some embodiments, method 1600 further includes performing aspects of univariate data analysis on the model training data at operation 1620. Such data analysis includes evaluating a particular single adsorbent variable (e.g., a particular component or feature) relative to other variables of the entire training data body (e.g., another component, feature, or performance value). The analysis can be used to identify high-level trends relative to a particular component or feature.

[0397] In this exemplary embodiment, the PCC modeling system 1440 can provide a graphical user interface to the analyst 1402 that displays a plot of a particular feature relative to other target features of interest, thereby allowing the analyst 1402 to investigate trends and relationships between these particular features. The interface can allow the analyst 1402 to select a primary variable of interest (e.g., as the domain) and a secondary variable of interest (e.g., as the range), and the PCC modeling system 1440 can then calculate the mean / average / median and / or range of values of a bar chart, forest plot, etc. (e.g., for a domain variable with discrete values and a continuous secondary variable) across all the training data with those variables, or can generate a scatter plot, etc. (e.g., for continuous primary and secondary variables). For example, the PCC modeling system 1440 can generate a plot of an organic linker relative to the isosteric heat of adsorption or Henry's law constant or average pore diameter, and can identify physical adsorbents or chemical adsorbents respectively (e.g., via different colors or shadings). In another example, the PCC modeling system 1440 can generate a plot of the metals identified in the training data relative to the isosteric heat of adsorption or selectivity ratio.

[0398] At operation 1630, in an exemplary embodiment, the PCC modeling system 1440 generates secondary features to be used during model training. A secondary feature is a combination of two or more primary features. The term "primary feature" refers to one of the known variables (e.g., a pre-existing primary effect parameter of a historical adsorbent), such as the heat of adsorption at zero coverage, Henry's law constant, pore diameter, pore volume, surface area, etc. The term "secondary feature" refers to a combination of two or more of those primary features that relate to the interaction between two primary features (e.g., an interaction parameter). In some embodiments, the analyst 1402 may manually create secondary features within the PCC modeling system 1440 by specifying two or more primary features and combining them into a new secondary feature of the model. In one example, secondary feature "A" may be created as (BET area * pore volume (V pore ), secondary feature "B" is created as (V pore * heat of adsorption at zero coverage (Q st ), and secondary feature "C" is created as (BET area * Q st ). These secondary features may be used for model training and analysis described below.

[0399] In some embodiments, the PCC modeling system 1440 may select secondary features to be used during model training by using an automatic selection process. For example, the PCC modeling system 1440 may analyze the statistical significance of each primary feature, such as by a probability value. A probability value (p-value) is a measure of the significance of a variable to the model. A p-value less than 0.05 means that the factor in the model is statistically significant at a 95% confidence level, indicating strong evidence against the result being random, with a probability of less than 5% that the result is random.

[0400] In some embodiments, the PCC modeling system 1440 may select a set number of secondary features. For example, for the number n of primary features analyzed by the PCC modeling system 1440, the set number of secondary features may be n C. In this example, the PCC modeling system 1440 may automatically select a total number of primary and secondary features equal to (n + n C).

[0401] At operation 1640, in an exemplary embodiment, the PCC modeling system 1440 performs correlation and bivariate analysis of the model data. Now refer to Figure 16B, the analysis includes identifying a feature set for model training. At operation 1642, an expected feature set is identified for model training. The feature set includes a list of primary features 1602 (or first-order features) and secondary features 1604 (or second-order features) to be used in model training. As described above, the primary features 1602 include a list of physical characteristics or known variables provided for the adsorbent in the model 1460 (e.g., heat of adsorption, pore size, pore volume, Henry's constant, etc.), and the secondary features 1604 include those combined features defined in operation 1630. The primary features 1602 and the secondary features 1604 are collectively referred to as the "feature set" 1606 for model training. In one exemplary embodiment, the primary features 1602 include PCC capacity, BET area, Langmuir surface area, pore volume (V pore ), isosteric heat of adsorption (Q st ) and average pore size And the secondary features 1604 include the three exemplary secondary features described above, i.e., "A" = (BET area * pore volume (V pore ), "B" = (V pore * isosteric heat of adsorption (Q st )) and "C" = (BET area * Q st ). Thus, the training data can be considered to define an n-dimensional space, where n is the number of features 1606 used in model training.

[0402] At operation 1644, the PCC modeling system 1440 can generate a paired graph or scatter plot for each unique combination of the primary features 1602 and the secondary features 1604 in the feature set 1606 and using the training data adsorbents selected from the model data 1460. For example, the PCC modeling system 1440 can generate a first pair of graphs showing the BET area and PCC capacity on the training data, a second pair of graphs showing the Langmuir surface area and PCC capacity on the training data, a third pair of graphs showing the V pore and PCC capacity on the training data, and so on, for each unique combination of the features 1606. The PCC modeling system 1440 can display these graphs in a graphical user interface for the analyst 1402 to examine and consider. For some combinations, these graphs can help the analyst 1402 identify whether there is any correlation between these two variables within the training data, whether the correlation is linear or non-linear, and whether it is a positive or negative correlation. Additionally, these graphs can help the analyst 1402 identify statistically significant variables within the training data.

[0403] At operation 1646, the PCC modeling system 1440 generates a correlation matrix 1608 of the correlation coefficients of each pair of primary features 1602 and secondary features 1604 in the feature set 1606. More specifically, in this exemplary embodiment, the correlation matrix 1608 is an n by n matrix, where each unique feature 1602, 1604 in the feature set 1606 is assigned a row and a column (e.g., a square, a reflection matrix). Each cell of the matrix 308 represents a certain combination of two features 1602, 1604 in the feature set 1606 (e.g., based on the specific row and column of the cell), and the value contained in the cell is a correlation coefficient representing the degree or magnitude of the correlation between these two specific features. For each combination of two features 1602, 1604, the PCC modeling system 1440 calculates the correlation coefficient of these two features (e.g., across the training data) at operation 1648. In this exemplary embodiment, the correlation coefficient is normalized from a range between +1.0 - 1.0, where the more positive the correlation between two features, the closer to +1.0, the more negative the correlation, the closer to -1.0, and a neutral (e.g., weak or non-existent) correlation is closer to 0.0 (e.g., Pearson correlation coefficient). At operation 1650, the PCC modeling system 1440 fills a specific cell with the correlation coefficient associated with these two features 1602, 1604. When completed, the correlation matrix and the associated values can be displayed to the analyst 1402 for inspection and consideration, and in some embodiments, can be presented as a heat map (e.g., coloring each individual cell based on the value of each individual cell), thus allowing the analyst 1402 to more easily see the positive and negative correlations between specific features. Additional details regarding the exemplary correlation matrix 1608 are as Figure 17 shown.

[0404] Returning again to Figure 16A , the exemplary method 1600 continues at operation 1660, where the PCC modeling system 1440 performs a regression analysis to generate a transfer function that can help roughly estimate the PCC performance of other (e.g., untested) adsorbents. More specifically, Figure 16C shows an exemplary regression analysis process for operation 1660.

[0405] In this exemplary embodiment, a set of model training data is identified from the model data 1460 for use during the regression operation 1660. In some embodiments, and as described above, specific instances of the training data can be manually identified (e.g., by the analyst 1402) or can be selected by the PCC modeling system 1440 (e.g., automatically). Thus, the training data represents which known adsorbents are within the scope of this particular regression analysis, where the remaining model data can be used to validate the results of this training.

[0406] At operation 1664, a set of features is selected for the initial feature set 1680 (e.g., from the primary features 1602 and secondary features 1604 of the complete feature set 1606). In some embodiments, all features of the complete feature set 1606 may initially be used as the initial feature set 1680. In other embodiments, the analyst 1402 may manually select the features in the initial feature set 1680 (e.g., based on viewing the pairing plots and / or correlation matrices). In other embodiments, the PCC modeling system 1440 may automatically select the initial feature set 1680. For example, the PCC modeling system 1440 may selectively add all features 1602, 1604 having a correlation coefficient with the PCC capacity higher than a predetermined threshold (e.g., greater than 0.2) or lower than a predetermined threshold (e.g., less than -0.2) to the initial feature set 1680. Then a plurality of these features, i.e., f, are used as the current feature set 1682 to start the regression.

[0407] At operation 1666, the PCC modeling system 1440 performs multiple linear regression on the model training data using the current feature set (e.g., using an ordinary least squares model fit of the training data, where the PCC productivity is the dependent variable of interest, as determined based on the PCC capacity and the CO2 absorption rate (e.g., adsorption kinetics)). Here, the linear regression method is applied to Equation 1 to study the parameters of interest (e.g., the PCC capacity ) and the various physical properties selected for the initial feature set 1680 (e.g., the BET area, pore volume, isosteric heat of adsorption, and the second-order features "A", "B", and "C" described above):

[0408]

[0409] In this regression, each of the f current features 1682 in the current feature set is represented by X i and an associated linear coefficient b i in Equation 1. Initially, as the regression iterates, all of the initial features 1680 are included in the transfer function of Equation 1, and then the current feature 1682 with the highest p-value is removed until all current features 1682 have a p-value less than a predetermined value (e.g., less than 0.05, meaning they have a 95% probability of being statistically significant). The relevant variables in the model are those variables having a probability value ("p-value") less than a predetermined threshold.

[0410] More specifically, in this exemplary embodiment, at each step of the iteration, a p-value is generated for each remaining feature in the current feature set 1682. At test 1668, the PCC modeling system 1440 tests whether the regression is complete by evaluating the p-values of the current features 1682. If all of the p-values of the remaining current features 1682 are below a predetermined threshold, the iteration terminates. Otherwise, the iteration continues to operation 1670. At operation 1670, the PCC modeling system 1440 identifies the current feature having the highest p-value and removes that particular feature from the current feature set 1682 for the next iteration. The regression process returns to operation 1666, continues on the reduced current feature set 1682, generates new p-values again, until all remaining features are below the predetermined threshold. If a primary feature has a p-value above the threshold, but a secondary feature that includes the primary feature has a p-value below the threshold, the primary feature is kept as part of the model, even though its individual p-value is greater than the threshold. This is necessary in order for the secondary feature with a p-value below the threshold to be part of the model.

[0411] Upon completion and exit of the regression iteration, the PCC modeling system 1440 may have identified one or more remaining features to be included in the final feature set 1684, each remaining feature having a p-value equal to or below a predetermined threshold and thus being statistically significant. In this exemplary embodiment, the PCC modeling system 1440 examines the final results to determine possible indications of overfitting in the model. For the final feature set 1684, the PCC modeling system 1440 also generates an r-squared value and an adjusted r-squared value, and the difference between these two values can be an indication of overfitting (e.g., if they are too far apart). If the difference between the r-squared value and the adjusted r-squared value (e.g., abs(r-squared - adjusted r-squared)) is greater than a predetermined threshold, then there is a likelihood of overfitting in the model. In this case, the PCC modeling system 1440 then analyzes each unique combination of the remaining features in the final feature set 1684, runs the model with that combination to generate an r-squared value and an adjusted r-squared value for each combination, and then selects the particular combination having the closest r-squared value and adjusted r-squared value (e.g., the minimum abs(r-squared - adjusted r-squared)).

[0412] The remaining features and their associated values are used to generate a final transfer function from the model. More specifically, the regression yields a final coefficient for each remaining feature in the final feature set 1684, as well as a constant coefficient (e.g., the y-intercept value). Thus, each of the X f variables in Equation 1 is identified with each of the remaining features in the remaining features, and each associated coefficient b fAdded to Equation 1, along with the constant coefficient b0, to generate the final transfer function. Thus, this transfer function can be used with the expected adsorbent and its associated values to determine the expected PCC capacity for that particular adsorbent.

[0413] In some embodiments, the PCC modeling system 1440 can use a model on test data to evaluate its performance in predicting capacity. For example, the PCC modeling system 1440 can generate residual plots for linear regression models for both training data and test data, allowing the analyst 1402 to evaluate how well the model performs.

[0414] In a particular example, a regression operation 1660 is performed on an exemplary training set, starting with an initial feature set of isosteric heat of adsorption (Q st ), BET area, pore volume (V pore ), and three exemplary secondary features "A", "B", and "C". In the first iteration, the p-value for the BET area is identified as the highest at 0.948 and is removed. In the second iteration, the p-value for the "A" secondary feature is identified as the highest at 0.769 and is removed. In the third iteration, the p-value for the "B" secondary feature is identified as the highest at 0.441 and is removed. In the fourth iteration, the p-values for all remaining current features (e.g., Q st , V pore , and the "C" secondary feature) are below 0.05, and thus the regression iteration terminates with these three features as the final feature set. However, in this example, the final r-squared value is 0.400 and the adjusted r-squared value is 0.363, a difference that triggers overfitting analysis. Since there are three remaining features in the final feature set 1684, each combination of those features is examined with the model (e.g., a total of 3! = 6 unique combinations, namely [Q st , [Q st , V pore , [Q st , V pore , "C"], [V pore , [V pore , "C"], and ["C"]). In this example, only the combination of [Q st produces an r-squared of 0.567 and an adjusted r-squared of 0.560, with a minimum difference of 0.007. Thus, only the Q st feature and its associated value are used to generate a final transfer function with only one remaining feature (e.g., X1 = Q st ), i.e., where b1 = 0.0318 is for Q stThe resulting final coefficients, and where b0 = -0.4243 is the constant coefficient. In this particular example, applying the test data to the trained model results in a test r-squared value of 0.331, where the r-squared of the trained model is 0.567. Thus, the formula includes only features with p-values less than 0.05. Additionally, the positive r-squared of the test data indicates that the model is able to use the heat of adsorption (Q st ) to explain approximately 60% of the capacity.

