Sorbent compositions, systems and methods

Abstract

Described herein are adsorbents functionalized with ligands having aminosilicone functionality, methods for making the same, and methods for using the same. Also described herein are methods for preparing aminoalkyl-substituted disiloxanes and the aminoalkyl-substituted disiloxanes produced thereby. Moisture management and the use of the functionalized adsorbents (114) Adsorbent Also described herein are systems that facilitate optimizing the adsorption and desorption of carbon dioxide gas by beds. Also described herein are methods of systems and methods for modeling the predicted performance of adsorbents in post-combustion carbon capture systems and operating the post-combustion carbon capture systems using one or more predicted adsorbents based on carbon capture performance values ​​determined by modeling. Described herein are adsorbents functionalized with polyamines having cyclic units, methods for making the same, and methods for using the same.

Description

[Technical Field]

[0001] The present disclosure generally relates to adsorbents functionalized with ligands having aminosilicone functionality, methods for making the same, and methods for using the same. The disclosure also generally relates to aminoalkyl-substituted disiloxanes and methods for preparing the aminoalkyl-substituted disiloxanes produced thereby. The disclosure also generally relates to capture systems, and more specifically, to systems that facilitate optimization of carbon dioxide gas adsorption and desorption by adsorbent beds using moisture management and functionalized adsorbents. The disclosure also generally relates to modeling post-combustion or direct air carbon capture systems, and more specifically, to systems and methods for modeling the predicted 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 predicted adsorbents based on carbon capture performance values ​​determined by modeling. The disclosure also generally relates to adsorbents functionalized with polyamines having cyclic units, methods for making the same, and methods for using the same. [Background technology]

[0002] Solid sorbents are useful for a wide variety of purposes. For example, they are particularly useful in carbon capture sorbent systems, such as those used in point-source, post-combustion carbon capture (PCC) and direct air capture (DAC) of carbon dioxide (CO2). Solid sorbents used for carbon capture offer a viable and superior techno-economic alternative to traditional liquid amine-based CO2 capture processes. For example, solid sorbents tend to have better adsorption capacity, lower regeneration energy requirements, and reduced system complexity and environmental and safety risks compared to activated liquid amines.

[0003] There are two types of adsorbent materials based on the underlying adsorption mechanism. The first type, physical adsorbents, rely on non-covalent interactions (e.g., van der Waals interactions, dipole-dipole interactions, etc.) to adsorb gaseous species such as CO and HO. Examples of physical adsorbents include activated carbon, zeolites, and metal-organic frameworks (MOFs). The second type, chemical adsorbents, adsorb CO through a reversible chemical reaction and the formation of 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).

[0004] As a result of chemical bonding, chemisorbent materials generally have superior selectivity for CO adsorption compared to physisorbent materials for interfering species such as N, methane, and CO. However, the effectiveness of chemisorption systems can be limited by the compositional nature of the functionalizing molecules that carry out the chemisorption and functionalization processes. Therefore, there is a need for functionalized sorbents that contain chemically and thermally stable molecular species that selectively take up CO with high capacity and rapid rates.

[0005] Relatedly, at least some known industrial and power generation processes may result in the production of gas streams that contain pollutants, such as in the form of CO. Accordingly, capture systems may be used to facilitate the removal of pollutants from gas streams before the exhaust streams are released into the atmosphere. For example, carbon capture systems may be used to capture CO and store it underground in an attempt to reduce the amount of CO released into the atmosphere.

[0006] At least some known carbon capture systems can use sorbent beds to capture and release CO. In some known systems, solid sorbent materials can be used in conjunction with the sorbent bed to facilitate CO adsorption and desorption, in contrast to other known systems that use liquid amine-based CO capture processes, to improve the adsorption capacity and efficiency of the system. However, the effectiveness of chemical adsorption systems is often limited by functionalization and detailed operating conditions.

[0007] To facilitate increased CO2 capture, at least some known carbon capture systems use water to improve CO2 capture efficiency. For example, carbon capture systems can use humid conditions to improve CO2 adsorption performance. However, interference from H2O molecules can reduce the CO2 adsorption capacity of chemical sorbent materials used in the adsorbent bed if too much H2O is adsorbed. Therefore, there is a need for a capture system that uses functionalized chemical sorbents in the presence of water to optimize carbon dioxide adsorption and desorption efficiency and productivity.

[0008] Relatedly, aminoalkyl-substituted disiloxanes are useful for a wide variety of purposes, for example, they are particularly useful in carbon capture systems or aminosilicone-based products.

[0009] Substituted disiloxanes are often produced by known reactions. However, known reactions may be limited in scope and may not be effective for producing aminoalkyl-substituted disiloxanes. For example, the process described in Chinese Patent No. 102675596 involves a reaction route that is not suitable for aminoalkyl-substituted disiloxanes due to a side reaction that preferentially forms a cyclic product. Similarly, the process described in Chinese Patent No. 102351893 begins with a material that can only be hydrolyzed to one compound. Furthermore, some processes, such as the process described in Li, et al., Thermochimica Acta, 2012, 545, 75, may require a relatively large number of reaction steps and / or require multi-step reaction routes and intermediate purification steps, which may reduce the overall yield and increase the cost and complexity of the process.

[0010] Therefore, opportunities for preparing aminoalkyl-substituted disiloxanes are limited. Therefore, there is a need for a simplified method for preparing aminoalkyl-substituted disiloxanes.

[0011] Relatedly, some power plant systems can include post-combustion carbon capture systems configured to capture carbon dioxide (CO2) from generated exhaust gases (flue gases). PCC systems can be used to capture CO2 from exhaust gases generated by power plants, including, for example, coal-burning systems, gas turbines, and / or boilers. Some types of PCC systems use metal-organic frameworks to facilitate carbon capture. Metal-organic frameworks typically contain two main components: an inorganic metal component (often called a secondary building unit, or SBU) and an organic component (often called a linker). Various different MOFs have been developed and tested for their capture capacity (e.g., a measure of how effectively a particular MOF performs in capturing CO2). However, while there are potentially millions of combinations of metals, linkers, and other functional groups that can be used in MOFs, some of which may result in greater capture capacity and productivity than existing MOFs, real-world creation and research of each possible combination of building blocks is economically prohibitive.

[0012] What is needed are systems and methods for modeling MOF performance using known MOFs to predict how other proposed MOFs may perform and to adjust the operation of carbon capture systems to use the MOFs based on the predicted carbon capture performance.

[0013] This disclosure addresses these related needs separately and together. [Prior art documents] [Patent documents]

[0014] [Patent Document 1] US Patent Application Publication No. 2008 / 0293976 Summary of the Invention

[0015] In one aspect, a functionalized sorbent is provided, comprising a sorbent and at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit.

[0016] In another aspect, a method of making a functionalized adsorbent is provided, the method comprising: (I) forming a mixture comprising an adsorbent; at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit; optionally, at least one functionalizing ligand not comprising a polyamine comprising at least one cyclic unit; optionally, a solvent; and optionally, a non-solvent; and (II) functionalizing the adsorbent.

[0017] In another aspect, a method for capturing at least one gas is provided, the method including: (I) receiving a gas source containing at least one gas with a functionalized adsorbent, the functionalized adsorbent including an adsorbent and at least one functionalizing ligand including a polyamine including at least one cyclic unit; and (II) capturing a quantity of the at least one gas with the functionalized adsorbent.

[0018] In another aspect, a method for recovering at least one gas is provided, the method including: (I) receiving a gas source containing at least one gas with a functionalized adsorbent, the functionalized adsorbent including an adsorbent and at least one functionalizing ligand including a polyamine including at least one cyclic unit; (II) capturing a quantity of the at least one gas with the functionalized adsorbent; and (III) releasing the at least one gas from the functionalized adsorbent.

[0019] These and other features, aspects, and advantages of the present disclosure will be better understood from the following detailed description when read in conjunction with the accompanying drawings, in which like characters represent like parts throughout. [Brief explanation of the drawings]