[0415] The PCC modeling system 1440 can operate a post-combustion carbon capture system using the generated transfer function, such as but not limited to by determining one or more expected sorbents to be used by the post-combustion carbon system. For example, the PCC modeling system 1440 can identify one or more expected sorbents based on the carbon capture performance values determined by the transfer function to facilitate improving the overall carbon capture performance of the post-combustion carbon capture system.

[0416] Figure 17 An exemplary correlation matrix 1608 is shown. In some embodiments, the correlation matrix 1608 is generated by the PCC modeling system 1440 and used in the method 1600 described in Figures 16B to 16C . In this exemplary embodiment, the correlation matrix 1608 is a 9×9 square reflection matrix. It has nine rows 1702 and nine columns 1704, and nine features 1712 for this exemplary model subject. Each of the nine features 1712 has an associated row 1702 and an associated column 1704. The features 1712 include six first-order (“primary”) features 1712A and three second-order (“secondary”) features 1712B, similar to the example provided in Figures 16B to 16C . Each cell of the matrix includes a correlation coefficient calculated between the two specific intersecting features of that cell. For example, the correlation coefficient between the BET area and the PCC capacity is -0.12.

[0417] Other aspects of the invention are provided by the subject matter of the following clauses:

[0418] 1. A power generation system, comprising: a capture system configured to capture carbon dioxide; a controller configured to operate the capture system; and a modeling system including a processor configured to: identify a model training data set, each instance of the model training data set identifying an adsorbent used by the capture system, a carbon capture performance value of the adsorbent, and a plurality of primary feature values associated with a plurality of primary features; generate one or more secondary features based on one or more of the plurality of primary features, each of the one or more secondary features being a combination of at least two of the plurality of primary features; determine a plurality of correlation magnitude values, the plurality of correlation magnitude values including a correlation magnitude value between each of the plurality of primary features and each of the one or more secondary features; identify a first subset of the model training data set based on the plurality of correlation magnitude values; determine the statistical significance of each instance of the first subset of the model training data set; identify a second subset of the model training data set based on the statistical significance, wherein the statistical significance of each instance of the second subset of the model training data set is lower than a predetermined threshold; generate a transfer function based on the second subset of the model training data set; and use the transfer function to determine one or more expected adsorbents to be used by the capture system based on the carbon capture performance value, wherein the controller operates the capture system using the one or more expected adsorbents determined by the modeling system.

[0419] 2. The power generation system according to the preceding clause, wherein generating the one or more secondary features based on one or more of the plurality of primary features includes performing univariate data analysis on the plurality of primary features.

[0420] 3. The power generation system according to any one of the preceding clauses, wherein determining the plurality of correlation magnitude values includes generating a correlation matrix including a plurality of cells arranged in a plurality of rows and a plurality of columns for the plurality of primary features and the one or more secondary features, each of the plurality of cells including one of the plurality of correlation magnitude values.

[0421] 4. The power generation system according to any one of the preceding clauses, wherein the processor of the modeling system is configured to select an initial feature set from the plurality of primary features and the one or more secondary features.

[0422] 5. The power generation system according to any one of the preceding clauses, wherein selecting the initial feature set includes receiving user input from a user indicating a selection of one or more of the plurality of primary features and the one or more secondary features.

[0423] 6. The power generation system according to any one of the preceding clauses, wherein selecting the initial feature set includes selecting one or more features from the plurality of primary features and the one or more secondary features, and each of the one or more features has a correlation coefficient greater than a predetermined threshold.

[0424] 7. The power generation system according to any one of the preceding clauses, wherein each of the one or more features has one or more PCC performance data values greater than a predetermined threshold.

[0425] 8. The power generation system according to any one of the preceding clauses, wherein the processor of the modeling system is configured to: determine an r-squared value and an associated adjusted r-squared value for each unique combination of each instance of the second subset of the model training data set; determine the difference between the r-squared value and the associated adjusted r-squared value for each instance of the second subset of the model training data set; and identify a third subset of the model training data set based on the difference, wherein the difference for each instance of the third subset of the model training data set is greater than a predetermined difference threshold.

[0426] 9. The power generation system according to any one of the preceding clauses, wherein the difference for each instance of the third subset of the model training data set is less than the predetermined difference threshold.

[0427] 10. The power generation system according to any one of the preceding clauses, wherein the plurality of primary features at least includes carbon capture capacity and isosteric adsorption heat value.

[0428] 11. The power generation system according to any one of the preceding clauses, wherein the one or more secondary features are based on one or more of selectivity ratio, pore volume, and isosteric adsorption heat value.

[0429] 12. A method of selecting one or more prospective sorbents for operating a capture system to capture carbon dioxide, the method comprising: identifying a model training data set, each instance of the model training data set identifying a sorbent used by the capture system, a carbon capture performance value of the sorbent, and a plurality of principal feature values associated with a plurality of principal features; generating one or more secondary features based on one or more of the plurality of principal features, each of the one or more secondary features being a combination of at least two of the plurality of principal features; determining a plurality of correlation magnitude values, the plurality of correlation magnitude values including a correlation magnitude value between each of the plurality of principal features and each of the one or more secondary features; identifying a first subset of the model training data set based on the plurality of correlation magnitude values; determining the statistical significance of each instance of the first subset of the model training data set; identifying a second subset of the model training data set based on the statistical significance, wherein the statistical significance of each instance of the second subset of the model training data set is below a predetermined threshold; generating a transfer function based on the second subset of the model training data set; and using the transfer function to determine, based on the carbon capture performance value, one or more prospective sorbents to be used by the capture system, wherein a controller operates the capture system using the one or more prospective sorbents determined according to the transfer function.

[0430] 13. The method according to the preceding clause, wherein generating the one or more secondary features based on one or more of the plurality of principal features includes performing univariate data analysis on the plurality of principal features.

[0431] 14. The method according to any one of the preceding clauses, wherein determining the plurality of correlation magnitude values includes generating a correlation matrix including a plurality of cells arranged in a plurality of rows and a plurality of columns for the plurality of principal features and the one or more secondary features, each of the plurality of cells including one of the plurality of correlation magnitude values.

[0432] 15. The method according to any one of the preceding clauses, further comprising selecting an initial feature set from the plurality of principal features and the one or more secondary features.

[0433] 16. The method according to any one of the preceding clauses, wherein selecting the initial feature set includes receiving user input from a user indicating a selection of one or more of the plurality of principal features and the one or more secondary features.

[0434] 17. The method according to any one of the preceding clauses, wherein selecting the initial feature set includes selecting one or more features from the plurality of primary features and the one or more secondary features, each of the one or more features having a correlation coefficient greater than a predetermined threshold.

[0435] 18. The method according to any one of the preceding clauses, further comprising: determining an r-squared value and an associated adjusted r-squared value for each unique combination of each instance of the second subset of the model training dataset; determining a difference between the r-squared value and the associated adjusted r-squared value for each instance of the second subset of the model training dataset; and identifying a third subset of the model training dataset based on the difference.

[0436] 19. The method according to any one of the preceding clauses, wherein identifying the third subset of the model training data includes the difference for each instance of the third subset of the model training dataset being greater than a predetermined difference threshold.

[0437] 20. The method according to any one of the preceding clauses, wherein identifying the third subset of the model training data includes the difference for each instance of the third subset of the model training dataset being less than a predetermined difference threshold.

[0438] Solid Adsorbent Material

[0439] In one aspect, a functionalized adsorbent is provided. The functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising an aminoorganosilane group. The adsorbent has an average particle length of ≤3 μm. In another aspect, the adsorbent has an average particle length of ≤2 μm. In another aspect, the adsorbent has an average particle length of ≤1 μm.

[0440] It has been found that one or more of reduced adsorbent particle size, increased adsorbent aspect ratio, and aqueous adsorbent synthesis result in an adsorbent with significantly improved CO2 absorption kinetics.

[0441] Typically, the adsorbent can include any suitable particle size known in the art that promotes the functionalized adsorbents described herein. 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 ≥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.

[0442] Typically, the adsorbent can include any suitable aspect ratio known in the art that promotes the functionalized adsorbents described herein. As used herein, the 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 in the range of 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.

[0443] In some embodiments, the particle size is a single particle size. The single particle size measurement can be performed according to any suitable means known in the art, such as by measuring the particle size in a SEM image.

[0444] In some embodiments, the particle size measurement result is an average particle size measurement result. The average particle size measurement can be performed according to any suitable means known in the art, such as by analyzing particle size distribution information.

[0445] Generally, the particle size of the adsorbent can be controlled, altered, or reduced according to any suitable technique known in the art for facilitating the functionalized adsorbents described herein. In some embodiments, suitable techniques for controlling, altering, or reducing the particle size include mechanical grinding (e.g., mortar and pestle), using a microfluidizer, dry milling, wet milling, chemical size reduction (e.g., incorporating a crystal growth inhibitor), sonication, hydrodynamic cavitation, and combinations thereof.

[0446] Generally, the adsorbent can be in any suitable form known in the art for facilitating the functionalized adsorbents described herein. In some embodiments, the form of the adsorbent is selected from the group consisting of powders, pellets, composites, composites mixed with a binder, membranes, coatings, packed beds, columns, monoliths, and combinations thereof.

[0447] Exemplary embodiments described herein include adsorbent systems. Generally, the adsorbent system can be any suitable adsorbent system known in the art for facilitating 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 polymer membrane.

[0448] In some embodiments, the adsorbent system includes at least one contactor. In some embodiments, the adsorbent system includes more than one contactor. In some embodiments, the adsorbent system includes 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 for facilitating 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 the adsorbent system. In some embodiments, the contactor includes more than one adsorbent coating, wherein at least one adsorbent coating is the adsorbent system.

[0449] In some embodiments, the adsorbent system includes a framework. The framework can be any suitable framework known in the art for facilitating the functionalized adsorbents described herein. The framework can be included in a contactor or between two contactors. The framework can consist of one component or more than one component. In some embodiments, the framework is an air framework. In some embodiments, the configuration of the framework is selected from the group consisting of polygonal configurations, rectangular configurations, square configurations, circular configurations, asymmetric configurations, and combinations thereof. In some embodiments, the adsorbent system is mounted on the framework.

[0450] In some embodiments, the adsorbent system includes at least one concentrator. The concentrator can be any suitable concentrator known in the art for facilitating the functionalized adsorbents described herein. The concentrator can be a passive concentrator or an active concentrator.

[0451] 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 known in the art for facilitating the functionalized adsorbents described herein that is configured to drive fluid flow. In some embodiments, the component configured to drive fluid flow is selected from the group consisting of pumps, fans, and combinations thereof.

[0452] 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 known in the art for facilitating the functionalized adsorbents described herein that is configured to change temperature. In some embodiments, the component configured to change temperature is selected from the group consisting of heaters, coolers, and combinations thereof.

[0453] In some embodiments, the adsorbent system includes at least one component configured to transport fluid. The component configured to transport fluid can be any suitable component known in the art for facilitating the functionalized adsorbents described herein that is configured to transport fluid. In some embodiments, the component configured to transport fluid is selected from the group consisting of pipes, perforated pipes, plastic perforated pipes, polymer perforated pipes, metal perforated pipes, composite perforated pipes, and combinations thereof.

[0454] Generally, the functionalized adsorbents can 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 an adsorbent system. In some embodiments, the functionalized adsorbents are used in a carbon capture adsorbent system. In some embodiments, the functionalized adsorbents are used in a moisture adsorbent system. In some embodiments, the functionalized adsorbents are used in a carbon capture adsorbent system 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 capture of CO2 and / or direct air capture of CO2.

[0455] The exemplary embodiments described herein include methods of preparing an adsorbent system. Generally, the functionalized adsorbents can be prepared according to any suitable synthetic methods known in the art that facilitate the functionalized adsorbents described herein.

[0456] In many embodiments, methods of preparing an adsorbent system include preparing an adsorbent, wherein the adsorbent has an average particle length of ≤3 μm, and optionally functionalizing the adsorbent with at least one functionalizing ligand comprising an aminoorganosilane group. In some embodiments, methods of preparing an adsorbent system include preparing an adsorbent, wherein the adsorbent has an average particle length of ≤2 μm, and optionally functionalizing the adsorbent with at least one functionalizing ligand comprising an aminoorganosilane group. In some embodiments, methods of preparing an adsorbent system include preparing an adsorbent, wherein the adsorbent has an average particle length of ≤1 μm, and optionally functionalizing the adsorbent with at least one functionalizing ligand comprising an aminoorganosilane group.