[0020] [Figure 1]FIG. 1 is a schematic diagram of an exemplary capture system that can be used to capture CO2 according to the present disclosure. [Figure 2] FIG. 1 is a schematic diagram of an alternative capture system that can be used to capture CO2 according to the present disclosure. [Figure 3] 3A-3C show moisture sorption isotherms of an exemplary type that the capture system of FIG. 2 may have in accordance with the present disclosure. [Figure 4] FIG. 3 is a schematic diagram of an exemplary control system that can be used with the capture system of FIGS. 1 and 2 in accordance with the present disclosure. [Figure 5] FIG. 1 shows exemplary potential HO adsorption capacities of adsorbents functionalized with AEAM, spermidine, a first hybrid of amine (hybrid compound 1, spermine:AEAM=0.65:0.35), or a second hybrid of amine (hybrid compound 2, spermine:AEAM=0.32:0.46), measured at 25° C. using dynamic vapor sorption (DVS) gravimetric method according to the present disclosure. [Figure 6] FIG. 1 shows exemplary potential HO adsorption capacities of adsorbents functionalized with the first hybrid of amines (hybrid compound 1, spermine:AEAM=0.65:0.35) as a function of HO partial pressure at various temperatures using dynamic vapor sorption (DVS) gravimetric analysis according to the present disclosure. [Figure 7] FIG. 1 shows exemplary potential HO adsorption capacities of adsorbents functionalized with a first amine hybrid (hybrid compound 1, spermine:AEAM=0.65:0.35) as a function of relative humidity at various temperatures using dynamic vapor sorption (DVS) gravimetric analysis according to the present disclosure. [Figure 8] FIG. 1 shows exemplary potential CO and HO adsorption capacities of an adsorbent functionalized with an amine first hybrid (hybrid compound 1, spermine:AEAM=0.65:0.35) as a function of relative humidity at 40° C. using a dynamic vapor sorption (DVS) gravimetric method according to the present disclosure. [Figure 9]FIG. 1 shows an exemplary potential CO adsorption capacity of an adsorbent functionalized with the first hybrid of amine (hybrid compound 1, spermine:AEAM=0.65:0.35) as a function of water pressure at various temperatures using the dynamic vapor sorption (DVS) gravimetric method according to the present disclosure. [Figure 10] FIG. 1 shows an exemplary potential HO adsorption capacity of an adsorbent functionalized with the first hybrid of amine (hybrid compound 1, spermine:AEAM=0.65:0.35) as a function of water pressure at various temperatures using the dynamic vapor sorption (DVS) gravimetric method according to the present disclosure. [Figure 11] FIG. 1 shows exemplary potential CO adsorption capacities of adsorbents functionalized with a first amine hybrid (hybrid compound 1, spermine:AEAM=0.65:0.35) as a function of relative humidity at various temperatures using dynamic vapor sorption (DVS) gravimetric analysis according to the present disclosure. [Figure 12A] FIG. 1 shows exemplary potential CO adsorption isotherms of an adsorbent functionalized with a first hybrid of amine (hybrid compound 1, spermine:AEAM=0.65:0.35) for dry and wet CO at 40° C. and 30% relative humidity using dynamic vapor sorption (DVS) gravimetric analysis according to the present disclosure. [Figure 12B] FIG. 1 shows exemplary CO adsorption and HO isotherms for an adsorbent functionalized with hybrid compound 3 (spermine:AEAM=0.69:0.23) for dry and wet CO at various relative humidities at 25° C. and a CO concentration of 400 ppmv measured using a breakthrough test rig with individual CO and HO sensors according to the present disclosure. [Figure 13] 1 is an exemplary method flowchart according to the present disclosure. [Figure 14] FIG. 1 illustrates an exemplary PCC modeling system that can be used to predict how particular MOFs may perform in capturing carbon dioxide (CO) from the exhaust gas of a coal-fired power plant in accordance with the present disclosure. [Figure 15]1 is a graph showing the decline in CO adsorption productivity of an exemplary adsorbent (e.g., an exemplary MOF) when going from a synthesized powder measured under equilibrium conditions to a final film coating on a substrate measured under dynamic conditions according to the present disclosure. [Figure 16A] 1 is a flowchart illustrating an exemplary method for analyzing the expected performance of a prospective sorbent in a post-combustion carbon capture system according to the present disclosure. [Figure 16B] 1 is a flowchart illustrating an exemplary method for analyzing the expected performance of a prospective sorbent in a post-combustion carbon capture system according to the present disclosure. [Figure 16C] 1 is a flowchart illustrating an exemplary method for analyzing the expected performance of a prospective sorbent in a post-combustion carbon capture system according to the present disclosure. [Figure 17] FIG. 10 illustrates an exemplary correlation matrix according to the present disclosure. [Figure 18] FIG. 1 shows a H NMR analysis of Mg2(dobpdc)1(IPA)1.92 according to the present disclosure. [Figure 19] 1 is a scanning electron microscope (SEM) image of exemplary MOF-274 (sample ID number A2111) made in accordance with the present disclosure. [Figure 20] 1A-1D show SEM images of exemplary MOF-274 prepared using salicylic acid (left) and fluoro-salicylic acid (right) as crystal growth inhibitors according to the present disclosure. [Figure 21] FIG. 1 shows the powder X-ray diffraction (XRD) spectrum of MOF-274 synthesized using 4,4′-biphenol as a crystal growth inhibitor per input molar ratio of 4,4′-biphenol:H4dobpdc indicated by the arrow, in accordance with the present disclosure. [Figure 22] 1A-1D show SEM images of exemplary MOF-274 made with no 4,4′-biphenol (left) and with 9.24 wt % 4,4′-biphenol (right) in accordance with the present disclosure. [Figure 23]FIG. 1 shows the crystal growth inhibitor 2,2′-bipyridine-5,5′-dicarboxylic acid (BPYDC) and powder XRD spectra of MOF-274 synthesized using BPYDC for each input molar ratio of BPYDC:H4dobpdc indicated above each line, in accordance with the present disclosure. [Figure 24] FIG. 1 shows SEM images of exemplary MOF-274 made using BPYDC as a crystal growth inhibitor (0.13 wt%, 2.29 wt%, and 24.78 wt% loadings) according to the present disclosure. [Figure 25] FIG. 1 shows the crystal growth inhibitor 2,2′-bipyridine-5,5′-dimethanol (BPYDM) and powder XRD spectra of MOF-274 synthesized using BPYDM for each input molar ratio of BPYDM:H4dobpdc indicated above each row, in accordance with the present disclosure. [Figure 26] FIG. 1 shows SEM images of exemplary MOF-274 made using BPYDM as a crystal growth inhibitor (1.17 wt %, 3.43 wt %, and 6.80 wt % loadings) according to the present disclosure. [Figure 27] FIG. 1 shows the chemical structures of spermine and exemplary aminosilicones according to the present disclosure. [Figure 28] 1 shows an SEM image of a comparative example of an adsorbent (GE115-A259) (Comparative Example-3) using MOF-274 (ID number: A21) synthesized according to conventional procedures. [Figure 29] FIG. 1 shows an SEM image of an inventive example of adsorbent (GE115-A272) (Invention-4) comprising mortar and pestle MOF-274 (ID#A21) in accordance with the present disclosure. [Figure 30] FIG. 1 shows an SEM image of an inventive example of an adsorbent (GE115-A279) (Invention-5) comprising mechanically milled MOF-274 according to the present disclosure. [Figure 31] 1 is a graph showing CO2 uptake of adsorbents containing pure spermine, pure APAP, and mixtures in different ratios as a function of spermine loading under 25°C, 50% RH, and 400 ppmv CO2, measured using a breakthrough test rig according to the present disclosure. [Figure 32] 1 is a graph showing CO2 uptake of adsorbents containing pure spermine, pure APAP, and mixtures of different ratios as a function of spermine loading at 120°C under 100 mBar CO2 partial pressure using dynamic vapor sorption (DVS) gravimetric method according to the present disclosure. [Figure 33] 1 is a graph showing the CO2 adsorption working capacity of adsorbents containing pure spermine, pure APAP, and mixtures of different ratios as a function of spermine loading according to the present disclosure. [Figure 34] 1 is an exemplary method flowchart according to the present disclosure. [Figure 35] 1 is an exemplary method flowchart according to the present disclosure. [Figure 36] 1 is an exemplary method flowchart according to the present disclosure. [Figure 37] 1 is an exemplary method flowchart according to the present disclosure. [Figure 38] FIG. 1 shows a 1H NMR analysis of GE181-A224 according to the present disclosure. [Figure 39] FIG. 1 shows a 1H NMR analysis of GE182-A225 according to the present disclosure. [Figure 40] Figure 1 shows 1H NMR analysis of BEDCH in 600 μL of MeOD. 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) according to the present disclosure. [Figure 41] FIG. 1 shows H NMR analysis of GE248 (DMSO-d, DO) δ 7.85 (dd, 2H), 7.69 (m, 5H), 6.98 (dd, 2H), 1.74-1.59 (m, 6H), 0.91 (m, 4H) in accordance with the present disclosure. [Figure 42] FIG. 1 shows an SEM image of an exemplary mechanically milled MOF-274 according to the present disclosure. [Figure 43] FIG. 1 shows a 1H NMR analysis of GE183-A226A according to the present disclosure. [Figure 44]FIG. 1 shows a H NMR analysis of Ph-3-ED in 600 μL of DO, H NMR(DO)δ 7.25(s, 1 H), 3.78(s,6H), 2.76(t,6H), 2.66(t,6H) in accordance with the present disclosure. [Figure 45] FIG. 1 shows a H NMR analysis performed on GE223-67A after digestion with 20 μL of 20% DCl in DO, 200 μL DO, and 600 μL DMSO-d, H NMR (DMSO-d, DO) 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) in accordance with the present disclosure. [Figure 46] FIG. 1 shows the HO isotherm of GE181 (1,3-cyclohexanediamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 47] FIG. 1 shows the HO isotherm for GE182 (trans 1,4-cyclohexanediamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 48] FIG. 1 shows the HO isotherm for GE183 (1,3-xylylenediamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 49] FIG. 1 shows the HO isotherm for GE186 (1,4-xylylenediamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 50] FIG. 1 shows the HO isotherm of GE195 (furan-2,5-diamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 51] FIG. 1 shows the HO isotherm of GE193 (1,4-bis-(aminomethyl)-cyclohexane) at 25° C. measured using the DVS gravimetric method according to the present disclosure. [Figure 52] FIG. 1 shows the HO isotherm of GE205 (4-(aminomethyl)cyclohexanamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 53]FIG. 1 shows the HO isotherm of GE206 (1,3-bis-(aminomethyl)-cyclohexane) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 54] FIG. 1 shows the HO isotherm of GE214 (bis(aminomethyl)norbornane) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 55] FIG. 1 shows the HO isotherm of GE216 (4,4′-methylenebis(2-methylcyclohexylamine)) at 25° C. measured using the DVS gravimetric method according to the present disclosure. [Figure 56] FIG. 1 shows the HO isotherm of GE217 (tetrafluoro-p-xylylenediamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 57] FIG. 1 shows the HO isotherm of GE218 (rac-(1r,4r)-N1,N4-dimethylcyclohexane-1,4-diamine) at 25° measured using DVS gravimetric method according to the present disclosure. [Figure 58] FIG. 1 shows the HO isotherm for GE220 (1,3,5-benzenetrimethanamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 59] FIG. 1 shows the HO isotherm for GE221 (1,3,5-cyclohexanetriyltrimethanamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 60] FIG. 1 shows the HO isotherm of GE223(Ph-3-ED) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 61] FIG. 1 shows the HO isotherm of GE225 (methyl({4-[(methylamino)methyl]phenyl}methyl)amine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 62] FIG. 1 shows the HO isotherm of GE226 (a mixture of 1,4-xylylenediamine and 1,3,5-benzenetrimethanamine) at 25° C. measured using the DVS gravimetric method according to the present disclosure. [Figure 63] FIG. 1 shows the HO isotherm of GE227 (a mixture of 1,4-xylylenediamine and 1,3,5-benzenetrimethanamine) at 25° C. measured using the DVS gravimetric method according to the present disclosure. [Figure 64] FIG. 1 shows the HO isotherm of GE230 (4-(2-aminoethyl)aniline) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 65] FIG. 1 shows the HO isotherm of GE234 (a mixture of spermine and 1,4-bis-(aminomethyl)-cyclohexane) at 25° C. measured using the DVS gravimetric method according to the present disclosure. [Figure 66] FIG. 1 shows the HO isotherm of GE235 (a mixture of spermine and 1,4-bis-(aminomethyl)-cyclohexane) at 25° C. measured using the DVS gravimetric method according to the present disclosure. [Figure 67] FIG. 1 shows the HO isotherm of GE238 (1,4-bis-(aminomethyl)-cyclohexane) at 25° C. measured using the DVS gravimetric method according to the present disclosure. [Figure 68] FIG. 1 shows the HO isotherm of GE240 (4-(2-aminoethyl)cyclohexylamine) at 25° C. measured using the DVS gravimetric method according to the present disclosure. [Figure 69] FIG. 1 shows the HO isotherm for GE241 (1,3-bis(aminomethyl)cyclohexane) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 70] FIG. 1 shows the HO isotherm of GE248 (N1,N4-bis(2-aminoethyl)-1,4-cyclohexanedimethanamine, BEDCH) at 25° C. measured using the DVS gravimetric method according to the present disclosure. [Figure 71] FIG. 1 shows the CO2 isotherm of GE181 (1,3-cyclohexanediamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 72]FIG. 1 shows the CO2 isotherm of GE182 (trans 1,4-cyclohexanediamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 73] FIG. 1 shows the CO2 isotherm of GE183 (1,3-xylylenediamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 74] FIG. 1 shows the CO2 isotherm of GE186 (1,4-xylylenediamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 75] FIG. 1 shows the CO2 isotherm of GE193 (1,4-bis-(aminomethyl)-cyclohexane) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 76] FIG. 1 shows the CO isotherm of GE206 (1,3-bis-(aminomethyl)-cyclohexane) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 77] FIG. 1 shows the CO isotherm of GE214 (bis(aminomethyl)norbornane) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 78] FIG. 1 shows the CO2 isotherm of GE205 (4-(aminomethyl)cyclohexanamine (AMCHA)) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 79] FIG. 1 shows the CO2 isotherm of GE222(Ph-3-ED) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 80] FIG. 1 shows the CO isotherm of GE225 (N-methyl-1-[4-(methylaminomethyl)phenyl]methanamine) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 81] FIG. 1 shows the CO isotherm of GE226 (1,4-xylylenediamine and 1,3,5-benzenetriyltrimethanamine) at 25° C. measured using the DVS gravimetric method according to the present disclosure. [Figure 82]FIG. 1 shows the CO isotherm of GE227 (1,4-xylylenediamine and 1,3,5 benzenetriyltrimethanamine) at 25° C. measured using the DVS gravimetric method according to the present disclosure. [Figure 83] FIG. 1 shows the CO2 isotherm of GE303-169 (N1,N1′-(cyclohexane-1,4-diyl)bis(propane-1,3-diamine)) at 25° C. measured using DVS gravimetric method according to the present disclosure. [Figure 84] FIG. 1 shows the CO2 uptake of adsorbents containing pure spermine, pure BEDCH and different ratios of mixtures as a function of spermine loading under 22°C, 50% RH and 400 vppm CO2 measured using a breakthrough test rig according to the present disclosure. [Figure 85] FIG. 1 shows the CO2 uptake of adsorbents containing pure spermine, pure BEDCH and mixtures of different ratios as a function of spermine loading at 120°C under 100 mBar CO2 partial pressure measured using DVS gravimetric method according to the present disclosure. [Figure 86] FIG. 1 shows the CO2 adsorption working capacity of adsorbents containing pure spermine, pure BEDCH, and mixtures of various ratios as a function of spermine loading, according to the present disclosure. [Figure 87] 1 is an exemplary method flowchart according to the present disclosure. [Figure 88] 1 is an exemplary method flowchart according to the present disclosure. [Figure 89] 1 is an exemplary method flowchart according to the present disclosure. [Figure 90] 1 is an exemplary method flowchart according to the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0021] Unless otherwise specified, the drawings provided herein illustrate features of embodiments of the present disclosure. These features are believed to be applicable in a wide variety of systems incorporating one or more embodiments of the present disclosure. Thus, the drawings are not intended to include all conventional features known to those skilled in the art to be required for the practice of the embodiments disclosed herein.

[0022] The embodiments of the present disclosure can be combined in any manner, including various combinations of composition embodiments, system embodiments, and method embodiments. Subject headings are provided for convenience and do not separate or limit the embodiments of the present disclosure. Accordingly, the following embodiments should be construed as merely illustrative and in no way limiting of the present disclosure.