[0457] In some embodiments, methods of preparing an adsorbent system include functionalizing an adsorbent with at least one functionalizing ligand comprising an aminoorganosilane group. In some embodiments, methods of preparing an adsorbent system include functionalizing an adsorbent with at least two functionalizing ligands each comprising an aminoorganosilane group, wherein the aminoorganosilane groups are different from each other. In some embodiments, methods of preparing an adsorbent system further include functionalizing an adsorbent with at least one functionalizing ligand that does not comprise an aminoorganosilane group. In some embodiments, methods of preparing an adsorbent system include controlling the ratio between at least one functionalizing ligand comprising an aminoorganosilane group and at least one functionalizing ligand that does not comprise an aminoorganosilane group.

[0458] In some embodiments, methods of preparing an adsorbent system further include annealing the functionalized adsorbent. Annealing the adsorbent system can remove excess ligand. In some embodiments, annealing the functionalized adsorbent includes annealing the functionalized 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.

[0459] Figure 34It is the exemplary method flow chart 3410. In this exemplary embodiment, the method flow chart 3410 depicts the exemplary steps of the method embodiments described herein and is not intended to limit these method embodiments. In this exemplary embodiment, the method includes forming 3412 a mixture that includes: an adsorbent precursor; a crystal growth inhibitor; an optional solvent; and an optional non-solvent. The method further includes reacting 3414 the mixture. In some embodiments, the adsorbent has an average particle length of ≤3 μm. In some embodiments, the adsorbent has an average particle length of ≤2 μm. In some embodiments, the adsorbent has an average particle length of ≤1 μm.

[0460] Forming 3412 the mixture can be carried out 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.

[0461] In some embodiments, the adsorbent precursor includes a MOF linker and a MOF metal or a metal-containing cluster. The adsorbent precursor can be formed before the mixture is formed 3412 and added to the mixture as a single component, or can be formed in situ in the mixture during the formation 3412 of the mixture. For example, the MOF linker can be deprotonated separately and then added in situ or deprotonated. Similarly, the MOF metal or the metal-containing cluster can be pre-formed and then added in situ or formed.

[0462] 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 advantages in terms of scalability, safety, cost, and waste treatment. In addition, MOF compounds prepared with an aqueous solvent are generally easier to purify than the same MOF compounds prepared according to known methods, for example, by solvent washing. This improved purification results from the relatively easy removal of solvent molecules (e.g., water) from the MOF compounds described herein compared with the removal of strongly bound solvent molecules (e.g., dimethylformamide (DMF)) used to prepare the same MOF compounds according to known methods. 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, the purification is improved by a purification method that requires less toxicity.

[0463] 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.

[0464] Generally, a non-solvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, the non-solvent is a liquid-based component included in the reaction mixture. In some embodiments, the non-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, the non-solvent is selected from the group consisting of organic solvents, aqueous solvents, and combinations thereof.

[0465] In some embodiments, the crystal growth inhibitor is selected from the group consisting of salicylic acid, 4-fluorosalicylic acid, 4,4'-biphenol, 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC), 2,2'-bipyridine-5,5'-dimethanol (BPYDM), benzoic acid, biphenol, bipyridine, and combinations thereof.

[0466] Figure 35 Exemplary method flow chart 3510. In this exemplary embodiment, method flow chart 3510 depicts exemplary steps of the method embodiments described herein and is not intended to limit these method embodiments. In this exemplary embodiment, the method includes forming 3512 a mixture that includes: an adsorbent; at least one functionalized ligand comprising an aminoorganosilane group; optionally at least one functionalized ligand that does not comprise an aminoorganosilane group; an optional solvent, and an optional non-solvent. The method further includes functionalizing 3514 the adsorbent.

[0467] In some embodiments, functionalizing 3514 the adsorbent includes stirring the mixture.

[0468] In some embodiments, functionalizing 3514 the adsorbent includes functionalizing 3514 the adsorbent in the presence of an inert gas.

[0469] In some embodiments, functionalizing 3514 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 3514 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 3514 the adsorbent includes functionalizing 3514 the adsorbent at a temperature in the range of about 20 °C to about 60 °C.

[0470] In some embodiments, functionalizing 3514 the adsorbent includes functionalizing 3514 the adsorbent for a time in the range of about 1 minute to about 7 days. In some embodiments, functionalizing 3514 the adsorbent includes functionalizing 3514 the adsorbent for a time in the range of about 1 hour to about 3 days.

[0471] In some embodiments, the adsorbent is desolvated before functionalizing 3514. In some embodiments, the adsorbent is dry before functionalizing.

[0472] In some embodiments, the adsorbent is annealed after functionalization 3514. 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.

[0473] 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.

[0474] Generally, an anti-solvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, the anti-solvent is a liquid-based component included in the reaction mixture. In some embodiments, the anti-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, the anti-solvent is selected from the group consisting of organic solvents, aqueous solvents, and combinations thereof.

[0475] In some embodiments, the anti-solvent aids in functionalization. In some embodiments, the selectivity of functionalization is controlled by relative solubility. For example, one or more adsorbents or amines may have different solubilities in a liquid-based reaction mixture compared to another adsorbent or amine or functionalized adsorbent. Thus, relative solubility introduces limitations on the reaction and / or the reagents.

[0476] In many embodiments, the method may further include any other suitable processing steps known in the art to facilitate the success of the methods described herein. Such processing steps may include, but are not limited to, only washing, drying, filtering, purifying, separating, centrifuging, and any combination thereof. In some embodiments, the method 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.

[0477] Exemplary embodiments described herein include a method of trapping at least one gas.

[0478] Figure 36is an exemplary method flow chart 3610. In this exemplary embodiment, the method flow chart 3610 depicts exemplary method steps of the method embodiments described herein and is not intended to limit these method embodiments. The method includes receiving 3612, at a functionalized adsorbent, a gas source comprising at least one gas, wherein the functionalized adsorbent comprises: an adsorbent; and at least one functionalized ligand comprising an aminoorganosilane group. In some embodiments, the functionalized adsorbent comprises at least two functionalized ligands each comprising an aminoorganosilane group, wherein the aminoorganosilane groups are different from each other. In some embodiments, the functionalized adsorbent further comprises at least one functionalized ligand that does not comprise an aminoorganosilane group. The method further includes trapping 3614, with the functionalized adsorbent, an amount of at least one gas. The adsorbent has an average particle length of ≤3 μm.

[0479] In some embodiments, the method includes: (I) receiving 3612, at a functionalized adsorbent, a gas source comprising at least one gas, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising an aminoorganosilane group; and (II) trapping 3614, with the functionalized adsorbent, an amount of the at least one gas.

[0480] 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, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0481] 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, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0482] In some embodiments, the at least one gas is present in the source gas in an amount in the range of 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 in the range of 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 in the range of 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 in the range of 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 in the range of 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 in the range of 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).

[0483] In some embodiments, the at least one gas is present in the source gas in an amount in the range of 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 in the range of 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 in the range of from about 300 ppmv to about 5000 ppmv.

[0484] In some embodiments, the at least one gas does not include water vapor.

[0485] In some embodiments, the at least one gas includes water vapor. In some embodiments, the at least one gas includes water vapor in an amount in the range of from about 0.001% (v / v) to about 25% (v / v). In some embodiments, the at least one gas includes water vapor in an amount in the range of from about 0.01% (v / v) to about 20% (v / v). In some embodiments, the at least one gas includes water vapor in an amount in the range of from about 0.5% (v / v) to about 15% (v / v). In some embodiments, the at least one gas includes water vapor in an amount in the range of from about 0.5% (v / v) to about 4% (v / v). In some embodiments, the at least one gas includes water vapor in an amount in the range of from about 4% (v / v) to about 15% (v / v).

[0486] In some embodiments, the at least one gas is present in the source gas in an amount in the range of 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 in the range of 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 in the range of 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 in the range of from about 0.001% (v / v) to about 25% (v / v). In some embodiments, water vapor is present in an amount in the range of from about 0.01% (v / v) to about 20% (v / v). In some embodiments, water vapor is present in an amount in the range of from about 0.5% (v / v) to about 10% (v / v).

[0487] In some embodiments, capturing a quantity of the at least one gas with a functionalized adsorbent comprises adsorbing a quantity of the at least one gas with the functionalized adsorbent. In some embodiments, capturing a quantity of the at least one gas with a functionalized adsorbent comprises adsorbing a quantity of the at least one gas with the functionalized adsorbent in the presence of water vapor.

[0488] In some embodiments, the amount of the at least one gas captured with the functionalized adsorbent is in the range of from about 1% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured with the functionalized adsorbent is in the range of from about 10% (v / v) to about 90% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured with the functionalized adsorbent is in the range of from about 20% (v / v) to about 80% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured with the functionalized adsorbent is in the range of from about 30% (v / v) to about 70% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of the at least one gas captured with the functionalized adsorbent is in the range of from about 40% (v / v) to about 60% (v / v) of the at least one gas present in the source gas.

[0489] In some embodiments, the amount of at least one gas of 3614 captured by 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 of 3614 captured by 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 of 3614 captured by 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 of 3614 captured by 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 of 3614 captured by the functionalized adsorbent is in the range of about 1% (v / v) to about 5% (v / v) of the at least one gas present in the source gas.

[0490] In some embodiments, the amount of at least one gas of 3614 captured by 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 of 3614 captured by 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 of 3614 captured by 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 of 3614 captured by 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.

[0491] 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 decreasing 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, decreasing 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.

[0492] In many embodiments, the functionalized adsorbent, the source gas, at least one gas, or a combination thereof is at a certain temperature. Each temperature can be varied to facilitate the methods described herein. Each temperature can have a uniform temperature distribution, a gradient temperature distribution, a discrete temperature distribution, or a combination thereof.

[0493] 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, at least one gas, or a combination thereof is at a temperature in the range of about 0 °C to about 150 °C. In some embodiments, during the gas desorption cycle, at least one of the functionalized adsorbent, the source gas, at least one gas, or a combination thereof is at a temperature in the range of about 60 °C to about 250 °C.

[0494] In some embodiments, the method includes controlling the temperature. The temperature of the functionalized adsorbent, the source gas, at least one gas, or a combination thereof can be controlled.

[0495] Exemplary embodiments described herein include a method of collecting at least one gas from a gas source.

[0496] Figure 37 Is exemplary method flowchart 3710. In this exemplary embodiment, method flowchart 3710 depicts exemplary method steps of the method embodiments described herein and is not intended to limit these method embodiments. The method includes receiving 3712 at a functionalized adsorbent a gas source comprising at least one gas, wherein the functionalized adsorbent comprises: an adsorbent; and at least one functionalized ligand comprising an aminoorganosilane group. In some embodiments, the functionalized adsorbent comprises at least two functionalized ligands each comprising an aminoorganosilane group, wherein the aminoorganosilane groups are different from each other. In some embodiments, the functionalized adsorbent further comprises at least one functionalized ligand that does not comprise an aminoorganosilane group. The method further includes trapping 3714 a quantity of at least one gas with the functionalized adsorbent. The method further includes releasing 3716 at least one gas from the functionalized adsorbent. The adsorbent has an average particle length of ≤ 3 μm.

[0497] In some embodiments, the method includes: (I) receiving 3712 at a functionalized adsorbent a gas source comprising at least one gas, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising an aminoorganosilane group; (II) trapping 3714 a quantity of the at least one gas with the functionalized adsorbent; and (III) releasing 3716 the at least one gas from the functionalized adsorbent.

[0498] In some embodiments, releasing the at least one gas from the functionalized adsorbent includes purging the at least one gas from the functionalized adsorbent with a purge gas. In some embodiments, releasing the at least one gas from the functionalized adsorbent includes receiving a change in temperature or pressure at the functionalized adsorbent.

[0499] In some embodiments, releasing the at least one gas from the functionalized adsorbent to 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 compared to the source gas.

[0500] Other aspects of the disclosure are provided by the subject matter of the following clauses:

[0501] 1. A functionalized adsorbent comprising:

[0502] an adsorbent; and

[0503] at least one functionalized ligand comprising an aminoorganosilane group;

[0504] wherein the adsorbent has an average particle length of ≤3 μm.

[0505] 2. The functionalized adsorbent according to the preceding embodiment, further comprising at least one functionalized ligand that does not comprise an aminoorganosilane group.

[0506] 3. The functionalized adsorbent according to any one of the preceding embodiments, wherein the at least one functionalized ligand comprising an aminoorganosilane group and the at least one functionalized ligand that does not comprise an aminoorganosilane group are present in a ratio in the range of about 10:1 to about 1:10.

[0507] 4. The functionalized adsorbent according to any one of the preceding embodiments, wherein the functionalized adsorbent is a functionalized MOF compound of formula (A-I)

[0508]

[0509] wherein:

[0510] M is a MOF metal or a metal-containing cluster;

[0511] L is a MOF linker;

[0512] F A is the at least one functionalized ligand comprising an aminoorganosilane group;

[0513] F Bis at least one functionalized ligand that does not contain an amino organosilicon group;

[0514] x is a value in the range of 1 to 6;

[0515] y is a value in the range of 1 to 6;

[0516] a is a value greater than 0 and less than or equal to 2; and

[0517] b is a value in the range of 0 to 2.