[0023] Systems for carbon dioxide capture using functionalized sorbents and water management

[0024] In one aspect, a capture system for use in capturing carbon dioxide is provided. The capture system includes an adsorbent bed including at least one adsorption module and a functionalized adsorbent, the at least one adsorption module being oriented to receive a gas stream, adsorb carbon dioxide from the gas stream via the functionalized adsorbent, and output a vent stream. The capture system further includes a contactor for use in 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 facilitate increasing the amount of carbon dioxide captured by the adsorbent bed.

[0025]

[0003] Embodiments described herein relate to systems that use functionalized chemical sorbents in the presence of water to facilitate optimization of carbon dioxide adsorption and desorption by adsorbent beds. Advantages of the systems described herein include at least: (i) improving carbon dioxide adsorption and desorption efficiency and performance through the use of temperature variations in the adsorbent bed; (ii) improving carbon dioxide adsorption and desorption efficiency and performance through the use of functionalized sorbents within the adsorbent bed; (iii) improving carbon dioxide adsorption and desorption efficiency and performance through the use of variations in water relative humidity within the adsorbent bed; and (iv) enhancing the performance of the capture system through adjustment of temperature and water relative humidity within one or more adsorption modules within the adsorbent bed based on the functionalized sorbents within one or more adsorption modules.

[0026] 1 is a schematic diagram of an exemplary capture system 100 that may be used to capture CO2 using a sorbent bed 102. In an exemplary embodiment, Adsorbent Bed 102 includes at least one adsorption module 104. More specifically, in the exemplary embodiment, adsorbent bed 102 includes four adsorption modules 104a-104d. In some embodiments, capture system 100 can include more or less than four adsorption modules 104. Further, in the exemplary embodiment, adsorbent bed 102 includes an inlet 106 and an outlet 108. Inlet 106 and outlet 108 are oriented such that, during operation, gas stream 110 received through inlet 106 is directed serially through each adsorption module 104 toward outlet 108. As gas stream 110 is directed through each adsorption module 104, adsorbent bed 102 captures CO2 from gas stream 110, and exhaust stream 112 is discharged through outlet 108.

[0027] The adsorption module 104 may include a solid adsorbent for preferentially capturing certain components of the gas stream 110, such as CO and HO. In an exemplary embodiment, the adsorption module 104 includes a functionalized adsorbent 114 comprising an adsorbent and a functionalized ligand including at least one amine group, such as, but not limited to, an aminosilicone group, to facilitate increased CO capture capacity and productivity of the adsorbent bed 102. Generally, the functionalized adsorbent 114 may be in any form known in the art that facilitates the systems described herein. For example, the functionalized adsorbent 114 may be in the form of a powder, a composite mixed with a binder, a film or coating, a packed bed, and / or a column.

[0028] In the exemplary embodiment, after being received by inlet 106 , gas stream 110 is directed through first module 104 a of adsorption module 104 . adsorption Each of the modules 104 includes a functionalized adsorbent 114 for adsorbing CO contained in the gas stream 110. In some embodiments, the functionalized adsorbent 114 may be the same for each adsorption module 104. In other embodiments, the functionalized adsorbent 114 may vary within at least one adsorption module 104.

[0029] Generally, gas stream 110 may be any suitable gas known in the art that facilitates the systems described herein. For example, gas stream 110 may be air, flue gas, post-combustion gas, natural gas, and / or combinations thereof. In exemplary embodiments, gas stream 110 includes CO and HO. In some embodiments, CO may be present in gas stream 110 in a range of about 1% to about 10% by volume. In other embodiments, CO may be present in gas stream 110 in an amount less than 1% by volume, for example, about 300-500 ppm or less by volume. In still other embodiments, CO may be present in gas stream 110 in an amount greater than 10% by volume. In some embodiments, HO may be present in gas stream 110 in a range of about 0.01% to about 20% by volume. In other embodiments, HO may be present in gas stream 110 in amounts less than 7v%, such as in hot, humid summer air, e.g., between about 2v% and 7v%, or less than 2v%, such as in cold winter air. In still other embodiments, HO may be present in gas stream 110 in amounts greater than 5v%, such as in post-combustion gases.

[0030] In the exemplary embodiment, the concentration of CO in gas stream 110 is generally highest when gas stream 110 enters inlet 106. As CO is adsorbed by the functionalized adsorbent 114 in each subsequent adsorption module 104, the concentration of CO in gas stream 110 decreases as gas stream 110 is directed through adsorption modules 104a-104d toward outlet 108. In the exemplary embodiment, the concentration of CO in gas stream 110 flowing through adsorption modules 104a-104d is lowest at outlet 108 during a given adsorption cycle.

[0031] In the exemplary embodiment, capture system 100 also includes a controller 116 that dynamically adjusts the operation of capture system 100. For example, controller 116 can facilitate maximizing the capture of CO by altering the temperature of one or more adsorption modules 104 and / or altering the HO content within one or more adsorption modules 104, as further described herein.

[0032] The controller 116 adjusts the operating conditions of the capture system 100 by dynamically adjusting the temperature of each adsorption module 104a-104d. In the exemplary embodiment, the adsorption module 104 includes a contactor 118. The contactor 118 includes a contactor inlet 120 and a contactor outlet 121. In the exemplary embodiment, contactor The first stream 122 received through 118 regulates the temperature of the adsorption module 104 via heat transfer. The contactor 118 can use indirect or direct heat transfer to regulate the temperature of the adsorption module 104. For example, the contactor 118 can include a fluid circuit (not shown) defined between and extending from a contactor inlet 120 and a contactor outlet 121, whereby 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. Further, for example, the contactor 118 can be in direct flow communication with the adsorption module 104, whereby 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-104d can be coupled in series and / or in parallel.

[0033] The controller 116 adjusts the regulated temperature T of the first stream 122. reg The temperature of the one or more adsorption modules 104 may be adjusted while monitoring the first stream 122. In some embodiments, the first stream 122 may be in liquid form. In other embodiments, the first stream 122 may be in gaseous form. Direct or indirect heat transfer between the first stream 122 and the functionalized adsorbent 114 in the one or more adsorption modules 104 facilitates control of the temperature of the functionalized adsorbent 114. The controller 116 uses a contactor sensor 130 (shown in FIG. 4 ) to adjust the adjusted temperature T of the first stream 122. reg Additionally, the controller 116 may monitor the controlled temperature T of the at least one adsorption module 104 using a module sensor 134 (shown in FIG. 4). cntl The controlled temperature T of at least one adsorption module 104 can be monitored. cntlAt operating conditions where T is lower than desired, the controller 124 adjusts the regulated temperature T of the first stream 122. reg , thereby increasing the temperature of the at least one adsorption module 104. Alternatively, the controlled temperature T cntl At operating conditions where T is higher than desired, the controller 124 adjusts the regulated temperature T of the first stream 122. reg may be selectively reduced, thereby reducing the temperature of at least one adsorption module 104.

[0034] Generally, the adjusted temperature T of the first stream 122 reg The temperature of the adsorption module 104, and therefore the temperature of the adsorption module 104, can be any suitable temperature known in the art that facilitates the capture of CO by the systems described herein. In some embodiments, the adjusted 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 adjusted temperature T of the first stream 122 reg may range from about 60° C. to about 250° C. In an exemplary embodiment, the adjusted temperature T of the first stream 122 reg is monitored in each adsorption module 104a-104d. In some embodiments, the regulated temperature T of the first stream 122 reg may be substantially uniform across each adsorption module 104. In other embodiments, the adjusted temperature T of the first stream 122 reg may vary across the different adsorption modules 104a-104d.

[0035] Additionally, the controller 116 may adjust the regulated temperature T of the first stream 122 in any of the adsorption modules 104a-104d. reg For example, one or more of the adsorption modules 104a-104d may include multiple module sensors 134 (shown in FIG. 4). Accordingly, the controller 116 may adjust the adjusted temperature T of the first stream 122 in any or all of the adsorption modules 104a-104d. regA temperature profile can be created that includes various values ​​of T. In some embodiments, the adjusted temperature T of the first stream 122 reg Varying values ​​of may form a gradient temperature profile within any or all of the adsorption modules 104a-104d. In other embodiments, the regulated temperature T of the first stream 122 reg The various values ​​of may form discrete temperature profiles within any or all of the adsorption modules 104a-104d.

[0036] FIG. 2 is a schematic diagram of an exemplary capture system 200 that can be used to capture CO using an adsorbent bed 102. The embodiment illustrated in FIG. 2 is similar to the embodiment illustrated in FIG. 1, with the differences described herein; therefore, the same reference numerals used in FIG. 1 are used in FIG. 2. The controller 116 facilitates adjustment of the operating conditions of the capture system 200 by dynamically adjusting the HO relative humidity by adjusting the HO content within each adsorption module 104a-104d. In the 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 facilitates adjustment of the HO relative humidity by adjusting the HO content within the adsorption module 104. In the exemplary embodiment, the second stream 206 includes HO. The second stream 206 may include HO in liquid (e.g., water) or gas (e.g., water vapor) form. In some embodiments, HO may be present in second stream 206 in a range of about 0.1 v% to about 20 v%. In other embodiments, HO may be present in second stream 206 in a range of about 4 v% to about 15 v%. In still other embodiments, HO may be present in second stream 206 in a range of about 0.5 v% to about 4 v%, as typically occurs in ambient air.

[0037] The controller 116 may adjust the HO content in one or more adsorption modules 104 by adjusting the flow of second stream 206 to the one or more adsorption modules 104. For example, the controller 116 may use module sensor 134 (shown in FIG. 4 ) to monitor the relative humidity level for the HO concentration C of the adsorption module 104. At operating conditions where the HO relative humidity level for the HO concentration C is lower than desired in at least one adsorption module 104, the controller 116 may selectively increase the flow of second stream 206, thereby injecting additional HO into the at least one adsorption module 104. At operating conditions where the HO relative humidity level is higher than desired in at least one adsorption module 104, the controller 116 may selectively decrease the flow of second stream 206, thereby decreasing the amount of additional HO injected into the at least one adsorption module 104. In another embodiment, at the beginning of the adsorption cycle, the controller 116 can selectively increase the flow of the second stream 206, thereby injecting additional HO into the at least one adsorption module 104 to increase the relative humidity above the desired relative humidity level and enable rapid HO adsorption. Then, at a later stage in the adsorption cycle, the controller 116 may selectively decrease or stop the flow of the second stream 206 to reduce the relative humidity level in the at least one adsorption module 104.

[0038] The controller 116 also controls the regulated temperature T of the first stream 122 of the one or more absorption modules 104. reg The H2O relative humidity may be adjusted within one or more of the adsorption modules 104 by monitoring the H2O relative humidity. In operating conditions where the H2O relative humidity level is higher than desired in at least one adsorption module 104, the controller 116 may adjust the adjustment temperature T of the first stream 122. regmay be selectively increased, thereby increasing the temperature of at least one adsorption module 104 and causing a decrease in the HO relative humidity due to increased saturation vapor pressure at higher temperatures. At operating conditions where the HO relative humidity is lower than desired in at least one adsorption module 104, the controller 116 may selectively increase the adjusted temperature T of the first stream 122. reg may be selectively decreased, thereby decreasing the temperature of at least one adsorption module 104 and causing an increase in the H2O relative humidity. reg can be increased or decreased using any of the systems described herein.

[0039] The controller 116 adjusts the operating conditions of the capture system 200 to facilitate optimization of CO2 adsorption and desorption by maintaining the relative humidity of each adsorption module 104a-104d. The relative humidity of each adsorption module 104a-104d is adjusted to the regulated temperature T of the first stream 122. reg and the HO concentration C in the adsorption module 104. In an exemplary embodiment, the controller 116 adjusts the adjusted temperature T of the first stream 122 based on the HO adsorption isotherm of the functionalized adsorbent 114 in the adsorption module 104. reg and adjusting the H2O concentration C in the adsorption module 104 to facilitate optimization of CO2 adsorption and desorption by monolayer adsorption of H2O.

[0040] In general, the capture system 200 can have any suitable adsorption isotherm that facilitates the capture of CO by the systems described herein. There are six types of moisture adsorption isotherms defined by IUPAC, whose shapes depend on relative humidity and temperature (shown in FIG. 3). Of these six types, Type II, Type IV, and Type VI each exhibit a plateau region (e.g., an "inflection point") up to a knee point that generally corresponds to monolayer coverage and adsorption of HO (shown in FIG. 3). In an exemplary embodiment, the controller 116 adjusts the operating conditions of the capture system 200 for monolayer coverage and adsorption of HO by the functionalized adsorbent 114, thereby facilitating optimization of CO adsorption and desorption. For example, the capture system 200 can have a Type II, Type IV, or Type VI adsorption isotherm (shown in FIG. 3), which are particularly advantageous for ensuring monolayer coverage and adsorption of HO, thereby increasing the CO adsorption capacity of the functionalized adsorbent 114.

[0041] In addition to being dependent on relative humidity and temperature, the adsorption isotherm is dependent on the adsorbent material. In many embodiments, the functionalized adsorbent 114 may be any functionalized adsorbent material that facilitates the capture of CO by the systems described herein. In an exemplary embodiment, the functionalized adsorbent 114 comprises a adsorbent and at least one functionalized ligand comprising an aminosilicone group to optimize the capacity and productivity of CO capture relative to the adsorption of HO.

[0042] In general, functionalized adsorbents according to the present disclosure can be used with compositions according to the present disclosure, systems according to the present disclosure, and methods according to the present disclosure. The functionalized adsorbents are not limited to any particular embodiment disclosed herein.

[0043] In some embodiments, the functionalized adsorbent comprises a first type of functionalized ligand, the first type of functionalized ligand comprising at least one functionalized ligand comprising an aminosilicone group. Generally, the at least one functionalized ligand comprising an aminosilicone group can comprise any suitable ligand that facilitates the functionalized adsorbent described herein. The at least one functionalized ligand comprising an aminosilicone group can comprise only one functionalized ligand comprising an aminosilicone group, or two or more functionalized ligands, each comprising an aminosilicone group.

[0044] Generally, the adsorbent can be any suitable adsorbent known in the art that facilitates the functionalized adsorbents described herein. In some embodiments, the adsorbent is selected from the group consisting of coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCPs), covalent organic framework (COF) compounds, zeolitic imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open frameworks, network chemistry, silica particles, zeolites, silicoaluminophosphates (SAPOs), aluminophosphates (AlPOs), polyaromatic frameworks (PAFs), activated carbons, molecular organic solids, and combinations thereof.

[0045] As used herein, MOF compounds are a class of compounds containing metal ions or clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures. The metal ions or clusters are connected by multidirectional organic ligands that act as binders and linkers in the network structure. MOF compounds possess modularity that allows for synthetic tunability, resulting in fine chemical and structural control. Properties such as porosity, stability, particle morphology, and conductivity can be tailored to specific applications.

[0046] In many embodiments, the adsorbent is a MOF compound comprising a MOF metal or metal-containing cluster and a MOF linker.

[0047] In some embodiments, the MOF metal can be any suitable MOF metal known in the art that facilitates 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, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof. In some embodiments, the MOF metal comprises Mg.

[0048] In some embodiments, the MOF metal-containing cluster can be any suitable MOF metal-containing cluster known in the art that facilitates the functionalized adsorbents described herein. In some embodiments, the MOF metal-containing cluster comprises a MOF metal node and a linker strut, where the MOF metal and linker are each defined as described herein. In other embodiments, the MOF metal-containing cluster comprises a MOF metal-oxycluster.

[0049] In some embodiments, the MOF linker can be any suitable MOF linker known in the art that facilitates the functionalization of the adsorbents described herein. Generally, the geometry and connectivity of the linker contribute to the structure of the resulting MOF compound. Adjusting the geometry, length, ratio, and functional groups of the linker can tailor the size, shape, and internal surface properties of the MOF compound for targeted applications.

[0050] In at least some embodiments, the MOF linker is a linker selected from the group consisting of a ditopic linker, a tritopic linker, a tetratopic linker, a pentatopic linker, a hexatopic linker, a heptatopic linker, an octatopic linker, a mixed linker, a desymmetrized linker, a metal linker, an N-heterocyclic linker, and combinations thereof.

[0051] In at least some embodiments, the MOF linker is a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4”-dioxide-[1,1':4',1”-terphenyl]-3,3”-dicarboxylate (dotpdc 4- ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-DOBDC 4- ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4- ), 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), their protonated, partially 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 a dicarboxylate (e.g., terephthalic acid), a tricarboxylate (e.g., 1,3,5-benzenetricarboxylic acid), an azolate, a tetrazolate, and combinations thereof.

[0052] As another example, in at least some embodiments, the MOF linker is selected from the group consisting of 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, and the like. carboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimidedicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol E200 Dicarboxylic Acid, 3,6-Dioxaoctanedicarboxylic Acid, 3,5-Cyclohexadiene-1,2-dicarboxylic Acid, Octanedicarboxylic Acid, Pentane-3,3-carboxylic Acid, 4,4'-Diamino-1,1'-diphenyl-3,3'-dicarboxylic Acid, 4,4'-Diaminodiphenyl-3,3'-dicarboxylic Acid, Benzidine-3,3'-dicarboxylic Acid, 1,4-Bis-(phenylamino)benzene-2,5-dicarboxylic Acid, 1,1'-Dinaphthyl-8,8'-dicarboxylic Acid carboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-Dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cisdicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzonedicarboxylic acid, Pluriol E300 dicarboxylic acid, Pluriol E400 dicarboxylic acid, Pluriol E600 Dicarboxylic Acid, Pyrazole-3,4-dicarboxylic Acid, 2,3-Pyrazinedicarboxylic Acid, 5,6-Dimethyl-2,3-pyrazinedicarboxylic Acid, 4,4'-Diaminodiphenyletherdiimidedicarboxylic Acid, 4,4'-Diaminodiphenylmethanediimidedicarboxylic Acid, 4,4'-Diaminodiphenylsulfonediimidedicarboxylic Acid, 2,6-Naphthalenedicarboxylic Acid, 1,3-Adamantanedicarboxylic Acid, 1,8-Naphthalenedicarboxylic Acid, 2,3-Naphthalenedicarboxylic Acid, 8-Methoxy-2,3-naphthalenedicarboxylic Acid, 8-Nitro-2,3-naphthalenedicarboxylic Acid, 8-Sulfo-2,3-naphthalenedicarboxylic Acid, Anthracene-2,3-dicarboxylic Acid, 2'-3'-Diphenyl-p-terphenyl-4,4"-dicarboxylic Acid, Diphenylether-4,4'-dicarboxylic Acid Acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,The dicarboxylic acid linker is selected from the group consisting of 3-dicarboxylic acid, 2,9-dichlorofluorine-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.

[0053] 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.

[0054] As another example, in at least some embodiments, the MOF linker is selected from the group consisting of 1,1-dioxide-perillo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, meso-1,2,3,4-butane tetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzyl ...2, The tetracarboxylic acid linker is selected from the group consisting of 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, and combinations thereof.

[0055] In an exemplary embodiment, the MOF linker is 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc) and / or 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- In some embodiments, dobpdc comprises 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid, its monocarboxylate form, its dicarboxylate form, its monophenoxide form, its diphenoxide form, and combinations thereof.

[0056] In some embodiments, the MOF linker is the following linker: [ka] JPEG2026501066000003.jpg219142JPEG2026501066000004.jpg74170 and / or [ka] One or more of the following:

[0057] In some embodiments, the MOF linker is one or more of the following linkers:

[0058] 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).

[0059] In some embodiments, the functionalized adsorbent is a functionalized MOF compound of formula (AI):

number

[0060] In some embodiments, the functionalized adsorbent comprises a second type of functionalizing ligand, wherein the second type of functionalizing ligand comprises at least one functionalizing ligand that does not comprise an aminosilicone group. In some embodiments, the functionalized adsorbent also comprises at least one functionalizing ligand that does not comprise an aminosilicone group. Generally, the at least one functionalizing ligand that does not comprise an aminosilicone group can comprise any suitable ligand that facilitates the functionalized adsorbent described herein. The at least one functionalizing ligand that does not comprise an aminosilicone group can comprise only one functionalizing ligand that does not comprise an aminosilicone group, or two or more functionalizing ligands that each do not comprise an aminosilicone group.

[0061] In some embodiments, the at least one functionalized ligand that does not comprise an aminosilicone group is selected from the group consisting of amine ligands, monoamine ligands, diamine ligands, triamine ligands, tetra-amine ligands, penta-amine ligands, hexa-amine ligands, polyamine ligands, alkylamine ligands, and amino-alcohol ligands. Exemplary ligands include ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, di(N-methyl)ethylenediamine, N-isopropylethylenediamine, N,N-dimethyl-N-methylethylenediamine, di(N,N-dimethyl)ethylenediamine, N,N-diisopropylethylenediamine, 2,2-dimethyl-1,3-diaminopropane, 1,3-diaminopentane, diethylenetriamine, N-(2-aminoethyl)-1,3 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.

[0062] Generally, the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone 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 aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group are present in a ratio ranging from about 10:1 to about 1:10. In some embodiments, the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group are present in a ratio ranging from about 9:1 to about 1:9. In some embodiments, the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group are present in a ratio ranging from about 8:1 to about 1:8. In some embodiments, the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group are present in a ratio ranging from about 7:1 to about 1:7. In some embodiments, the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group are present in a ratio ranging from about 6:1 to about 1:6. In some embodiments, the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group are present in a ratio ranging from about 5:1 to about 1:5. In some embodiments, the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group are present in a ratio ranging from about 4:1 to about 1:4. In some embodiments, the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group are present in a ratio ranging from about 3:1 to about 1:3. In some embodiments, the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group are present in a ratio ranging from about 2:1 to about 1:2.In some embodiments, the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group are present in a ratio in the range of about 1:1.

[0063] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group is present in an amount less than the at least one functionalized ligand that does not comprise an aminosilicone group.

[0064] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group are present in a ratio of about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, or about 1:10.

[0065] In many embodiments, the at least one functionalizing ligand comprising an aminosilicone group can be any suitable at least one functionalizing ligand comprising an aminosilicone group known in the art to facilitate the functionalized adsorbents described herein.

[0066] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group comprises at least one amine selected from the group consisting of a primary amine, a secondary amine, a tertiary amine, and combinations thereof. In some embodiments, the at least one functionalized ligand comprising an aminosilicone group comprises at least one primary amine or at least one secondary amine.

[0067] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, penta-amines, hexa-amines, polyamines, and combinations thereof.

[0068] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group comprises at least one aminosilicone selected from the group consisting of linear aminosilicones, cyclic aminosilicones, branched aminosilicones, amino-substituted siloxanes, linear amino-substituted disiloxanes, cyclic amino-substituted disiloxanes, linear amino-substituted trisiloxanes, cyclic amino-substituted trisiloxanes, linear amino-substituted tetrasiloxanes, cyclic amino-substituted tetrasiloxanes, linear amino-substituted polysiloxanes, cyclic amino-substituted polysiloxanes, silsesquioxanes, polyoctahedral silsesquioxanes, and combinations thereof.

[0069] In some embodiments, at least one functionalized ligand comprising an aminosilicone group comprises a symmetric structure. In some embodiments, at least one functionalized ligand comprising an aminosilicone group comprises an asymmetric structure.

[0070] In some embodiments, when at least one functionalized ligand comprising an aminosilicone group comprises a disiloxane group, the at least one functionalized ligand comprising an aminosilicone group comprises the same amine on either side of the disiloxane group. In some embodiments, when at least one functionalized ligand comprising an aminosilicone group comprises a disiloxane group, the at least one functionalized ligand comprising an aminosilicone group comprises different amines on either side of the disiloxane group.

[0071] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group is an amino-substituted siloxane of Formula (A-II), Formula (A-III), Formula (A-IV), Formula (AV), Formula (A-VI), or Formula (A-VII): [ka] JPEG2026501066000008.jpg240144In formula, R1, R2, R3, R4, R9, R 10 , R 13 , R 14 and R 18are 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 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; R5, R6, R 11 , R 15 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 alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; 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 alkyl, a C1 alkyl, a C2 alkyl, a C3 alkyl, a C4 alkyl, a C5 alkyl, a C6 alkyl, and a substituent of formula (A-VIII); [ka] During the ceremony, the wavy bond indicates the position of attachment to formula (A-II) or formula (A-III) or formula (A-IV) or formula (AV) or formula (A-VI) or formula (A-VII), R 19 , R 20 , R 21 , R 22 , R 23 and R 24 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted 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 C1-C6 straight chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R25 and 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 alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, and substituted or unsubstituted C4-C6 cycloalkyl, or R 25 and R 26 are taken together to form a monocyclic ring selected from the group consisting of heterocycloalkyl and heteroaryl; R 27 , R 28 and R 29 are each independently selected from the group consisting of a direct bond, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-; R 30 is selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C1-C3 straight chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl; j is an integer ranging from 0 to 20, k is an integer ranging from 0 to 20; m is an integer ranging from 0 to 20, and n is an integer ranging from 0 to 20.