[0518] 5. The functionalized adsorbent according to any one of the preceding embodiments, wherein the MOF metal or metal-containing cluster comprises a metal selected from the group consisting of: alkali metals, alkaline earth metals, transition metals, Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, their ions, their hydrates, their salts, their halides, their fluorides, their chlorides, their bromides, their iodides, their nitrates, their acetates, their sulfates, their phosphates, their carbonates, their oxides, their formates, their carboxylates, and combinations thereof.

[0519] 6. The functionalized adsorbent according to any one of the preceding embodiments, wherein the MOF linker comprises a linker selected from the group consisting of: polyhedral linkers, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxobiphenyl-3,3'-dicarboxylate (dobpdc 4- )、4,4"-dioxo-[1,1':4',1"-terphenyl]-3,3"-dicarboxylate (dotpdc 4- )、2,5-dioxobenzene-1,4-dicarboxylate (dobdc 4- )、4,6-dihydroxyisophthalic acid (m-dobdc 4- )、3,3'-dioxo-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4-), 4,4'-[oxybis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), dicarboxylates, terephthalic acid, tricarboxylates, 1,3,5-benzenetricarboxylic acid, azoles, tetrazoles, 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, terephthalic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxyphenyl)-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindane dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9 - Trioxaundecanedicarboxylic acid, o - Hydroxybenzophenonedicarboxylic acid, Pluriol E 300 - dicarboxylic acid, Pluriol E 400 - dicarboxylic acid, Pluriol E 600 - dicarboxylic acid, Pyrazole - 3,4 - dicarboxylic acid, 2,3 - Pyrazinedicarboxylic acid, 5,6 - Dimethyl - 2,3 - pyrazinedicarboxylic acid, 4,4'-Diaminodiphenyletherdiimide dicarboxylic acid, 4,4'-Diaminodiphenylmethanedimide dicarboxylic acid, 4,4'-Diaminodiphenylsulfonedimide dicarboxylic acid, 2,6 - Naphthalenedicarboxylic acid, 1,3 - Adamantanedicarboxylic acid, 1,8 - Naphthalenedicarboxylic acid, 2,3 - Naphthalenedicarboxylic acid, 8 - Methoxy - 2,3 - naphthalenedicarboxylic acid, 8 - Nitro - 2,3 - naphthalenedicarboxylic acid, 8 - Sulfonyl - 2,3 - naphthalenedicarboxylic acid, 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, Eicosenedicarboxylic acid, 4,4'-Dihydroxydiphenylmethane - 3,3'-dicarboxylic acid, 1 - Amino - 4 - methyl - 9,10 - dioxo - 9,10 - dihydroanthracene - 2,3 - dicarboxylic acid, 2,5 - Pyridinedicarboxylic acid, Cyclohexene - 2,3 - dicarboxylic acid, 2,9 - Dichlorofluorescein ring - 4,11 - dicarboxylic acid, 7 - Chloro - 3 - methylquinoline - 6,8 - dicarboxylic acid, 2,4 - Dichlorobenzophenone - 2',5'-dicarboxylic acid, 1,3 - Benzenedicarboxylic acid, 2,6 - Pyridinedicarboxylic acid, 1 - Methylpyrrole - 3,4 - dicarboxylic acid, 1 - Benzyl - 1H - pyrrole - 3,4 - dicarboxylic acid, Anthraquinone - 1,5 - dicarboxylic acid, 3,5 - Pyrazoledicarboxylic acid, 2 - Nitrobenzene - 1,4 - dicarboxylic acid, Heptane - 1,7 - dicarboxylic acid, Cyclobutane - 1,1 - dicarboxylic acid, 1,14 - Tetradecanedicarboxylic acid, 5,6 - Dehydronorbornane - 2,3 - dicarboxylic acid, 5 - Ethyl - 2,3 - pyridinedicarboxylic acid, 2 - Hydroxy - 1,2,3 - propanetricarboxylic acid, 7 - Chloro - 2,3,8 - quinolinetricarboxylic acid, 1,2,4 - Benzenetricarboxylic acid, 1,2,4 - Butanetricarboxylic acid, 2 - Phosphono - 1,2,4 - butanetricarboxylic acid, 1,3,5 - Benzenetricarboxylic acid, 1 - Hydroxy - 1,2,3 - propanetricarboxylic acid, 4,5 - Dihydro - 4,5 - dioxo - 1H - pyrrolo[2,3 - f]quinoline - 2,7,9 - tricarboxylic acid, 5 - Acetyl - 3 - amino - 6 - methylbenzene - 1,2,4 - tricarboxylic acid, 3 - Amino - 5 - benzoyl - 6 - methylbenzene - 1,2,4 - tricarboxylic acid, 1,2,3 - Propanetricarboxylic acid, Aurintricarboxylic acid, 1,1 - Dioxide - perylene[1,12 - bcd]thiophene - 3,4,9,10 - pyromellitic acid, perylene tetracarboxylic acid, perylene - 3,4,9,10 - tetracarboxylic acid, perylene - 1,12 - sulfone - 3,4,9,10 - tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4 - butane tetracarboxylic acid, meso - 1,2,3,4 - butane tetracarboxylic acid, decane - 2,4,6,8 - tetracarboxylic acid, 1,4,7,10,13,16 - hexaoxacyclooctadecane - 2,3,11,12 - tetracarboxylic acid, 1,2,4,5 - benzenetetracarboxylic acid, 1,2,11,12 - dodecanetetracarboxylic acid, 1,2,5,6 - hexanetetracarboxylic acid, 1,2,7,8 - octanetetracarboxylic acid, 1,4,5,8 - naphthalenetetracarboxylic acid, 1,2,9,10 - decanetetracarboxylic acid, benzophenone tetracarboxylic acid, 3,3',4,4' - benzophenone tetracarboxylic acid, tetrahydrofuran tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclopentane - 1,2,3,4 - tetracarboxylic acid, polyhedral linker, double - sided linker, triple - sided linker, quadruple - sided linker, penta - sided linker, hexa - sided linker, hepta - sided linker, octa - sided linker, mixed linker, asymmetric linker, metal linker, N - heterocyclic linker, their protonated, partially or fully deprotonated forms, and combinations thereof.,

[0520] 7. The functionalized adsorbent according to any one of the preceding embodiments, wherein the adsorbent has an aspect ratio > 0.2.

[0521] 8. The functionalized adsorbent according to any one of the preceding embodiments, wherein the adsorbent has an average particle length < 1 μm.

[0522] 9. The functionalized adsorbent according to any one of the preceding embodiments, wherein the at least one functionalized ligand comprising an amino - organic silicon group is an amino - substituted siloxane of formula (A - II), formula (A - III), formula (A - IV), formula (A - V), formula (A - VI) or formula (A - VII)

[0523]

[0524]

[0525]

[0526] Wherein:

[0527] R1, R2, R3, R4, R9, R 10 , R 13 , R 14 and R 18Each 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-chain heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0528] R5, R6, R 11 , R 15 and R 17 Each independently selected from the group consisting of: direct bond, 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,

[0529] R7, R8, R 12 and R 16 Each independently selected from the group consisting of: direct bond, 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, C6 alkyl, and the substituent of formula (A-VIII)

[0530]

[0531] Wherein:

[0532] The wavy bond represents the bonding position with formula (A-II) or formula (A-III) or formula (A-IV) or formula (A-V) or formula (A-VI) or formula (A-VII);

[0533] 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;

[0534] R 25 and R 26Each 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 form a monocyclic ring selected from the group consisting of heterocycloalkyl and heteroaryl;

[0535] R 27 、R 28 and R 29 Each independently selected from the group consisting of: a direct bond, 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, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-;

[0536] R 30 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, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl;

[0537] j is an integer in the range of 0 to 20;

[0538] k is an integer in the range of 0 to 20;

[0539] m is an integer in the range of 0 to 20; and

[0540] n is an integer in the range of 0 to 20.

[0541] 10. The functionalized adsorbent according to any one of the preceding embodiments, wherein the at least one functionalized ligand comprising an aminoorganosilane group is selected from the group consisting of:

[0542]

[0543]

[0544]

[0545]

[0546]

[0547] and

[0548]

[0549] 11. An adsorbent system comprising the functionalized adsorbent according to any one of the foregoing embodiments.

[0550] 12. A method for preparing an adsorbent, the method comprising:

[0551] (I) forming a mixture comprising:

[0552] an adsorbent precursor;

[0553] a crystal growth inhibitor;

[0554] an optional solvent; and

[0555] an optional non-solvent; and

[0556] (II) reacting the mixture;

[0557] wherein the adsorbent has an average particle length of ≤ 3 μm.

[0558] 13. The method according to the foregoing embodiment, wherein the adsorbent precursor comprises a MOF linker and a MOF metal or a metal-containing cluster.

[0559] 14. The method according to any one of the foregoing embodiments, wherein the solvent comprises an aqueous solvent.

[0560] 15. The method according to any one of the foregoing embodiments, wherein the crystal growth inhibitor is selected from the group consisting of salicylic acid, 4-fluorosalicylic acid, 4,4'-biphenol, 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC), 2,2'-bipyridine-5,5'-dimethanol (BPYDM), benzoic acid, biphenol, bipyridine, and combinations thereof.

[0561] 16. A method for preparing a functionalized adsorbent, the method comprising:

[0562] (I) forming a mixture comprising:

[0563] the adsorbent prepared according to any one of the foregoing embodiments;

[0564] at least one functionalized ligand comprising an amino organosilicon group;

[0565] Optionally, at least one functionalized ligand that does not contain an amino organosilicon group;

[0566] Optionally, a solvent; and

[0567] Optionally, a non-solvent; and

[0568] (II) Functionalize the adsorbent.

[0569] 17. A method for capturing at least one gas, the method comprising:

[0570] (I) Receiving a gas source containing the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises:

[0571] An adsorbent, wherein the adsorbent has an average particle length of ≤ 3 μm;

[0572] At least one functionalized ligand containing an amino organosilicon group; and

[0573] (II) Capturing a certain amount of the at least one gas with the functionalized adsorbent.

[0574] 18. The method according to the foregoing embodiment, wherein the gas source is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0575] 19. The method according to any one of the foregoing embodiments, wherein the at least one gas is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0576] 20. A method for collecting at least one gas from a gas source, the method comprising:

[0577] Capturing the at least one gas according to the method of any one of the foregoing embodiments, and

[0578] (III) □ Releasing the at least one gas from the functionalized adsorbent.

[0579] A solid adsorbent material functionalized with a polyamine having a cyclic unit.

[0580] This disclosure describes a polyamine-functionalized solid adsorbent material with at least one cyclic ring unit, where the cyclic ring unit includes an alicyclic unit or an aromatic unit or a combination of both. For example, magnesium-based metal-organic framework 274 (MOF-274) is functionalized using various polyamines containing cyclic units. The adsorbent materials developed in this disclosure exhibit high adsorption capacity for carbon dioxide and low desorption residues under mild desorption conditions.

[0581] Generally, the functionalized adsorbents according to this disclosure can be used in conjunction with the compositions, systems, and methods according to this disclosure. The functionalized adsorbents are not limited to any specific embodiments disclosed herein.

[0582] In some embodiments, the functionalized adsorbent includes a first type of functionalized ligand, where the first type of functionalized ligand includes at least one functionalized ligand, and the functionalized ligand includes a polyamine containing at least one cyclic unit. Generally, at least one functionalized ligand including a polyamine containing at least one cyclic unit can include any such suitable ligand that promotes the functionalized adsorbents described herein. At least one functionalized ligand including a polyamine containing at least one cyclic unit can include only one functionalized ligand, or two or more functionalized ligands, where the one functionalized ligand includes a polyamine containing at least one cyclic unit, and the two or more functionalized ligands each include a polyamine containing at least one cyclic unit.

[0583] Generally, the adsorbent can be any suitable adsorbent known in the art that promotes the functionalized adsorbents described herein. Suitable adsorbents are described in detail above.

[0584] In addition, in some embodiments, the functionalized adsorbent includes a metal-organic framework (MOF), where the first amine of the polyamine is attached to the first metal site of the MOF, and optionally where the second amine of the polyamine is attached to the second metal site of the MOF.

[0585] In some embodiments, the functionalized adsorbent is a functionalized MOF compound of formula (C-V)

[0586]

[0587] where:

[0588] M is a MOF metal or a metal-containing cluster;

[0589] L is a MOF linker;

[0590] F A is at least one functionalized ligand, and the functionalized ligand includes a polyamine containing at least one cyclic unit;

[0591] F B is at least one functionalized ligand that does not include a polyamine containing at least one cyclic unit;

[0592] x is a value in the range of 1 to 6;

[0593] y is a value in the range of 1 to 6;

[0594] a is a value greater than 0 and less than or equal to 2; and

[0595] b is a value in the range of 0 to 2.