[0072] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group is [ka] JPEG2026501066000011.jpg232148JPEG2026501066000012.jpg223146JPEG2026501066000013.jpg213119JPEG2026501066000014.jpg104119 and [ka] is selected from the group consisting of:

[0073] 4 is a schematic diagram of an exemplary control system 400 that may be used to capture CO2 in a capture system, such as capture system 100 (shown in FIG. 1) and / or capture system 200 (shown in FIG. 2). In the exemplary embodiment, controller 116 includes a memory 402 and a processor 404. Controller 116 controls, for example, the regulated temperature T of first stream 122. reg The temperature of one or more of the adsorption modules 104a-104d may be adjusted based on data received by the control system 400 from the contactor sensors 130. The controller 116 adjusts the temperature T reg The temperature of one or more of the adsorption modules 104a-104d can be adjusted based on a comparison with data stored in memory 402, such as a desired range of temperature, instructions stored in memory 402, and / or data analyzed by processor 404.

[0074] Additionally, the controller 116 may include, but is not limited to, a controlled temperature T cntl The controller 116 may adjust the temperature of one or more of the adsorption modules 104a-104d based on data received by the control system 400 from the module sensors 134, such as the H2O relative humidity within the one or more adsorption modules 104a-104d. cntland / or the temperature of one or more of the adsorption modules 104a-104d may be adjusted based on a comparison with data stored in memory 402, such as a desired range of HO relative humidity, instructions stored in memory 402, and / or data analyzed by processor 404.

[0075] Described herein is an exemplary system for using a functionalized chemical sorbent in the presence of water to facilitate optimization of carbon dioxide adsorption and desorption by an adsorbent bed. The exemplary system described herein offers several advantages over conventional designs and processes, including at least improving carbon dioxide adsorption and desorption efficiency and performance through the use of temperature variation in the adsorbent bed, improving carbon dioxide adsorption and desorption efficiency and performance through the use of functionalized adsorbents in the adsorbent bed, improving carbon dioxide adsorption and desorption efficiency and performance through the use of variation in the relative humidity of the water in the adsorbent bed, and improving capture system performance through modulation of the temperature and relative humidity of the water in one or more adsorption modules in adsorbent beds based on the functionalized adsorbents in one or more adsorption modules.

[0076] Further aspects of the invention are provided by the subject matter of the following clauses.

[0077] 1. A capture system for use in capturing carbon dioxide, comprising: an adsorbent bed comprising at least one adsorption module and a functionalized adsorbent; the at least one adsorption module oriented to receive a gas stream, adsorb carbon dioxide from the gas stream via the functionalized adsorbent, and discharge a vent stream; a contactor for use in 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 adsorbent bed.

[0078] 2. The capture system of any preceding clause, wherein the contactor is oriented to receive a conditioning fluid for use in dynamically controlling the temperature of at least one adsorption module.

[0079] 3. A capture system according to any preceding clause, further comprising at least one injector oriented to discharge a moisture stream to control the water relative humidity of the at least one adsorption module.

[0080] 4. The capture system of any preceding clause, wherein the controller is further configured to reduce a fluid temperature of the conditioning fluid received by the contactor to facilitate increasing the relative humidity of the water.

[0081] 5. The capture system of any preceding clause, wherein the controller is further configured to adjust the water relative humidity of the at least one adsorption module to facilitate increasing the amount of carbon dioxide captured by the adsorbent bed.

[0082] 6. The capture system according to any of the preceding clauses, wherein the controller is further configured to increase the water relative humidity of the at least one adsorption module to promote an increase in the amount of carbon dioxide adsorbed by the functionalized adsorbent.

[0083] 7. The capture system of any of the preceding clauses, wherein the controller is further configured to increase the pressure of the water stream exiting the injector to facilitate an increase in the water relative humidity of the at least one adsorption module.

[0084] 8. The capture system of any of the preceding clauses, wherein the controller is further configured to adjust the temperature and water relative humidity of the at least one adsorption module to achieve a desired relative humidity based on the moisture adsorption isotherm of the functionalized adsorbent.

[0085] 9. The capture system of any of the preceding clauses, wherein the temperature and water relative humidity of at least one adsorption module is based on the relative humidity at the knee point of the moisture adsorption isotherm of the functionalized adsorbent.

[0086] 10. A capture system according to any of the preceding clauses, wherein at least one adsorption module comprises a plurality of adsorption modules coupled in a serial flow arrangement.

[0087] 11. A capture system according to any of the preceding clauses, wherein the at least one injector includes an injector coupled to each of the plurality of adsorption modules.

[0088] 12. A capture system according to any preceding clause, wherein the controller is further configured to regulate the temperature and water relative humidity of each of the plurality of adsorption modules.

[0089] 13. A capture system according to any of the preceding clauses, wherein the functionalized sorbent comprises an adsorbent and at least one functionalized ligand comprising an amine group.

[0090] 14. A capture system according to any of the preceding clauses, wherein the at least one functionalized ligand comprising an amine group comprises at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof.

[0091] 15. A capture system according to any of the preceding clauses, wherein the at least one functionalized ligand comprising an amine group comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, penta-amines, hexaamines, polyamines, and combinations thereof.

[0092] 16. A capture system according to any of the preceding clauses, wherein the functionalized sorbent comprises an adsorbent and at least one functionalized ligand comprising an aminosilicone group.

[0093] 17. The functionalized adsorbent is a functionalized MOF compound of formula (AI),

number

[0094] 18. The capture system of any 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, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof.

[0095] 19. The MOF linker is a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4”-dioxide-[1,1':4',1”-terphenyl]-3,3”-dicarboxylate (dotpdc 4- ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-DOBDC 4- ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4-), 4,4'-[oxalylbis(imino)bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), dicarboxylate, terephthalic acid, tricarboxylate, 1,3,5-benzotricarboxylic acid, azolate, tetrazolate, 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butanedicarboxylic acid Diene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimidedicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol 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-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxo Imidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cisdicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenone dicarboxylic acid, Pluriol 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'-Diaminodiphenyldiimidecarboxylic acid, 4,4'-Diaminodiphenylmethanedicarboxylic acid, 4,4'-Diaminodiphenylsulfonediimidedicarboxylic acid, 2,6-Naphthalenedicarboxylic acid, 1,3-Adamantanedicarboxylic acid, 1,8-Naphthalenedicarboxylic acid, 2,3-Naphthalenedicarboxylic acid, 8-Methoxy-2,3-naphthalenedicarboxylic acid, 8-Nitro-2,3-naphthalenedicarboxylic acid, 8-Sulfo-2,3-naphthalenedicarboxylic acid anthracene-2,3-dicarboxylic acid, 2'-3'-diphenyl-p-terphenyl-4,4"-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-Dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosene dicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorine-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-dehydrobornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, 2-hydroxy-1,2,3-propanedicarboxylic acid 1,2,4-Benzenetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene- 1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurintricarboxylic acid, 1,1-dioxide-perillo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-Hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentanetetracarboxylic acid, The capture system of any preceding clause, comprising a linker selected from the group consisting of: ditopic linkers, tritopic linkers, tetratopic linkers, pentatopic linkers, hexatopic linkers, heptatopic linkers, octatopic linkers, mixed linkers, demetallated linkers, metallo linkers, N-heterocyclic linkers, protonated, partially and fully deprotonated forms, and combinations thereof.

[0096] 20. A capture system according to any of the preceding clauses, wherein the at least one functionalized ligand comprising an aminosilicone group comprises at least one aminosilicone selected from the group consisting of linear aminosilicones, cyclic aminosilicones, branched aminosilicones, amino-substituted siloxanes, linear amino-substituted disiloxanes, cyclic amino-substituted disiloxanes, linear amino-substituted trisiloxanes, cyclic amino-substituted trisiloxanes, linear amino-substituted tetrasiloxanes, cyclic amino-substituted tetrasiloxanes, linear amino-substituted polysiloxanes, cyclic amino-substituted polysiloxanes, silsesquioxanes, polyoctahedral silsesquioxanes, and combinations thereof.

[0097] Synthesis of aminoalkyl-substituted disiloxanes

[0098] In one aspect, a method for preparing an aminoalkyl-substituted disiloxane is provided, the method comprising: I) forming a mixture comprising a di- or polyamine containing at least one primary amine group and a silane, II) reacting the mixture in a first reaction, III) adding a hydrolysis agent to the mixture, and IV) reacting the mixture in a second reaction to form the aminoalkyl-substituted disiloxane.

[0099] In another aspect, there is provided an aminoalkyl-substituted disiloxane of formula (BI), which is as follows: [ka] During the ceremony, 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 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; 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 alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; R 18 and R 19 are each independently selected from the group consisting of substituents of formula (B-IV), [ka] During the ceremony, The wavy bond indicates the point of attachment to formula (BI), 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 alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C1-C6 straight chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R 31 and R 32 are each individually selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C1-C3 straight chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, and substituted or unsubstituted C4-C6 cycloalkyl, or when taken together, R 31 and R 32 forms a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl; 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 alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-; R 36is selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C1-C3 straight chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl; m is an integer ranging from 0 to 20; However, aminoalkyl-substituted disiloxanes [ka] isn't it.

[0100] The embodiments described herein overcome at least some of the drawbacks of aminoalkyl-substituted disiloxanes and known methods for preparing aminoalkyl-substituted disiloxanes. Exemplary embodiments described herein include a method for preparing aminoalkyl-substituted disiloxanes, the method comprising: I) forming a mixture containing a di- or polyamine containing at least one primary amine group and a silane; II) reacting the mixture in a first reaction; III) adding a hydrolysis agent to the mixture; and IV) reacting the mixture in a second reaction to form the aminoalkyl-substituted disiloxane. The exemplary embodiments described herein avoid side reactions and / or produce the desired product in superior yield and purity with fewer steps compared to known methods for preparing aminoalkyl-substituted disiloxanes.

[0101] 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 involve one reaction or two or more reactions. A one-pot synthesis is particularly advantageous for reducing the complexity of the reaction and avoiding lengthy and expensive separation and purification.

[0102] In many embodiments, the aminoalkyl-substituted disiloxane is an amino-C1-C6 alkyl-substituted disiloxane. Embodiments containing a C1-C6 alkyl group are thermodynamically favored to form compared to other compounds containing larger aminoalkyl substituents or alternative substituents. In some embodiments, the aminoalkyl-substituted disiloxane is an aminomethyl-substituted disiloxane.

[0103] 13 is an exemplary method flowchart 1310. In this exemplary embodiment, the method flowchart 1310 illustrates the essential method steps of exemplary embodiments described herein and is not intended to limit the method embodiments. Initially, a mixture is formed 1312 including a di- or polyamine containing at least one primary amine group and a silane. The mixture is reacted 1314 in a first reaction, and a hydrolysis agent is added 1316 to the mixture. The mixture is then reacted 118 in a second reaction to form an aminoalkyl-substituted disiloxane.

[0104] In some embodiments, the aminoalkyl-substituted disiloxane according to the present disclosure is selected from the group consisting of aminoalkyl-substituted disiloxanes of formula (BI): [ka] During the ceremony, 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 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; R 16 and R 17are 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 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; R 18 and R 19 are each independently selected from the group consisting of substituents of formula (B-IV), [ka] During the ceremony, The wavy bond indicates the point of attachment to formula (BI), 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 alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C1-C6 straight chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R 31 and R 32 are each individually selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C1-C3 straight chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, and substituted or unsubstituted C4-C6 cycloalkyl, or when taken together, R 31 and R 32 forms a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl; R 33 , R34 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 alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-; 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 alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl; m is an integer ranging from 0 to 20, preferably ranging from 0 to 10, and even more preferably ranging from 0 to 3; However, aminoalkyl-substituted disiloxanes [ka] isn't it.

[0105] In some embodiments, the aminoalkyl-substituted disiloxane is [ka] JPEG2026501066000024.jpg58146 and [ka] is selected from the group consisting of:

[0106] In some embodiments, the di- or polyamine containing at least one primary amine group can be any suitable di- or polyamine containing at least one primary amine group known in the art that facilitates the methods described herein. In other embodiments, the di- or polyamine containing at least one primary amine group is a compound of formula (B-II): [ka] During the ceremony, R1, R2, R 3, R4, R5 and R6 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; R7 and R8 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C1-C3 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, and substituted or unsubstituted C4-C6 cycloalkyl, or when taken together, R7 and R8 form a monocycle selected from the group consisting of heterocycloalkyl or heteroaryl; 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 alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2CH2-, -OCH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2- and -NHCH2CH2CH2CH2-; n is an integer in the range of 0 to 20, preferably in the range of 0 to 10, and even more preferably in the range of 0 to 3.

[0107] In some embodiments, the silane can be any suitable silane known in the art that facilitates 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): [ka] During the ceremony, R 20 is selected from the group consisting of halides, fluorides, chlorides, bromides, and iodides; R 21 and R 22 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 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; R 23 and R 24 are each independently selected from the group consisting of substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, aryl, and phenyl.

[0108] In some embodiments, R 23 and R 24 are each independently selected from the group consisting of substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl, preferably C1-C6 straight chain alkyl.

[0109] In some embodiments, R 23 is a C1 alkyl.

[0110] In some embodiments, R 24 is C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, aryl or phenyl.

[0111] In some embodiments, the silane is [ka] In some embodiments, the silane is [ka] is.

[0112] In many embodiments, reacting the mixture in a first reaction 1314 can be carried out under any suitable reaction conditions known in the art that facilitate the methods described herein, hi some embodiments, reacting the mixture in a first reaction 1314 includes stirring the mixture.

[0113] In many embodiments, reacting the mixture in the first reaction 1314 can be carried out for any suitable time known in the art that facilitates the methods described herein. In some embodiments, the mixture is reacted in the first reaction 1314 for an elapsed time in the range of about 1 second to about 12 hours. In some embodiments, the mixture is reacted in the first reaction 1314 for an elapsed time in the range of about 1 second to about 6 hours. In some embodiments, the mixture is reacted in the first reaction 1314 for an elapsed time in the range of about 1 second to about 3 hours. In some embodiments, the mixture is reacted in the first reaction 1314 for an elapsed time in the range of about 1 hour to about 3 hours. In some embodiments, the mixture is reacted in the first reaction 1314 for an elapsed time in the range of about 2 hours to about 3 hours.

[0114] In some embodiments, reacting the mixture in a first reaction 1314 involves adding a silane (e.g., chloromethyldimethylethoxysilane) dropwise over about 1 hour to a neat di- or polyamine containing at least one primary amine group. The reaction temperature is allowed to rise to about 90°C due to the reaction exotherm and held at this temperature for the duration of the reaction (about 2-3 hours total). During this time, the HCl salt of the amine forms and may precipitate to varying degrees depending on the amine.

[0115] In some embodiments, the hydrolyzing agent is added dropwise to the mixture 1316. 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 over a period of time ranging from about 1 second to about 12 hours 1316. In some embodiments, the hydrolyzing agent is added over 30 minutes and exothermic conditions 1316, and cooled to room temperature before reacting 118 the mixture in a second reaction.

[0116] In some embodiments, the hydrolyzing agent is added 1316 over 30 minutes and exothermic conditions before reacting the mixture in a second reaction 1318. In these embodiments, the reaction 1318 is completed before allowing the reaction mixture to cool to room temperature.

[0117] In many embodiments, the hydrolysis agent can be any suitable hydrolysis agent known in the art that facilitates the methods described herein. In some embodiments, the hydrolysis agent is an aqueous solution. In some embodiments, the hydrolysis agent is water.

[0118] In many embodiments, reacting 1318 the mixture in a second reaction can be carried out under any suitable reaction conditions known in the art that facilitate the methods described herein. In some embodiments, reacting 1318 the mixture in a second reaction includes adjusting the temperature of the mixture. In some embodiments, reacting 1318 the mixture in a second reaction includes cooling the mixture.

[0119] 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 using an organic solvent.

[0120] In some embodiments, extracting the aminoalkyl-substituted disiloxane from the reaction mixture comprises adding an organic solvent (e.g., chloroform and / or toluene) dropwise 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 isolated, the aqueous layer is back-extracted with a minimum of organic solvent, and the combined organic layers are concentrated under vacuum, triturated once with organic solvent, and then dried under vacuum.

[0121] In some embodiments, the aminoalkyl-substituted disiloxane is further purified. In some embodiments, further purification includes the use of distillation, vacuum distillation, and / or heat. In some embodiments, further purification includes the use of vacuum distillation to remove impurities and by-products. In these embodiments, the remaining material in the distillation pot is a higher purity product compared to the product prior to purification.

[0122] In many embodiments, reacting the mixture in the second reaction 1318 can be carried out for any suitable time known in the art that facilitates the methods described herein. In some embodiments, the mixture is reacted in the second reaction 1318 for an elapsed time in the range of about 1 second to about 12 hours. In some embodiments, the mixture is reacted in the second reaction 1318 for an elapsed time in the range of about 1 second to about 6 hours. In some embodiments, the mixture is reacted in the second reaction 1318 for an elapsed time in the range of about 1 second to about 3 hours. In some embodiments, the mixture is reacted in the second reaction 1318 for an elapsed time in the range of about 1 hour to about 3 hours. In some embodiments, the mixture is reacted in the second reaction 1318 for an elapsed time in the range of about 2 hours to about 3 hours.

[0123] In many embodiments, the methods can also include any additional suitable processing steps known in the art that facilitate the success of the methods described herein. Such processing steps include, but are not limited to, washing, drying, filtering, purifying, separating, centrifuging, and any combination thereof. In some embodiments, the methods further include washing the aminoalkyl-substituted disiloxane compound. In some embodiments, the methods further include purifying the aminoalkyl-substituted disiloxane compound. In some embodiments, the purification includes distillation, vacuum distillation, and / or the use of heat. In some embodiments, the methods further include removing volatile reaction by-products.

[0124] In some embodiments, the method includes: I) forming a mixture comprising a di- or polyamine containing at least one primary amine group and a chloromethyldimethylalkoxysilane; II) reacting the mixture in a first reaction by controlled exothermic nature; III) adding a hydrolysis 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.

[0125] In many embodiments, the aminoalkyl-substituted disiloxanes can be used according to any suitable purpose known in the art. In some embodiments, the aminoalkyl-substituted disiloxanes are used in carbon capture systems. In some embodiments, the aminoalkyl-substituted disiloxanes are used in aminosilicone-based products.

[0126] Further aspects of the present disclosure are provided by the subject matter of the following clauses.

[0127] 1. A method for preparing an aminoalkyl-substituted disiloxane, the method comprising: I) forming a mixture comprising a di- or polyamine containing at least one primary amine group and a silane; II) reacting the mixture in a first reaction; III) adding a hydrolysis agent to the mixture; and IV) reacting the mixture in a second reaction to form the aminoalkyl-substituted disiloxane.

[0128] 2. The aminoalkyl-substituted disiloxane is a compound of formula (BI): [ka] During the ceremony, 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 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; 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 alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; R 18 and R 19 are each independently selected from the group consisting of substituents of formula (B-IV), [ka] During the ceremony, The wavy bond indicates the point of attachment to formula (BI), 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 alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C1-C6 straight chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R 31 and R 32 are each individually selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C1-C3 straight chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, and substituted or unsubstituted C4-C6 cycloalkyl, or when taken together, R 31 and R 32 forms a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl; 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 alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-; R 36is selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C1-C3 straight chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl; m is an integer ranging from 0 to 20; The method described in the preceding clause.

[0129] 3. The aminoalkyl-substituted disiloxane is [ka] JPEG2026501066000033.jpg155146 and [ka] The method of any of the preceding clauses, wherein the compound is selected from the group consisting of:

[0130] 4. The di- or polyamine containing at least one primary amine group is a compound of formula (B-II): [ka] During the ceremony, R1, R2, R 3, R4, R5 and R6 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; R7 and R8 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C1-C3 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, and substituted or unsubstituted C4-C6 cycloalkyl, or when taken together, R7 and R8 form a monocycle selected from the group consisting of heterocycloalkyl or heteroaryl; 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 alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2CH2-, -OCH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2- and -NHCH2CH2CH2CH2-; n is an integer ranging from 0 to 20; Any method described in any of the preceding clauses.

[0131] 5. In at least some embodiments, the silane is a compound of formula (B-III): [ka] During the ceremony, R 20 is selected from the group consisting of halides, fluorides, chlorides, bromides, and iodides; R 21 and R 22 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 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; R 23 and R 24 are each independently selected from the group consisting of substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, aryl, and phenyl; Any method described in any of the preceding clauses.

[0132] 6. Cilantro [ka] or [ka] 10. The method of any of the preceding clauses, wherein

[0133] 7. The method of any of the preceding clauses, wherein reacting the mixture in the first reaction comprises stirring the mixture.

[0134] 8. The method of any of the preceding clauses, wherein reacting the mixture in a first reaction comprises reacting the mixture for a first period of time.

[0135] 9. The method of any preceding clause, wherein the first period of time is a time in the range of about 1 second to about 12 hours.

[0136] 10. The method of any of the preceding clauses, wherein the hydrolyzing agent is an aqueous solution.

[0137] 11. The method of any of the preceding clauses, wherein the hydrolyzing agent is water.

[0138] 12. The method of any of the preceding clauses, wherein a hydrolyzing agent is added to the mixture over a second period of time.

[0139] 13. The method of any preceding clause, wherein the second period of time is a time period ranging from about 1 second to about 12 hours.

[0140] 14. The method of any one of the preceding clauses, wherein the hydrolyzing agent is added dropwise to the mixture.

[0141] 15. The method of any of the preceding clauses, further comprising purifying the aminoalkyl-substituted disiloxane.

[0142] 16. The method of any of the preceding clauses, wherein at least one method step includes adjusting the temperature of the mixture.

[0143] 17. The method of any of the preceding clauses, wherein reacting the mixture in the second reaction includes adjusting the temperature of the mixture.

[0144] 18. The method of any of the preceding clauses, wherein reacting the mixture in a second reaction includes cooling the mixture.

[0145] 19. The method of any one of the preceding clauses, wherein the method is a one-pot synthesis.

[0146] 20. An aminoalkyl-substituted disiloxane prepared by the method described in any of the preceding clauses.

[0147] 21. Aminoalkyl-substituted disiloxanes of formula (BI): [ka] During the ceremony, 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 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; R16 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 alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; R 18 and R 19 are each independently selected from the group consisting of substituents of formula (B-IV), [ka] During the ceremony, The wavy bond indicates the point of attachment to formula (BI), 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 alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C1-C6 straight chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R 31 and R 32 are each individually selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C1-C3 straight chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, and substituted or unsubstituted C4-C6 cycloalkyl, or when taken together, R 31 and R 32 forms a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl; R 33 , R34 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 alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-; 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 alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl; m is an integer ranging from 0 to 20; However, aminoalkyl-substituted disiloxanes [ka] isn't it, An aminoalkyl-substituted disiloxane of formula (BI):

[0148] 22. An aminoalkyl-substituted disiloxane is [ka] JPEG2026501066000043.jpg155146 and [ka] The aminoalkyl-substituted disiloxane of the preceding clause selected from the group consisting of:

[0149] Machine learning models incorporating physical characteristics of sorbents for post-combustion carbon capture

[0150] 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 dataset, each instance of the model training dataset identifying a sorbent used by the capture system, a carbon capture performance value of the sorbent, and a plurality of primary feature values ​​associated with a plurality of primary features. The processor is also 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 to determine a plurality of correlation strength values ​​including a correlation strength value between each of the plurality of primary features and each of the one or more secondary features. The processor is also configured to identify a first subset of the model training dataset based on the plurality of correlation strength values, determine a statistical significance of each instance of the first subset of the model training dataset, and identify a second subset of the model training dataset based on the statistical significance, wherein the statistical significance of each instance of the second subset of the model training dataset is below a predetermined threshold. The processor is further configured to generate a transfer function based on a second subset of the model training dataset and to use the transfer function to determine one or more expected sorbents to be used by the capture system based on the carbon capture performance values. The controller causes the capture system to operate using the one or more expected sorbents determined by the modeling system.

[0151] In another aspect, a method for selecting one or more promising sorbents for use in operating a capture system to capture carbon dioxide includes identifying a model training dataset, each instance of the model training dataset identifying a sorbent used by the capture system, a carbon capture performance value of the sorbent, and a plurality of primary feature values ​​associated with a plurality of primary features. The method also 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 strength values ​​including a correlation strength 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 dataset based on the plurality of correlation strength values. The method also includes determining a statistical significance of each instance of the first subset of the model training dataset; identifying a second subset of the model training dataset based on the statistical significance, wherein the statistical significance of each instance of the second subset of the model training dataset is below a predetermined threshold; and generating a transfer function based on the second subset of the model training dataset. The method further includes using the transfer function to determine one or more expected sorbents to be used by the capture system based on the carbon capture performance values, and the controller causes the capture system to operate using the one or more expected sorbents determined using the transfer function.