[0596] 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 cyclic unit. In some embodiments, the functionalized adsorbent further includes at least one functionalized ligand that does not include a polyamine containing at least one cyclic unit. Generally, at least one functionalized ligand that does not include a polyamine containing at least one cyclic unit can include any such suitable ligand that promotes the functionalized adsorbent described herein. At least one functionalized ligand that does not include a polyamine containing at least one cyclic unit can include only one functionalized ligand, or two or more functionalized ligands, the one functionalized ligand not including a polyamine containing at least one cyclic unit, the two or more functionalized ligands each not including a polyamine containing at least one cyclic unit.

[0597] In some embodiments, at least one functionalized ligand that does not include a polyamine containing at least one cyclic unit is selected from the group consisting of: aminoorganosilane ligands, amine ligands, monoamine ligands, diamine ligands, triamine ligands, tetraamine ligands, pentaamine ligands, hexaamine ligands, polyamine ligands, alkylamine ligands, and amino alcohol ligands. Exemplary ligands include, but are not limited to, ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, bis(N-methyl)ethylenediamine, N-isopropylethylenediamine, N,N-dimethyl-N-methylethylenediamine, bis(N,N-dimethyl)ethylenediamine, N,N-diisopropylethylenediamine, 2,2-dimethyl-1,3-diaminopropane, 1,3-diaminopentane, diethylenetriamine, N-(2-aminoethyl)-1,3-propanediamine, bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane (spermidine), triethylenetetramine, N,N'-bis(2-aminoethyl)-1,3-propanediamine, 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, N,N'-bis(3-aminopropyl)-1,4-diaminobutane (spermine), tetraethylenepentamine, and / or combinations thereof.

[0598] In some embodiments, at least one functionalized ligand comprising a polyamine that does not contain at least one cyclic unit comprises at least one aminoorganosilane selected from the group consisting of: linear aminoorganosilanes, cyclic aminoorganosilanes, branched aminoorganosilanes, amino-substituted siloxanes, linear amino-substituted disiloxanes, cyclic amino-substituted disiloxanes, linear amino-substituted trisiloxanes, cyclic amino-substituted trisiloxanes, linear amino-substituted tetrasiloxanes, cyclic amino-substituted tetrasiloxanes, linear amino-substituted polysiloxanes, cyclic amino-substituted polysiloxanes, silsesquioxanes, polyhedral silsesquioxanes, and combinations thereof.

[0599] Typically, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit can be present in any suitable ratio known in the art to facilitate the functionalized adsorbents described herein. In some embodiments, the ratio is selected from the group consisting of molar ratio, weight ratio, and volume ratio. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio in the range of about 10:1 to about 1:10. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio in the range of about 9:1 to about 1:9. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio in the range of about 8:1 to about 1:8. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio in the range of about 7:1 to about 1:7. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio in the range of about 6:1 to about 1:6. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio in the range of about 5:1 to about 1:5. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio in the range of about 4:1 to about 1:4. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio in the range of about 3:1 to about 1:3. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio in the range of about 2:1 to about 1:2. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio of about 1:1.

[0600] In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit is present in an amount less than the at least one functionalized ligand that does not comprise a polyamine comprising at least one cyclic unit.

[0601] In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit 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.

[0602] In many embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit can be any suitable at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit known in the art to facilitate the formation of the functionalized adsorbents described herein.

[0603] 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 primary amines, secondary amines, tertiary amines, and combinations thereof. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises at least one primary amine or at least one secondary amine.

[0604] In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentamines, hexamines, polyamines, and combinations thereof.

[0605] In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises a symmetric structure. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises an asymmetric structure.

[0606] In some embodiments, the at least one cyclic unit is selected from the group consisting of alicyclic units, aromatic units, and combinations thereof.

[0607] In many embodiments, polyamines comprising at least one cyclic unit are described herein. In some embodiments, the polyamine comprising at least one cyclic unit is a functionalized ligand. In some embodiments, the polyamine comprising at least one cyclic unit is a functionalized ligand for functionalizing an adsorbent.

[0608] In many embodiments, the functionalized ligand comprising a polyamine comprises at least one cyclic unit according to formula (C-I):

[0609]

[0610] in:

[0611] B, C and D each independently comprise at least one amine group;

[0612] x, y and z are each independently 0 or 1; and

[0613] A comprises an aromatic ring structure according to formula (C-II), or an alicyclic structure according to formula (C-III):

[0614]

[0615] in:

[0616] n is an integer ranging from about 3 to about 8;

[0617] m is an integer in the range of about 3 to about 5; and

[0618] A 1 , A 2 , A 3 and A 4 Each independently includes at least one of carbon, oxygen and silicon.

[0619] In some embodiments, A 1 , A 2 , A 3 and A 4 Each independently selected from the group consisting of:

[0620] 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;

[0621] unsubstituted oxygen;

[0622] Silicon 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; and

[0623] A combination of them.

[0624] In some embodiments, B, C, and D each independently comprise a structure according to Formula (C-IV):

[0625] E t -F u -G v -H w (Formula C-IV)

[0626] Wherein:

[0627] t, u, v, and w are each independently an integer in the range of about 0 to about 10; and

[0628] E, F, G, and H are each independently selected from the group consisting of:

[0629] 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;

[0630] NH2, NHR1, and NR1R2,

[0631] wherein R1 and R2 are each independently selected from the group consisting of: 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; and

[0632] their combinations.

[0633] In some embodiments, the polyamine includes at least two cyclic units, wherein the polyamine includes a polycyclic structure connected by at least one linking group selected from the group consisting of: 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.

[0634] In some embodiments, the polyamine includes at least one bicyclic unit.

[0635] In some embodiments, the polyamine includes at least two cyclic units, wherein the polyamine includes a bridged polycyclic structure containing at least one bridging group selected from the group consisting of: 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.

[0636] In some embodiments, the polyamine includes at least one bridged cyclic unit.

[0637] In some embodiments, t, u, v, and w are each independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0638] In some embodiments, n is 3, 4, 5, 6, 7, or 8.

[0639] In some embodiments, m is 3, 4, or 5.

[0640] 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, each of x, y, and z is 1.

[0641] Generally, each of B, C, and D can be attached to any suitable A atom that facilitates the formation of the functionalized adsorbent according to the present disclosure. In many embodiments, each of B, C, and D is attached to an independent atom of the A ring unit. In some embodiments, each of B, C, and D is attached to an 1 A 2 A 3 andA 4

[0642] In some embodiments, the polyamine includes at least one substituent at a substituent position selected from the group consisting of 1,2 (ortho), 1,3 (meta), 1,4 (para), and combinations thereof.

[0643] In some embodiments, at least two of B, C, and D are arranged ortho to each other in the A ring unit. In some embodiments, at least two of B, C, and D are arranged meta to each other in the A ring unit. In some embodiments, at least two of B, C, and D are arranged para to each other in the A ring unit.

[0644] In some embodiments, the polyamine includes an isomer selected from the group consisting of a cis isomer, a trans isomer, an R - enantiomer, an S - enantiomer, and combinations thereof.

[0645] In some embodiments, at least two of B, C, and D are different. In some embodiments, B, C, and D are different.

[0646] In some embodiments, at least two of B, C, and D are the same. In some embodiments, B, C, and D are the same.

[0647] 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.

[0648] Generally speaking, the polyamine can include any number of amine groups known in the art suitable for promoting the formation of a functionalized adsorbent. In some embodiments, the polyamine includes a total number of amine groups in the range of from about 2 to about 10. In some embodiments, the polyamine includes a total number of amine groups in the range of from about 2 to about 6. In some embodiments, the polyamine includes a total number of amine groups in the range of from about 2 to about 4. In some embodiments, the polyamine includes 2, 3, 4, 5, 6, 7, 8, 9, or 10 amine groups.

[0649] In some embodiments, the polyamine is a compound selected from the group consisting of

[0650]

[0651]

[0652]

[0653]

[0654]

[0655]

[0656] and

[0657] combinations thereof.

[0658] The following exemplary polyamines have cyclic units in accordance with the present disclosure:

[0659] Aliphatic cyclic (6-ring) amines:

[0660] GE201 (mixture of cis and trans); GE182 (trans); GE200 (cis); 1,4-cyclohexanediamine (p-CHD) (mw: 114; bp = 197 °C).

[0661]

[0662] GE181; GE187 (mixture of cis and trans); GE199 (cis); 1,3-cyclohexanediamine (m-CHD) (mw: 114; bp = 194 °C).

[0663]

[0664] GE202 (mixture of cis and trans); GE203 (cis); GE209 (trans); 1,2-cyclohexanediamine (o-CHD) (mw: 114; bp = 194 °C).

[0665]

[0666] Di- / Tri- / Tetra-amine:

[0667] GE221-A2109; 1,3,5-Cyclohexanetriyltrimethylamine (CHTM) (mw = 171.316; bp = 309 °C)

[0668]

[0669] GE254; GE255 (BPDCH)

[0670]

[0671] 3-Cyclo-3

[0672]

[0673] Primary / Secondary / Tertiary amine:

[0674] N,N-Dimethylcyclohexanediamine (N2MCHD) (mw: 142.24; bp at 18 mmHg = 80 °C)

[0675]

[0676] Cis or trans isomers and chirality:

[0677] (R,R)-1,2-Cyclohexanediamine (trans)

[0678]

[0679] (S,S)-Cyclohexanediamine (trans)

[0680]

[0681] (R,S)-Cyclohexanediamine (cis)

[0682]

[0683] Different lengths:

[0684] GE193 (mixture of isomers); 1,4-Bis(aminomethyl)-cyclohexane (BAMCH) (mw: 142.24; bp = 239 °C)

[0685]

[0686] GE206 (mixture of isomers); 1,3-Bis(aminomethyl)-cyclohexane (mBAMCH) (mw: 142.24; bp = 240 °C)

[0687]

[0688] GE248; GE249 (BEDCH)

[0689]

[0690] Structure with multiple cyclic units:

[0691] GE216; 4,4'-Methylenebis(2-methylcyclohexylamine) (mixture of isomers) (MCHA)

[0692]

[0693] Asymmetric structure:

[0694] GE205 (mixture of isomers); 4-(Aminomethyl)cyclohexylamine (AMCHA)

[0695]

[0696] GE240; 4-(2-Aminoethyl)cyclohexylamine (mixture of cis and trans) (ACHEA)

[0697]

[0698] GE256; N-(3-Aminopropyl)cyclohexylamine (BPDCH)

[0699]

[0700] Mixed amines:

[0701] GE234; GE235; Mixture of 1,4-bis(aminomethyl)cyclohexane (BAMCH) and spermine

[0702]

[0703] GE236; GE237; Mixture of 1,4-bis(aminomethyl)cyclohexane (BAMCH) and spermidine

[0704]

[0705] GE285; GE291; Mixture of BEDCH and spermine

[0706]

[0707] Substitution:

[0708] GE208; Isophorone diamine (IPRDA) (mw: 170.3; bp = 252.9 °C)

[0709]

[0710] Bridged bicyclic structure:

[0711] GE214 bis(aminomethyl)norbornane (BAMNB) (mixture of isomers) (mw: 154.25; bp = 259 °C)

[0712]

[0713] Heterocyclic amine:

[0714] GE204; [(2S,5R)-5-(aminomethyl)oxolan-2-yl]methanamine; tetrahydrofuran-2,5-diamine (AMTHF) (mw: 130.18)

[0715]

[0716] Aromatic(6) amine / substituted

[0717] GE183, GE184; m-xylenediamine (m-XYD) (mw: 136; bp = 265 °C)

[0718]

[0719] GE185; GE186; GE189; p-xylenediamine (p-XYD) (mw: 136; bp = 230 °C)

[0720]

[0721] Primary / secondary / tertiary amine:

[0722] GE225; N-methyl-1-[4-(methylaminomethyl)phenyl]methanamine (Me-p-XYD) (mw: 164.20)

[0723]

[0724] Mixed amine:

[0725] GE226; GE227; mixture of p-xylenediamine (p-XYD) and 1,3,5-benzenetriyltrimethylamine (BTM)

[0726]

[0727] GE247; GE251; mixture of p-xylenediamine (p-XYD) and N 1 ,N 1' -((1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(propane-1,3-diamine) (APAP)

[0728]

[0729] Heteroaromatic amines:

[0730] GE195; 2,5-bis(aminomethyl)furan (mw: 126.16 g / mol, bp = 230 °C).

[0731]

[0732] GE217; tetrafluoro-p-xylylenediamine (TF-p-XYD) (mw: 2018.16)

[0733]

[0734] Di- / tri- / tetra- / penta- / hexamines

[0735] GE220-A2107; 1,3,5-benzenetriyltrimethylamine (BTM) (mw: 165.24; bp = 329 °C)

[0736]

[0737] GE222; GE223 (Ph-3-ED)

[0738]

[0739] GE252; GE253 (Ph-3-PD)

[0740]

[0741] In some embodiments, the polyamine is selected from the group consisting of:

[0742]

[0743]

[0744] cyclohexanediamine, and

[0745] combinations thereof.