[0152] In one embodiment, a computer program is provided, the program embodied on a computer-readable medium. In an exemplary embodiment, the system runs on a single computer system without requiring connection to a server computer. In a further embodiment, the system runs in a Windows® environment (Windows is a registered trademark of Microsoft Corporation, Redmond, Washington). In yet another embodiment, the system runs on a mainframe environment and a UNIX® server environment (UNIX is a registered trademark of X / Open Company Limited, located in Reading, Berkshire, United Kingdom). In a further embodiment, the system runs in an iOS® environment (iOS is a registered trademark of Cisco Systems, Inc., located in San Jose, CA). In yet a further embodiment, the system runs on a MacOS® environment (MacOS is a registered trademark of Apple Inc., located in Cupertino, CA). In yet a further embodiment, the system operates on the Android® OS (Android is a registered trademark of Google, Inc., located in Mountain View, CA). In another embodiment, the system runs on the Linux® OS (Linux is a registered trademark of Linus Torvalds, Boston, MA). The application is flexible and designed to operate in a variety of different environments without compromising primary functionality. In some embodiments, the system includes multiple components hosted across multiple computing devices. One or more of the components may be in the form of computer-executable instructions embodied on a computer-readable medium.

[0153]

[0001] 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 components and their performance in carbon dioxide (CO2) capture capacity. In exemplary embodiments, a modeling system is configured to train a model based on the performance characteristics of known metal-organic frameworks (MOFs) and their associated components. This model can then be used to evaluate the expected performance of other MOFs based on their specific components. Such modeling can help scientists and engineers evaluate different MOFs without having to physically test each candidate, thus leading to faster development of MOFs with improved performance in CO2 capture capacity.

[0154] FIG. 14 shows an exemplary PCC modeling system 1440 that can be used to predict how a particular MOF might perform in capturing carbon dioxide (CO) from the exhaust gas 1416 of a coal-fired power plant 1410. In the exemplary embodiment, the power plant 1410 generates electricity 1412 that is distributed via a transmission and distribution grid 1414. The power plant 1410 also includes a post-combustion carbon capture (PCC) system 1420 configured to remove CO from the exhaust gas 1416 before the treated exhaust is released to 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: a metal 1424, an organic linker 1426, and one or more functional groups 1428. During operation, the PCC system 1420 produces several performance results, generally represented herein for purposes of explanation as “capture performance” 1430 (e.g., PCC capacity). The PCC modeling system 1440 is configured to estimate how a particular MOF (e.g., a particular combination of components and various associated physical characteristics) will perform when implemented in the PCC system 1420 (e.g., performance prediction in a "real-world" setting).

[0155] In an exemplary embodiment, PCC modeling system 1440 includes a data collection and preparation module 1442 configured to identify and store data used to train a machine learning model (e.g., a supervised predictive model). Preparation module 1442 stores historical records of various adsorbents (e.g., MOFs 1422) and their associated characteristics and known performance. Each historical record contains adsorbent data such as, for example, components of a particular adsorbent (e.g., information about the metals 1424 used in secondary building units or SBUs, information about the organic linkers 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., isothermal heat of adsorption (Q ) at a particular pressure and / or temperature). ST ), Henry's law constant, selectivity ratio, adsorbent capacity in millimoles of CO2 per gram of adsorbent, adsorbent productivity in millimoles of CO2 per gram of adsorbent per unit time, etc. Each of these historical records can be stored as model data 1460 (e.g., in a database) and can include other data described herein. Some of these records may be recovered from published literature, while other records may include data recovered from laboratory measurement data or operational performance data of the PCC system 1420 (e.g., data collected during operation).

[0156] The PCC modeling system 1440 also includes an exploratory data analysis module 1444 configured to help the analyst 1402 perform univariate data analysis on aspects of the historical data. In an exemplary embodiment, the exploratory data analysis module 1444 is configured to generate graphs displaying a single feature versus a single component of known MOFs, thereby allowing the analyst 1402 to see trends in the feature across various MOFs. For example, the analysis module 1444 can generate plots of chemisorbent and physisorbent MOFs and how they perform in terms of Henry's constants, selectivity ratios, heats of adsorption, PCC capacity, and PCC productivity (e.g., as a composite across these two types of MOFs). In another example, the analysis module 1444 can generate plots of various metal types in physisorbent or chemisorbent MOFs and their respective heats of adsorption (e.g., ranges of values ​​for each metal type, average values, etc.). These plots can be compiled and generated from historical records identified in the model data 1460 and displayed to the analyst 1402 via the display of the computing device 1404. From this data, the analyst 1402 can further identify one or more secondary features, which may be combinations of two or more of the primary features, as described further below. Such secondary features can be used in subsequent model training and analysis.

[0157] In an exemplary embodiment, the PCC modeling system 1440 also 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 of the historical records. For example, the analysis module 1446 can identify a set of primary features and possibly one or more secondary features and perform a correlation analysis between the associated features. For each particular pairing of two features, the analysis module 1446 calculates a correlation coefficient (e.g., across all records in the model data 1460) that identifies how those two features correlate with each other (e.g., a positive coefficient indicates a positive correlation between the two features, and a negative coefficient indicates a negative correlation between the two features). These correlation coefficients may be, for example, Pearson's correlation coefficients, etc. These correlation coefficients can be displayed to the analyst 1402 in a matrix format, allowing the analyst 1402 to see the strength of the correlations between various pairs of features. In some examples, the matrix may be a heat map colored along the spectrum based on the magnitude of the correlation coefficient, for example, displaying each correlation coefficient in a color on a color spectrum with a strong positive correlation at one end of the spectrum (e.g., dark blue) and a strong negative correlation at another color at the opposite end of the spectrum (e.g., dark red). In some examples, the analysis module 1446 may generate a pair plot for each of the feature pairs, thereby allowing the analyst 1402 to assess what type of relationship the two features have (e.g., linear, nonlinear, or the like).

[0158] The PCC modeling system 1440 also includes a regression analysis module 1448 configured to perform a regression analysis using the model data 1460. In an 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 inspect the correlation matrix and / or pair plots described above and select a subset of 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 with PCC capacity above a certain threshold (e.g., strongly positively correlated). In some embodiments, the regression analysis module 1448 can also select all features that have a negative correlation coefficient with PCC capacity below a certain threshold (e.g., strongly negatively correlated). In some embodiments, the features used to initiate the regression analysis are manually selected by a user or the like.

[0159] Once the subset of features is identified, the regression analysis module 1448 performs a regression analysis process starting with 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., used in this 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, each stage involving performing a multiple linear regression analysis on the current feature set. Based on the results of each stage, one or more features may be removed for subsequent stages of analysis, leaving a further subset of down-selected features for the next stage of analysis until a certain stopping criterion is achieved. In this final stage, the regression analysis module 148 generates a transfer function using the last remaining down-selected features (e.g., PCC capacity as a function of a particular down-selected feature). This transfer function can then be applied to a new MOF and its associated feature values ​​to predict how the new MOF may perform in terms of PCC capacity, productivity, etc.

[0160] Additional details and related functions performed by the PCC modeling system 1440 are described in more detail in connection with FIGS.

[0161] FIG. 15 is a graph 1500 illustrating the decline in CO adsorption productivity of an exemplary adsorbent (e.g., an exemplary MOF) when progressing from a synthetic powder measured under equilibrium conditions to a final film coating on a substrate measured under dynamic conditions. In an exemplary embodiment, the Y-axis 1502 of graph 1500 is the adsorbent productivity of the MOF in kilograms of CO per kg of adsorbent per hour (hr). The X-axis shows several stages 1504 of PCC productivity from an initial stage 1504A through a kinetic time effect stage 1504B, a film mass transfer effect stage 1504C, a thermodynamic effect (working capacity between adsorption and desorption) stage 1504D, and an equilibrium powder productivity stage 1504E. In this example, at the initial stage 1504A, the adsorbent exhibits a productivity of approximately 0.58 kg CO / kg / hr for the synthetic powder measured under equilibrium conditions. At each stage 1504A-1504E, the adsorbent experiences a different decline in productivity based on the various effects discussed above. For example, in dynamic time effect step 1504B, the adsorbent may experience a production decrease 1512 of about 0.2 to a total of about 0.35 kg CO / kg / hr. Further, for example, in film mass transfer effect step 1504C, the adsorbent may experience a second production decrease 1514 of about 0.05 to a total of just under about 0.3 kg CO / kg / hr. Further, for example, in thermodynamic effect working capacity step 1504D, the adsorbent may experience a third production decrease 1516 of about 0.1 to a final coating operation productivity 1520 of about 0.2 kg CO / kg / hr. Thus, in this example, the adsorbent may experience a total productivity drop 1522 of about 0.38 kg CO / kg / hr, or about a 65% drop (e.g., about a 35% utilization). This knockdown effect is specific to each adsorbent, film coating, and cycle time operation.

[0162] The shown decline in PCC productivity for the exemplary adsorbent in Figure 15 generally depends on coating type and measurement type characteristics and can be attributed to a combination of factors such as cycle time kinetics of adsorption where equilibrium is not achieved, coating mass transfer resistance, and isosteric heat of adsorption which heats the adsorbent and reduces performance capacity. In the absence of the PCC modeling system 1440 of Figure 14, all of these factors are generally determined experimentally to understand the final productivity of a given adsorbent.

[0163] For initial sorption at low concentrations, the Henry's law constant determines the equilibrium capacity of the adsorbent i, N i The adsorbent capacity is calculated by the gas phase concentration of the adsorbent, C i Henry's law constant H multiplied by i is a function of N i =H i C i The larger the value of Henry's constant, the steeper the initial slope of the isotherm. This means that adsorbents with higher H have a greater capacity for the adsorbate in this low-concentration linear region of the isotherm. H i Maximizing the Henry's Law constant also increases the adsorbent's productivity at low gas-phase adsorbate concentrations. Thus, the PCC modeling system 1440 attempts to find adsorbents with high Henry's Law constants for CO2 adsorption by analyzing how various MOF components independently vary with Henry's Law constant. Because Henry's Law constants are thermodynamic terms (e.g., not kinetic terms), adsorbent kinetics can also be evaluated to determine adsorbent productivity. These measurements are typically not reported in the literature for known MOFs, and therefore, this PCC modeling system 1440 can first focus on Henry's Law constants to identify MOF components with the highest CO2 capacity potential at the lowest CO2 gas-phase concentrations. When kinetic uptake data are available, they are used as data inputs into the PCC modeling system.

[0164] 16A-16C are flowcharts illustrating an exemplary method 1600 for analyzing the expected performance of a prospective sorbent in a post-combustion carbon capture system. In some embodiments, method 1600 may be performed by PCC modeling system 1440, and the identified sorbent may be installed in PCC system 1420 of FIG. 14. In the exemplary embodiment, method 1600 includes, in operation 1610, collecting or otherwise identifying model training data for a known sorbent (e.g., a MOF for which there is known performance data).

[0165] The identified model training data, in an exemplary embodiment, includes individual sorbent instances and their specific compositions, as well as known performance data stored in a database, such as a model data database (e.g., various variables of a particular known sorbent). Each sorbent can include information about the components of that particular sorbent instance (e.g., specific metals, organic linkers, and / or functional groups), various physical characteristics of the sorbent instance (e.g., pore size, pore volume, isometric heat of adsorption, Henry's law constant, selectivity ratio, Langmuir / BET area, uptake rate, etc.), known performance data of the sorbent instance (e.g., PCC capacity and productivity), and possibly other information about the sorbent instance, such as a unique identifier or other sorbent data (e.g., physisorption or chemisorption classification). Metals can include, for example, nickel, chromium, magnesium, copper, manganese, zirconium, zinc, cobalt, indium, iron, aluminum, dysprosium, titanium, potassium, etc., or some combination or alloy.Examples of organic linkers include 1,4-dioxide-2,5-benzenedicarboxylate (DOBDC), 1,4-benzenedicarboxylate (BDC), 4,4'-oxide-1,1'-biphenyl-3,3'-dicarboxylate (DOBPDC), 1,3,5-tri(1H-1,2,3 trizol-4-yl)benzene) (BTTri), 1,3,5-benzenetricarboxylate (BTC), 1H,5H-benzo(1,2-d:4,5-d')bistriazole (BBTA), 1,1'-biphenyl-4,4'-dicarboxylate (BPDC), 1,1'-biphenyl-3,3',5,5' tetracarboxylate (BPTC), 1,5-dioxide-2,6-naphthalenedicarboxylate (DONDC), 1,2,4,5-benzene-tetracarboxylate (BTEC), 1,4-bix(1H-pyrazol-4-ylethynyl)benzene (BPEP), 2,5-di(1H-1,2,4-triazol-1-yl)terephthalate (BTTA), 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine (TDPAT), 2,3,5,6-tetrachloroterephthalate (TCDC), 4,4'-dibenzoic acid-2,2' sulfone (SBPDC), etc. Functionalities can include, for example, open metal sites [OMS], microporosity [MP], Lewis basic sites [LBS], polar functional sites [PFS], post-synthetic modifications [PSM], etc. While 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 circumstances, such model training data for adsorbents can be collected and recorded manually (e.g., by analyst 1402) in a model data database. In some embodiments, PCC modeling system 1440 can be configured to collect such data (e.g., via other online databases, from performance or test data captured via PCC system 1420, etc.).