[0746] It has been found that one or more of a reduced adsorbent particle size, an increased adsorbent aspect ratio, and an aqueous adsorbent synthesis result in an adsorbent with significantly improved CO2 absorption kinetics.

[0747] Typically, the adsorbent can include any suitable particle size known in the art that promotes the functionalized adsorbents described herein. 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 ≥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.

[0748] Typically, the adsorbent can include any suitable aspect ratio known in the art that promotes the functionalized adsorbents described herein. As used herein, the 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 in the range of 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.

[0749] In some embodiments, the particle size is a single particle size. The single particle size measurement can be performed according to any suitable means known in the art, such as by measuring the particle size in a SEM image.

[0750] In some embodiments, the particle size measurement result is an average particle size measurement result. The average particle size measurement can be performed according to any suitable means known in the art, such as by analyzing particle size distribution information.

[0751] Generally, the particle size of the adsorbent can be controlled, altered, or reduced according to any suitable technique known in the art for facilitating the functionalized adsorbents described herein. In some embodiments, suitable techniques for controlling, altering, or reducing the particle size include mechanical grinding (e.g., mortar and pestle), using a microfluidizer, dry milling, wet milling, chemical size reduction (e.g., incorporating a crystal growth inhibitor), sonication, hydrodynamic cavitation, and combinations thereof.

[0752] Generally, the adsorbent can be in any suitable form known in the art for facilitating the functionalized adsorbents described herein. In some embodiments, the form of the adsorbent is selected from the group consisting of powders, pellets, composites, composites mixed with binders, membranes, coatings, packed beds, columns, monoliths, and combinations thereof.

[0753] Exemplary embodiments described herein include adsorbent systems. Generally, the adsorbent system can be any suitable adsorbent system known in the art for facilitating 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 polymer membrane.

[0754] In some embodiments, the adsorbent system includes at least one contactor. In some embodiments, the adsorbent system includes more than one contactor. In some embodiments, the adsorbent system includes 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 for facilitating 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 the adsorbent system. In some embodiments, the contactor includes more than one adsorbent coating, wherein at least one adsorbent coating is the adsorbent system.

[0755] In some embodiments, the adsorbent system includes a framework. The framework can be any suitable framework known in the art for facilitating the functionalized adsorbents described herein. The framework can be included in a contactor or between two contactors. The framework can consist of one component or more than one component. In some embodiments, the framework is an air framework. In some embodiments, the configuration of the framework is selected from the group consisting of polygonal configurations, rectangular configurations, square configurations, circular configurations, asymmetric configurations, and combinations thereof. In some embodiments, the adsorbent system is mounted on the framework.

[0756] In some embodiments, the adsorbent system includes at least one concentrator. The concentrator can be any suitable concentrator known in the art for facilitating the functionalized adsorbents described herein. The concentrator can be a passive concentrator or an active concentrator.

[0757] 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 known in the art for promoting the functionalized adsorbents described herein that is configured to drive fluid flow. In some embodiments, the component configured to drive fluid flow is selected from the group consisting of pumps, fans, and combinations thereof.

[0758] 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 known in the art for promoting the functionalized adsorbents described herein that is configured to change temperature. In some embodiments, the component configured to change temperature is selected from the group consisting of heaters, coolers, and combinations thereof.

[0759] In some embodiments, the adsorbent system includes at least one component configured to convey fluid. The component configured to convey fluid can be any suitable component known in the art for promoting the functionalized adsorbents described herein that is configured to convey fluid. In some embodiments, the component configured to convey fluid is selected from the group consisting of pipes, perforated pipes, plastic perforated pipes, polymer perforated pipes, metal perforated pipes, composite perforated pipes, and combinations thereof.

[0760] Generally, the functionalized adsorbents can 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 an adsorbent system. In some embodiments, the functionalized adsorbents are used in a carbon capture adsorbent system. In some embodiments, the functionalized adsorbents are used in a moisture adsorbent system. In some embodiments, the functionalized adsorbents are used in a carbon capture adsorbent system 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 CO2 capture and / or direct air capture of CO2.

[0761] The exemplary embodiments described herein include methods of preparing an adsorbent system. Generally, the functionalized adsorbents can be prepared according to any suitable synthetic methods known in the art for promoting the functionalized adsorbents described herein.

[0762] In many embodiments, the method of preparing an adsorbent system includes preparing an adsorbent, wherein the adsorbent has an average particle length of ≤3 μm, and optionally functionalizing the adsorbent with at least one functionalizing ligand comprising a polyamine including at least one cyclic unit.

[0763] In some embodiments, a method of preparing an adsorbent system includes functionalizing an adsorbent with at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit. In some embodiments, a method of preparing an adsorbent system includes functionalizing an adsorbent with at least two functionalizing ligands each comprising a polyamine comprising at least one cyclic unit, wherein the polyamines comprising at least one cyclic unit are different from each other. In some embodiments, a method of preparing an adsorbent system further includes functionalizing the adsorbent with at least one functionalizing ligand that does not include a polyamine comprising at least one cyclic unit. In some embodiments, a method of preparing an adsorbent system includes controlling the ratio between at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit and at least one functionalizing ligand that does not include a polyamine comprising at least one cyclic unit.

[0764] In some embodiments, a method of preparing an adsorbent system further includes annealing the functionalized adsorbent. Annealing the adsorbent system can remove excess ligand. In some embodiments, annealing the functionalized adsorbent includes annealing the functionalized 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.

[0765] Figure 87 is exemplary method flow diagram 8710. In this exemplary embodiment, method flow diagram 8710 depicts exemplary steps of the method embodiments described herein and is not intended to limit these method embodiments. In this exemplary embodiment, the method includes forming 8712 a mixture that includes: an adsorbent precursor; a crystal growth inhibitor; an optional solvent; and an optional non-solvent. The method further includes reacting 8714 the mixture. The adsorbent has an average particle length of ≤3 μm.

[0766] Forming 8712 the mixture can be carried out 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.

[0767] 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 mixture formation 8712 and added to the mixture as a single component, or can be formed in situ in the mixture during mixture formation 8712. For example, the MOF linker can be deprotonated separately and then added in situ or deprotonated. Similarly, the MOF metal or metal-containing cluster can be pre-formed and then added in situ or formed.

[0768] In some embodiments, the solvent comprises an aqueous solvent. In some embodiments, the solvent comprises water. Using an aqueous solvent can provide several benefits. In particular, compared to at least some known methods for preparing MOF compounds, using an aqueous solvent has advantages in terms of scalability, safety, cost, and waste treatment. In addition, MOF compounds prepared with an aqueous solvent are generally easier to purify than the same MOF compounds prepared according to known methods, for example, by solvent washing. This improved purification results from the relatively easy removal of solvent molecules (e.g., water) from the MOF compounds described herein compared to the removal of strongly bound solvent molecules (e.g., DMF) utilized in preparing the same MOF compounds according to known methods. 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, the purification is improved by a purification method that requires less toxicity.

[0769] 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.

[0770] Generally, an anti-solvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, the anti-solvent is a liquid-based component included in the reaction mixture. In some embodiments, the anti-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, the anti-solvent is selected from the group consisting of organic solvents, aqueous solvents, and combinations thereof.

[0771] In some embodiments, the crystal growth inhibitor is selected from the group consisting of salicylic acid, 4-fluorosalicylic acid, 4,4'-biphenol, 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC), 2,2'-bipyridine-5,5'-dimethanol (BPYDM), benzoic acid, biphenol, bipyridine, and combinations thereof.

[0772] In some embodiments, a method of preparing an adsorbent system includes functionalizing an adsorbent with at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit. In some embodiments, a method of preparing an adsorbent system includes functionalizing an adsorbent with at least two functionalizing ligands each comprising a polyamine comprising at least one cyclic unit, wherein the aminoorganosilane groups are different from each other. In some embodiments, a method of preparing an adsorbent system further includes functionalizing an adsorbent with at least one functionalizing ligand that does not include a polyamine comprising at least one cyclic unit. In some embodiments, a method of preparing an adsorbent system includes controlling the ratio between at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit and at least one functionalizing ligand that does not include a polyamine comprising at least one cyclic unit.

[0773] In some embodiments, a method of preparing an adsorbent system further includes annealing the functionalized adsorbent. Annealing the adsorbent system can remove excess ligand. In some embodiments, annealing the functionalized adsorbent includes annealing the functionalized 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.

[0774] Figure 88 is exemplary method flow chart 8810. In this exemplary embodiment, method flow chart 8810 depicts exemplary steps of the method embodiments described herein and is not intended to limit these method embodiments. In this exemplary embodiment, the method includes forming 8812 a mixture that includes: an adsorbent; at least one functionalizing ligand that includes a polyamine comprising at least one cyclic unit; optionally at least one functionalizing ligand that does not include a polyamine comprising at least one cyclic unit; optionally a solvent; and optionally a non-solvent. The method further includes functionalizing 8814 the adsorbent.

[0775] In some embodiments, functionalizing 8814 the adsorbent includes stirring the mixture.

[0776] In some embodiments, functionalizing 8814 the adsorbent includes functionalizing 8814 the adsorbent in the presence of an inert gas.

[0777] In some embodiments, the functionalized 8814 adsorbent comprises functionalizing the 3514 adsorbent at a temperature in the range of from about 0 °C to about 100 °C. In some embodiments, the functionalized 8814 adsorbent comprises functionalizing the 3514 adsorbent at a temperature in the range of from about 20 °C to about 80 °C. In some embodiments, the functionalized 8814 adsorbent comprises functionalizing the 3514 adsorbent at a temperature in the range of from about 20 °C to about 60 °C.

[0778] In some embodiments, the functionalized 8814 adsorbent comprises functionalizing the 8814 adsorbent for a time in the range of from about 1 minute to about 7 days. In some embodiments, the functionalized 8814 adsorbent comprises functionalizing the 8814 adsorbent for a time in the range of from about 1 hour to about 3 days.

[0779] In some embodiments, the adsorbent is desolvated prior to functionalizing 8814. In some embodiments, the adsorbent is dry prior to functionalization.

[0780] In some embodiments, the adsorbent is annealed after functionalizing 8814. 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 from about 50 °C to about 400 °C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of from about 100 °C to about 300 °C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of from about 150 °C to about 250 °C.

[0781] 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.

[0782] Generally, a non-solvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, the non-solvent is a liquid-based component included in the reaction mixture. In some embodiments, the non-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, the non-solvent is selected from the group consisting of organic solvents, aqueous solvents, and combinations thereof.

[0783] In some embodiments, the non-solvent aids in functionalization. In some embodiments, the selectivity of the functionalization is controlled by relative solubility. For example, one or more adsorbents or amines may have different solubilities in a liquid-based reaction mixture compared to another adsorbent or amine or functionalized adsorbent. In this way, relative solubility introduces limitations on the reaction and / or the reagents.

[0784] In many embodiments, the method may further include any other suitable processing steps known in the art to facilitate the success of the methods described herein. Such processing steps may include, but are not limited to, washing, drying, filtering, purifying, separating, centrifuging, 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.

[0785] Exemplary embodiments described herein include a method of trapping at least one gas.

[0786] Figure 89 is exemplary method flow chart 8910. In this exemplary embodiment, method flow chart 8910 depicts exemplary method steps of the method embodiments described herein and is not intended to limit these method embodiments. The method includes receiving 8912 a gas source containing at least one gas at a functionalized adsorbent, where the functionalized adsorbent includes: an adsorbent; and at least one functionalized ligand, the functionalized ligand including a polyamine containing at least one cyclic unit. In some embodiments, the functionalized adsorbent includes at least two functionalized ligands each including a polyamine containing at least one cyclic unit, where the polyamines containing at least one cyclic unit 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 cyclic unit. The method further includes trapping 8914 an amount of at least one gas with the functionalized adsorbent. The adsorbent may have an average particle length of ≤3 μm.

[0787] In some embodiments, the method includes: (I) receiving 8912 a gas source containing the at least one gas at a functionalized adsorbent, where the functionalized adsorbent includes an adsorbent and at least one functionalized ligand, the functionalized ligand including a polyamine containing at least one cyclic unit; and (II) trapping 8914 an amount of the at least one gas with the functionalized adsorbent.

[0788] 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, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0789] Typically, the at least one gas can be any suitable gas known in the art that facilitates the methods described herein. In some embodiments, the at least one gas is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0790] In some embodiments, the at least one gas is present in the source gas in an amount in the range of 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 in the range of 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 in the range of 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 in the range of 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 in the range of 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 in the range of 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).

[0791] In some embodiments, the at least one gas is present in the source gas in an amount in the range of 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 in the range of 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 in the range of from about 300 ppmv to about 5000 ppmv.

[0792] In some embodiments, the at least one gas does not include water vapor.

[0793] In some embodiments, the at least one gas comprises water vapor. In some embodiments, the at least one gas comprises an amount of water vapor in the range of from about 0.001% (v / v) to about 25% (v / v). In some embodiments, the at least one gas comprises an amount of water vapor in the range of from about 0.01% (v / v) to about 20% (v / v). In some embodiments, the at least one gas comprises an amount of water vapor in the range of from about 0.5% (v / v) to about 15% (v / v). In some embodiments, the at least one gas comprises an amount of water vapor in the range of from about 0.5% (v / v) to about 4% (v / v). In some embodiments, the at least one gas comprises an amount of water vapor in the range of from about 4% (v / v) to about 15% (v / v).

[0794] In some embodiments, the at least one gas is present in the source gas in an amount in the range of 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 in the range of 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 in the range of 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 in the range of from about 0.001% (v / v) to about 25% (v / v). In some embodiments, water vapor is present in an amount in the range of from about 0.01% (v / v) to about 20% (v / v). In some embodiments, water vapor is present in an amount in the range of from about 0.5% (v / v) to about 10% (v / v).

[0795] In some embodiments, capturing a quantity of the at least one gas with a functionalized adsorbent 8814 comprises adsorbing a quantity of the at least one gas with the functionalized adsorbent. In some embodiments, capturing a quantity of the at least one gas with a functionalized adsorbent 8814 comprises adsorbing a quantity of the at least one gas with the functionalized adsorbent in the presence of water vapor.

[0796] In some embodiments, the amount of at least one gas of 8814 captured by the functionalized adsorbent ranges from about 1% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas of 8814 captured by the functionalized adsorbent ranges from about 10% (v / v) to about 90% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas of 8814 captured by the functionalized adsorbent ranges from about 20% (v / v) to about 80% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas of 8814 captured by the functionalized adsorbent ranges from about 30% (v / v) to about 70% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas of 8814 captured by the functionalized adsorbent ranges from about 40% (v / v) to about 60% (v / v) of the at least one gas present in the source gas.

[0797] In some embodiments, the amount of at least one gas of 8814 captured by the functionalized adsorbent ranges from about 1% (v / v) to about 25% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas of 8814 captured by the functionalized adsorbent ranges from about 1% (v / v) to about 20% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas of 8814 captured by the functionalized adsorbent ranges from about 1% (v / v) to about 15% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas of 8814 captured by the functionalized adsorbent ranges from about 1% (v / v) to about 10% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas of 8814 captured by the functionalized adsorbent ranges from about 1% (v / v) to about 5% (v / v) of the at least one gas present in the source gas.

[0798] In some embodiments, the amount of at least one gas of 8814 captured by 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 of 8814 captured by 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 of 8814 captured by 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 of 8814 captured by 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.

[0799] 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 decreasing 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, decreasing 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.

[0800] In many embodiments, the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof is at a certain temperature. Each temperature can be changed to facilitate the methods described herein. Each temperature can have a uniform temperature distribution, a gradient temperature distribution, a discrete temperature distribution, or a combination thereof.

[0801] In some embodiments, the method includes an adsorption cycle. In some embodiments, the method includes a desorption cycle. In some embodiments, during the gas adsorption cycle, at least one of the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof is at a temperature in the range of about 0°C to about 150°C. In some embodiments, during the gas desorption cycle, at least one of the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof is at a temperature in the range of about 60°C to about 250°C.

[0802] In some embodiments, the method includes controlling the temperature. The temperature of the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof can be controlled.

[0803] Exemplary embodiments described herein include a method for collecting at least one gas from a gas source.

[0804] Figure 90is an exemplary method flow chart 9010. In this exemplary embodiment, the method flow chart 9010 depicts exemplary method steps of the method embodiments described herein and is not intended to limit these method embodiments. The method includes receiving 9012, at a functionalized adsorbent, a gas source comprising at least one gas, wherein the functionalized adsorbent comprises: an adsorbent; and at least one functionalized ligand, the functionalized ligand comprising a polyamine comprising at least one cyclic unit. In some embodiments, the functionalized adsorbent comprises at least two functionalized ligands each comprising a polyamine comprising at least one cyclic unit, wherein the polyamines comprising at least one cyclic unit are different from each other. In some embodiments, the functionalized adsorbent further comprises at least one functionalized ligand that does not comprise a polyamine comprising at least one cyclic unit. The method further includes trapping 9014, with the functionalized adsorbent, an amount of at least one gas. The method further includes releasing 9016, from the functionalized adsorbent, at least one gas. The adsorbent may have an average particle length of ≤ 3 μm.

[0805] In some embodiments, the method includes: (I) receiving 9012, at a functionalized adsorbent, a gas source comprising at least one gas, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand, the functionalized ligand comprising a polyamine comprising at least one cyclic unit; (II) trapping 9014, with the functionalized adsorbent, an amount of the at least one gas; and (III) releasing 9016, from the functionalized adsorbent, the at least one gas.

[0806] In some embodiments, releasing 9016, from the functionalized adsorbent, the at least one gas includes purging the at least one gas from the functionalized adsorbent with a purge gas. In some embodiments, releasing 9016, from the functionalized adsorbent, the at least one gas includes receiving a change in temperature or pressure at the functionalized adsorbent.

[0807] In some embodiments, releasing 9016 at least one gas 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 at least one gas compared to the source gas.

[0808] Other aspects of the present disclosure are provided by the subject matter of the following clauses:

[0809] 1. A functionalized adsorbent, the functionalized adsorbent comprising:

[0810] an adsorbent; and

[0811] At least one functionalized ligand, the functionalized ligand comprising a polyamine comprising at least one cyclic unit.

[0812] 2. The functionalized adsorbent according to the preceding clause, wherein the adsorbent comprises a metal-organic framework (MOF).

[0813] 3. The functionalized adsorbent according to the preceding clause, 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.

[0814] 4. The functionalized adsorbent according to any one of the preceding clauses, wherein the at least one cyclic unit is selected from the group consisting of an alicyclic unit, an aromatic unit, and combinations thereof.

[0815] 5. The functionalized adsorbent according to any one of the preceding clauses, the functionalized adsorbent comprising at least one functionalized ligand that does not comprise a polyamine comprising at least one cyclic unit.

[0816] 6. The functionalized adsorbent according to any one of the preceding clauses, wherein the polyamine comprises at least one amine selected from the group consisting of a primary amine, a secondary amine, a tertiary amine, and combinations thereof.

[0817] 7. The functionalized adsorbent according to any one of the preceding clauses, wherein the adsorbent has an aspect ratio of ≥ 0.2.

[0818] 8. The functionalized adsorbent according to any one of the preceding clauses, wherein the adsorbent has an average particle length of ≤ 3 μm.

[0819] 9. The functionalized adsorbent according to any one of the preceding clauses, wherein the polyamine comprises at least one cyclic unit according to formula (C-I):

[0820]

[0821] Wherein:

[0822] B, C, and D each independently comprise at least one amine group;

[0823] x, y, and z are each independently 0 or 1; and

[0824] A comprises an aromatic ring structure according to formula (C-II), or an alicyclic structure according to formula (C-III):

[0825]

[0826] Wherein:

[0827] n is an integer in the range of about 3 to about 8;

[0828] m is an integer in the range of about 3 to about 5; and

[0829] A 1 、A 2 、A 3 and A 4 each independently comprises at least one of carbon, oxygen, and silicon.

[0830] 10. The functionalized adsorbent according to the preceding clause, wherein:

[0831] A 1 、A 2 、A 3 and A 4 each independently is selected from the group consisting of:

[0832] 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;

[0833] unsubstituted oxygen;

[0834] silicon 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;

[0835] and

[0836] combinations thereof.

[0837] 11. The functionalized adsorbent according to any one of the preceding clauses, wherein:

[0838] B, C, and D each independently comprise a structure according to formula (C-IV):

[0839] E t -F u -G v -H w (Formula C-IV)

[0840] wherein:

[0841] t, u, v, and w are each independently an integer in the range of about 0 to about 10; and

[0842] E, F, G, and H are each independently selected from the group consisting of:

[0843] 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;

[0844] NH2, NHR1, and NR1R2,

[0845] wherein R1 and R2 are each independently selected from the group consisting of: 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; and

[0846] combinations thereof.

[0847] 12. The functionalized adsorbent according to any one of the preceding clauses, wherein the polyamine comprises at least two cyclic units, wherein:

[0848] the polyamine comprises a polycyclic structure connected by at least one linking group selected from the group consisting of: 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; or

[0849] the polyamine comprises a bridged polycyclic structure containing at least one bridging group selected from the group consisting of: 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.

[0850] 13. The functionalized adsorbent according to any one of the preceding clauses, wherein the polyamine is a compound selected from the group consisting of:

[0851]

[0852]

[0853]

[0854]

[0855]

[0856]

[0857]

[0858] and

[0859] their combinations.

[0860] 14. An adsorbent system, the adsorbent system comprising a functionalized adsorbent according to any one of the preceding clauses.

[0861] 15. A method for preparing a functionalized adsorbent, the method comprising:

[0862] (I) forming a mixture comprising:

[0863] an adsorbent;

[0864] at least one functionalized ligand, the functionalized ligand comprising a polyamine comprising at least one cyclic unit;

[0865] optionally at least one functionalized ligand that does not comprise a polyamine comprising at least one cyclic unit;

[0866] optionally a solvent; and

[0867] optionally a non-solvent; and

[0868] (II) functionalizing the adsorbent.

[0869] 16. The method according to the preceding clause, wherein the adsorbent has an average particle length of ≤ 1 μm.

[0870] 17. A method for trapping at least one gas, the method comprising:

[0871] (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises:

[0872] an adsorbent;

[0873] at least one functionalized ligand, the functionalized ligand comprising a polyamine comprising at least one cyclic unit; and

[0874] (II) trapping a quantity of the at least one gas with the functionalized adsorbent.

[0875] 18. The method according to the preceding clause, wherein the gas source is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and their combinations.

[0876] 19. The method according to any one of the preceding clauses, wherein the at least one gas is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0877] 20. A method for collecting at least one gas from a gas source, the method comprising:

[0878] trapping the at least one gas according to the method of any one of the preceding clauses, and

[0879] (III) releasing the at least one gas from the functionalized adsorbent.

[0880] Examples

[0881] Without further elaboration, it is believed that one of ordinary skill in the art can make the fullest use of the present invention with the foregoing description. Accordingly, the following examples are to be construed as illustrative only and not in any way limiting of the disclosure. The starting materials for the following examples need not be prepared by a specific preparative run, the procedure for which is described in other examples. It should also be understood that any numerical range recited herein includes all values from the lower value to the upper value. For example, if the range is stated as 10 to 50, values such as 12 to 30, 20 to 40, or 30 to 50 are intended to be expressly enumerated in this specification. These are merely examples of specific intentions, and all possible combinations of values between and including the lowest and highest values recited are considered to be expressly stated in this application.

[0882] Carbon dioxide capture system using functionalized adsorbent and water management

[0883] Example A1. Comparative Moisture Isotherms.

[0884] Figure 5 Shows the H2O adsorption capacity as a function of relative humidity of adsorbents functionalized with AEAM, spermidine, spermine: AEAM = 0.65:0.35 hybrid ("hybrid compound 1") and spermine: AEAM = 0.32:0.46 hybrid ("hybrid compound 2") measured at 25 °C using DVS gravimetry. The figure illustrates that the relative humidity at which the moisture adsorption isotherm and thus monolayer adsorption of H2O occurs changes with the chemical structure of the functionalized adsorbent. As Figure 5As shown, with the exception of AEAM, the moisture adsorption isotherms of all adsorbents are closest in shape to type IV, including a flat region that leads to an inflection point corresponding to monolayer coverage and H2O adsorption of the two hybrid compounds at approximately 30% relative humidity and spermidine at approximately 35% relative humidity.

[0885] Example A2. Moisture Adsorption Isotherm of Hybrid Compound 1.

[0886] Figure 6 Shows the H2O adsorption capacity of hybrid compound 1 (spermine: AEAM = 0.65:0.35) measured using DVS gravimetry as a function of relative humidity at different temperatures. Figure 7 Shows the H2O adsorption capacity of hybrid compound 1 (spermine: AEAM = 0.65:0.35) measured using DVS gravimetry as a function of H2O partial pressure (kPa) at different temperatures. These plots illustrate that although the absolute H2O partial pressure is different, when the temperature changes, the shape of the moisture isotherm and thus the relative humidity at which the H2O monolayer adsorption occurs remains approximately the same.

[0887] Example A3. Adsorption Performance of Hybrid Compound 1.

[0888] Figure 8 Shows the CO2 and H2O adsorption properties of hybrid compound 1 (spermine: AEAM = 0.65:0.35) measured using DVS gravimetry at 40 °C and 4.5 v% CO2 as a function of relative humidity. This plot shows that CO2 adsorption is sensitive to relative humidity. As shown for hybrid compound 1 in Figure 5 The inflection point of the H2O monolayer adsorption appears to be a critical threshold. Since DVS gravimetry is based on measuring the change in cumulative mass, in a binary system (e.g., CO2 and H2O in this case), due to the lack of discrimination of the individual components, the individual CO2 adsorption amount and H2O adsorption amount cannot be accurately calculated. However, a breakthrough test rig and analyzer with separate sensors designated for CO2 and H2O should be used to quantitatively evaluate discrete CO2 and H2O adsorption.

[0889] Example A4. Adsorption Performance of Hybrid Compound 1 as a Function of Temperature, Water Content, and Relative Humidity.

[0890] Figure 9 Shows the CO2 adsorption performance of hybrid compound 1 (spermine: AEAM = 0.65:0.35) at 4.5 v% CO2 as a function of water pressure (kPa) measured using DVS gravimetry at different temperatures. Figure 10Shows the H2O adsorption capacity of hybrid compound 1 (spermine: AEAM = 0.65:0.35) measured using DVS gravimetry as a function of water pressure (kPa) at different temperatures. Figure 11 Shows the CO2 adsorption performance of hybrid compound 1 (spermine: AEAM = 0.65:0.35) measured using DVS gravimetry as a function of relative humidity at different temperatures. These figures illustrate that although the adsorption performance of hybrid compound 1 varies with temperature and water pressure, high performance can be maintained by adjusting the relative humidity by regulating the temperature and water content. These figures further show that CO2 adsorption is sensitive to relative humidity. As Figure 5 shown for hybrid compound 1, the inflection point of H2O monolayer adsorption seems to be the critical threshold. Similarly, breakthrough test benches and analyzers with separate sensors designated for CO2 and H2O should be used to quantitatively evaluate discrete CO2 and H2O adsorption.

[0891] Example A5. Comparative Adsorption Capacity.

[0892] Figure 12A Shows the CO2 adsorption isotherms of hybrid compound 1 (spermine: AEAM = 0.65:0.35) for dry CO2 and wet CO2 at 30% relative humidity measured using DVS gravimetry at 40 °C. This figure illustrates that the adsorption capacity of hybrid compound 1 increases under wet conditions at 30% relative humidity compared to dry conditions.

[0893] Figure 12B Shows the CO2 adsorption of hybrid compound 3 (spermine: AEAM = 0.69:0.23) for dry CO2 and wet CO2 with different relative humidities measured using a breakthrough test rig with separate CO2 and H2O sensors under DAC-related conditions at 25 °C and 400 ppmv CO2 concentration. Figure 12B Also shows the isotherm of pure H2O adsorption of hybrid compound 3. This figure quantitatively illustrates that, at least for the test conditions relevant to DAC applications, (1) wet CO2 results in an increase in CO2 adsorption relative to dry CO2 (i.e., with 0% relative humidity), (2) the amount of CO2 adsorption is sensitive to the actual relative humidity, and (3) once the minimum relative humidity is reached, CO2 adsorption seems to level off, consistent with the inflection point of H2O monolayer adsorption, as Figure 12B shown for hybrid compound 3.

[0894] This document describes exemplary systems that use functionalized chemisorbents in the presence of water to facilitate optimized adsorption and desorption of carbon dioxide in adsorption beds. The exemplary systems described herein can provide several advantages over conventional designs and methods, including at least: improved efficiency and performance of carbon dioxide adsorption and desorption due to changes in temperature and / or water relative humidity within the adsorption bed, changes in the functionalized adsorbent within the adsorption bed, and / or improved performance of the capture system due to regulating the temperature and water relative humidity within one or more adsorption modules within the adsorption bed based on the functionalized adsorbent within one or more adsorption modules.

[0895] Synthesis of aminoalkyl-substituted disiloxanes.

[0896] Example B1. Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2-Aminoethylaminomethyl)Tetramethyldisiloxane with 4 Equivalents of Ethylenediamine Example B2. Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(3-Aminopropylaminomethyl)Tetramethyldisiloxane

[0897] Ethylenediamine (396 mL, 5.93 mol) was added to a 2 L three-necked round-bottom flask equipped with a addition funnel and a reflux condenser. The flask was placed in an ice-water bath and the headspace was purged with N2. Chloromethyldimethyl ethoxysilane (240 mL, 1.48 mol) was added to the addition funnel and added dropwise to the ethylenediamine over 1 hour, during which time the reactants exothermed to 90 °C to 100 °C. After an additional 1 hour, the reaction was judged complete by 1 1H NMR, at which point 300 mL of water was added dropwise to the reaction mixture over 30 minutes, resulting in exotherm. The reaction mixture was cooled to room temperature with stirring, at which point 300 mL of chloroform was added dropwise. The resulting mixture was stirred vigorously for 1 hour, after which the organic layer was separated and the aqueous layer was extracted with a minimum volume of chloroform. The combined organic layers were dried under reduced pressure at room temperature. The resulting material was then purified by vacuum distillation. The first fraction containing mainly cyclic by-products and some product was collected at 40 °C to 80 °C and 380 mTorr. By 1 1H NMR spectral analysis, the remaining material (167 g, 81% yield) had a purity > 75%. 1 1H NMR (CDCl3) δ: 2.80 (t, 4H, H2NCH2CH2), 2.65 (t, 4H, H2NCH2), 2.05 (s, 4H, SiCH2), 1.30 (br s, 6H, NH&NH2), 0.12 (s, 12H, SiCH3).

[0898] Example B3. Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2-Methyl-3-Aminopropylaminomethyl)Tetramethyldisiloxane Example B4. Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2,2-Dimethyl-3-Aminopropylaminomethyl)Tetramethyldisiloxane

[0899] The same procedure as in Example B1 was carried out, but in a 250 mL three-necked flask, 1,3-propanediamine (52 mL, 0.62 mol), chloromethyldimethylethoxysilane (25 mL, 0.15 mol), 40 mL of water and 40 mL of chloroform were used. The resulting material was then purified by vacuum distillation. The first fraction mainly containing cyclic by-products and some products was collected at 40 °C to 65 °C. By 1 1H NMR spectral analysis, the purity of the remaining material (17.6 g, 74% yield) was >95%. 1 1H NMR (CDCl3) δ: 2.75 (t, 4H, H2NCH2CH2CH2), 2.65 (t, 4H, H2NCH2), 2.05 (s, 4H, SiCH2), 1.60 (multiplet, 4H, H2NCH2CH2), 1.30 (br s, 6H, NH&NH2), 0.12 (s, 12H, SiCH3).

[0900] Example B5. Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2-Aminoethylaminomethyl)Tetramethyldisiloxane with 8 Equivalents of Ethylenediamine Example B6. Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2-Aminoethylaminomethyl)Tetramethyldisiloxane with 10 Equivalents of Ethylenediamine

[0901] The same procedure as in Example B1 was carried out, but in a 15 mL flask, 2-methyl-1,3-propanediamine (2.84 mL, 0.028 mol), chloromethyldimethylethoxysilane (1.14 mL, 0.0071 mol), 2 mL of water and 2 mL of chloroform were used. The resulting material was then purified by vacuum distillation. The first fraction containing by-products and some products was collected at 110 °C. By 1 1H NMR spectral analysis, the purity of the remaining material (0.60 g, 51% yield) was >95%. 1 1H NMR (CDCl3) δ: 2.8 - 2.5 (overlapping multiplets, 8H, H2NCH2CH(CH3)CH2), 2.05 (multiplet, 4H, SiCH2), 1.75 (multiplet, 2H, H2NCH2CH), 1.95 (br s, 6H, NH&NH2), 0.90 (d, 6H, H2NCH2CHCH3) 0.12 (s, 12H, SiCH3).

[0902] Comparative Example B1. Attempted Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2-Aminoethylaminomethyl)Tetramethyldisiloxane from 1,3-Bis(Chloromethyl)Tetramethyldisiloxane ​

[0903] The same procedure as in Example B1 was carried out, but in a 15 mL flask, 2,2-dimethyl-1,3-propanediamine (3.41 mL, 0.028 mol), chloromethyldimethylethoxysilane (1.12 mL, 0.0071 mol), 2 mL of water and 2 mL of chloroform were used. The resulting material was then purified by vacuum distillation. The first fraction containing by-products and some products was collected at 80 °C to 90 °C. By 11H NMR spectrum analysis showed that the purity of the remaining material (0.95 g, 74% yield) was >95%. 1 1H NMR (CDCl3) δ: 3.10 (br s, 6H, NH&NH2), 2.67 (s, 4H, H2NCH2), 2.60 (s, 4H, H2NCH2C(CH3)2CH2), 2.15 (s, 4H, SiCH2), 0.95 (s, 12H, H2NCH2C(CH3)2), 0.19 (s, 12H, SiCH3).

[0904] ​ ​

[0905] Ethylenediamine (793 mL, 11.9 mol) was added to a 2 L three-necked round-bottom flask equipped with a dropping funnel and a reflux condenser. The flask was placed in an ice-water bath and the headspace was purged with N2. Chloromethyldimethyl ethoxysilane (240 mL, 1.48 mol) was added to the dropping funnel and added dropwise to the ethylenediamine over 1 hour, during which the reaction mixture exothermed to 90 °C to 100 °C. After another 1 hour, the reaction was judged to be complete by 1 1H NMR. At this time, 300 mL of water was added dropwise to the reaction mixture within 30 minutes, resulting in exotherm. The reaction mixture was cooled to room temperature with stirring, and then 300 mL of chloroform was added dropwise. The resulting mixture was vigorously stirred for 1 hour, after which the organic layer was separated and the aqueous layer was extracted with a minimum volume of chloroform. The combined organic layers were dried under reduced pressure at room temperature. Then the resulting material was purified by vacuum distillation. The first fraction mainly containing cyclic...

Claims

1. A functionalized adsorbent, the functionalized adsorbent comprising: an adsorbent; and at least one functionalized ligand, the functionalized ligand comprising a polyamine comprising at least one cyclic unit.

2. The functionalized adsorbent according to claim 1, wherein the adsorbent comprises a metal-organic framework (MOF).

3. The functionalized adsorbent according to claim 2, 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.

4. The functionalized adsorbent according to claim 1, wherein the at least one cyclic unit is selected from the group consisting of an alicyclic unit, an aromatic unit, and combinations thereof.

5. The functionalized adsorbent according to claim 1, the functionalized adsorbent comprising at least one functionalized ligand that does not comprise a polyamine comprising at least one cyclic unit.

6. The functionalized adsorbent according to claim 1, wherein the polyamine comprises at least one amine selected from the group consisting of a primary amine, a secondary amine, a tertiary amine, and combinations thereof.

7. The functionalized adsorbent according to claim 1, wherein the adsorbent has an aspect ratio ≥ 0.

2.

8. The functionalized adsorbent according to claim 1, wherein the adsorbent has an average particle length ≤ 3 μm.

9. The functionalized adsorbent according to claim 1, wherein the polyamine comprises at least one cyclic unit according to formula (C-I): Wherein: B, C, and D each independently comprise at least one amine group; x, y, and z are each independently 0 or 1; and A comprises an aromatic ring structure according to formula (C-II), or an alicyclic structure according to formula (C-III): Wherein: n is an integer in the range of about 3 to about 8; m is an integer in the range of about 3 to about 5; and A 1 、 A 2 、 A 3 and A 4 each independently includes at least one of carbon, oxygen, and silicon.

10. The functionalized adsorbent according to claim 9, wherein: A 1 , A 2 , A 3 and A 4 Each independently selected from the group consisting of: 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 alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; unsubstituted oxygen; silicon substituted with at least one substituent selected from the group consisting of: hydrogen, B, C, D, substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; and combinations thereof.

11. The functionalized adsorbent according to claim 9, wherein: B, C, and D each independently comprise a structure according to formula (C-IV): E t -F u -G v -H w (Formula C-IV) Wherein: t, u, v, and w are each independently integers in the range of about 0 to about 10; and E, F, G, and H are each independently selected from the group consisting of: 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; NH2, NHR1, and NR1R2, wherein R1 and R2 are each independently selected from the group consisting of: 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; and combinations thereof.

12. The functionalized adsorbent according to claim 1, wherein 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: 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; or the polyamine comprises a bridged polycyclic structure containing at least one bridging group selected from the group consisting of: 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.

13. The functionalized adsorbent according to claim 1, wherein the polyamine is a compound selected from the group consisting of: and combinations thereof.

14. An adsorbent system comprising the functionalized adsorbent according to claim 1.

15. A method for preparing a functionalized adsorbent, the method comprising: (I) forming a mixture comprising: an adsorbent; at least one functionalized ligand, the functionalized ligand comprising a polyamine containing at least one cyclic unit; optionally at least one functionalized ligand that does not comprise a polyamine containing at least one cyclic unit; optionally a solvent; and optionally a non-solvent; and (II) functionalizing the adsorbent.

16. The method according to claim 15, wherein the adsorbent has an average particle length of ≤3 μm.

17. A method for trapping 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 comprises: an adsorbent; at least one functionalized ligand, the functionalized ligand comprising a polyamine containing at least one cyclic unit; and (II) trapping a quantity of the at least one gas with the functionalized adsorbent.

18. The method according to claim 17, wherein the gas source is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

19. The method according to claim 17, wherein the at least one gas is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, steam, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

20. A method for collecting at least one gas from a gas source, the method comprising: trapping the at least one gas according to the method of claim 17, and (III) releasing the at least one gas from the functionalized adsorbent.

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