[0166] This sorbent data, in exemplary embodiments, is used by the PCC modeling system 1440 as model training data for training machine learning models to analyze the expected performance of predicted sorbents (e.g., novel combinations of metals, linkers, and functional groups that have not yet been studied and tested under real-world conditions). This model training data can be used as labeled training data in model building (e.g., instances of model training data of specific “inputs” with known outcomes or “labels”). In some embodiments, one subset of the model training data can be identified for purposes of training the model, and another subset can be identified for purposes of testing the model (e.g., 60% of the sorbents identified for training, 40% identified for testing, 70% identified for training, 30% identified for testing, etc.). In some embodiments, the analyst 1402 can manually identify the sorbents to use for training and testing (e.g., specific rows in the database). In some embodiments, the PCC modeling system 1440 can automatically identify the training and test subsets (e.g., using preset percentages, randomly selected percentages, etc.).

[0167] In some embodiments, method 1600 also includes performing aspects of univariate data analysis on the model training data at operation 1620. This data analysis involves evaluating a particular individual sorbent variable (e.g., a particular component or feature) against other variables (e.g., other components, features, or performance values) across the body of training data. This analysis can be used to identify high-level trends related to a particular component or feature.

[0168] In an exemplary embodiment, the PCC modeling system 1440 can provide the analyst 1402 with a graphical user interface that displays plots of particular features against other target features of interest, thereby allowing the analyst 1402 to explore trends and relationships between those particular features. The interface can allow the analyst 1402 to select a primary variable (e.g., as a domain) and a secondary variable (e.g., as a range) of interest, and the PCC modeling system 1440 can then calculate the mean / average / median and / or range of values ​​across all of the training data with those variables (e.g., for domain variables with discrete values ​​with continuous secondary variables), or 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 the organic linker against the isosteric heat of adsorption or Henry's law constant or mean pore size, and can separately identify physisorbents or chemisorbents (e.g., via different colors or shading). In another example, the PCC modeling system 1440 can generate plots of isosteric heats of adsorption or selectivity ratios versus metals identified in the training data.

[0169] In operation 1630, in an exemplary embodiment, the PCC modeling system 1440 generates a secondary feature for use 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., existing main effect parameters of a past adsorbent), such as isosteric heat of adsorption, Henry's law constant, pore size, pore volume, surface area, etc. The term "secondary feature" refers to a combination of two or more of those primary features, including the interaction between two primary features (e.g., an interaction parameter). In some embodiments, the analyst 1402 can manually create a secondary feature within the PCC modeling system 1440 by specifying two or more primary features to be combined as a new secondary feature of the model. In one example, secondary feature "A" is calculated as (BET Area * Pore Volume (V pore )) and the secondary feature "B" is created as (V pore *Isosteric heat of adsorption (Q st )) and the secondary feature "C" is created as (BET area * Q st ) These secondary features can be used in model training and analysis, as described below.

[0170] In some embodiments, the PCC modeling system 1440 can select secondary features to use during model training by using an automated selection process. For example, the PCC modeling system 1440 can analyze the statistical significance of each of the primary features, such as via a probability value. The probability value (p-value) is a measure of the significance of a variable to the model. A p-value of less than 0.05 means that the factor in the model is statistically significant at a 95% confidence level, which indicates strong evidence against the outcome being random, and the probability that the outcome is random is less than 5%.

[0171] In some embodiments, the PCC modeling system 1440 can select a set number of secondary features. For example, for n as the number of primary features analyzed by the PCC modeling system 1440, the set number of secondary features can be n In this example, (n+ n The total number of primary and secondary features equal to C) can be automatically selected by the PCC modeling system 1440.

[0172] In operation 1640, in an exemplary embodiment, the PCC modeling system 1440 performs correlation and bivariate analysis of the model data. Referring now to FIG. 16B, this analysis includes identifying a feature set for model training. In operation 1642, a predicted feature set is identified for model training. This feature set includes a list of primary features 1602 (or primary features) and secondary features 1604 (or secondary features) used in model training. As described above, the primary features 1602 include a list of physical features or known variables provided for the adsorbent in the model data 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 secondary features 1604 are collectively referred to as a "feature set" 1606 for model training. In an exemplary embodiment, the primary features 1602 include PCC capacity, BET area, Langmuir surface area, pore volume (V pore ), steric heat of adsorption (Q st ), and average pore diameter (Å), and secondary features 1604 are the three exemplary secondary features listed above, namely, "A" = (BET area * pore volume (V pore )), "B"=(V pore *Steric heat of adsorption (Q st )), and "C" = (BET area * Q st ) In this way, the training data can be thought of as defining an n-dimensional space, where n is the number of features 1606 used in model training.

[0173] In operation 1644, the PCC modeling system 1440 may generate pair plots or scatter plots using the model data 1460 and the selected training data adsorbents for each unique combination of primary features 1602 and secondary features 1604 in the feature set 1606. For example, the PCC modeling system 1440 may generate, for each unique combination of features 1606, a first pair plot showing BET area and PCC capacity across the training data, a second pair plot showing Langmuir surface area and PCC capacity across the training data, and a third pair plot showing V across the training data. pore and a third pair plot showing PCC capacity, etc. The PCC modeling system 1440 can display these plots in a graphical user interface for inspection and review by the analyst 1402. For some combinations, these plots can help the analyst 1402 identify whether there is a correlation between those two variables in the training data, whether the correlation is linear or nonlinear, and whether it is a positive or negative correlation. Furthermore, these plots can help the analyst 1402 identify variables in the training data that are statistically significant.

[0174] In operation 1646, the PCC modeling system 1440 generates a correlation matrix 1608 of correlation coefficients for various pairs of primary features 1602 and secondary features 1604 in the feature set 1606. More specifically, in the 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 to both a row and a column (e.g., a square reflection matrix). Each cell of the matrix 1608 represents some combination of two of the features 1602, 1604 in the feature set 1606 (e.g., based on that cell's particular row and column), and the value contained in that cell is a correlation coefficient that represents the degree or magnitude of the correlation between those two particular features. For each combination of two features 1602, 1604, the PCC modeling system 1440 calculates the correlation coefficient of those two features (e.g., across the training data) in operation 1648. In an exemplary embodiment, the correlation coefficient is normalized from a range between +1.0 and −1.0, with a more positive correlation between two features closer to +1.0, a more negative correlation closer to −1.0, and a neutral (e.g., weak or non-existent) correlation closer to 0.0 (e.g., Pearson's correlation coefficient). In operation 1650, the PCC modeling system 1440 populates particular cells with the correlation coefficients associated with those two features 1602, 1604. Once completed, this correlation matrix and associated values ​​may be displayed to the analyst 1402 for inspection and review, and in some embodiments may be presented as a heat map (e.g., coloring each individual cell based on its value) so that the analyst 1402 can more easily see the positive and negative correlations between particular features. Further details regarding the exemplary correlation matrix 1608 are provided in connection with FIG. 17 .

[0175] 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 approximate the PCC performance of other (e.g., untested) adsorbents. More specifically, FIG. 16C illustrates the exemplary regression analysis process of operation 1660.

[0176] In an exemplary embodiment, a set of model training data is identified as model data 1460 for use during regression operation 1660. In some embodiments, as described above, specific instances of training data may be identified manually (e.g., by analyst 1402) or selected (e.g., automatically) by PCC modeling system 1440. Thus, the training data represents which known adsorbents fall within the scope of this particular regression analysis, and the remaining model data can be used to validate the results of this training.

[0177] In 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 of the features in the complete feature set 1606 can initially be used as the initial feature set 1680. In other embodiments, the analyst 1402 can manually select the features in the initial feature set 1680 (e.g., based on reviewing a pair plot and / or a correlation matrix). In still other embodiments, the PCC modeling system 1440 can automatically select the initial feature set 1680. For example, the PCC modeling system 1440 can selectively add to the initial feature set 1680 all features 1602, 1604 that have a correlation coefficient with the PCC capacity above a predetermined threshold (e.g., greater than 0.2) or below a predetermined threshold (e.g., less than −0.2). A number of these features f are then used as the current feature set 1682 to begin the regression.

[0178] In operation 1666, the PCC modeling system 1440 performs multiple linear regressions on the model training data using the current feature set (e.g., using an ordinary least squares model fit of the training data, where PCC productivity is the dependent variable of interest determined based on PCC capacity and CO2 uptake rate (e.g., adsorption kinetics)), where the linear regression method is applied to Eq. 1. to study the dependence between the parameters of interest (e.g., PCC capacity, Å) and various physical attributes selected for the initial feature set 1680 (e.g., BET area, pore volume, isosteric heat, and the secondary features "A," "B," and "C" described above). Å=b0+b1X1+b2X2+···+b p X p Eq.1

[0179] In this regression, each of the f current features 1682 has an associated linear coefficient b i Along with X i The p-value is expressed in Equation 1 by: Initially, all initial features 1680 are included in the transfer function of Equation 1, and as the regression iterates, the current feature 1682 with the highest p-value is removed until all current features 1682 have p-values ​​below a predetermined value (e.g., less than 0.05 means they have a 95% chance of being statistically significant). Relevant variables in the model are those with probability values ​​("p-values") below a predetermined threshold.

[0180] More specifically, in an exemplary embodiment, at each step of the iteration, a p-value is generated for each feature remaining in the current feature set 1682. In test 1668, the PCC modeling system 1440 tests whether the regression is complete by evaluating the p-value of the current feature 1682. If all p-values ​​of the remaining current features 1682 are below a predetermined threshold, the iteration ends. If not, the iteration continues to operation 1670. In operation 1670, the PCC modeling system 1440 identifies the current feature with the highest p-value and removes that particular feature from the current features 1682 for the next iteration. The regression process returns to operation 1666, continuing with the reduced current feature set 1682 and again generating new p-values ​​until all remaining features are below the predetermined threshold. If a primary feature has a p-value above the threshold, but secondary features that include the primary feature have p-values ​​below the threshold, the primary feature is retained as part of the model even if their individual p-values ​​are greater than the threshold. This is necessary to keep secondary features with p-values ​​below the threshold as part of the model.

[0181] Once the regression iterations are complete and finished, the PCC modeling system 1440 can identify one or more remaining features to be included in the final feature set 1684, each of which has a p-value below a predetermined threshold and is therefore statistically significant. In an exemplary embodiment, the PCC modeling system 1440 examines the final results for possible indications of overfitting in the model. For the final feature set 1684, the PCC modeling system 1440 also generates an r-squared 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 and adjusted r-squared values ​​(e.g., abs(r-squared - adjusted r-squared)) is greater than a predetermined threshold, the model may be overfitted. In such a situation, the PCC modeling system 1440 analyzes each unique combination of the remaining features in the final feature set 1684, runs the model on that combination to generate r-squared and adjusted r-squared values ​​for each combination, and then selects the particular combination with the closest r-squared and adjusted r-squared values ​​(e.g., smallest abs(r-squared-adjusted r-squared)).

[0182] The remaining features and their associated values ​​are used to generate a final transfer function from this model. More specifically, the regression results in final coefficients for each of the remaining features in the final feature set 1684, as well as a constant coefficient (e.g., a y-intercept value). Thus, X in Equation 1 f Each of the variables is identified using each of the remaining features, and each associated coefficient b f is added to Eq1, as well as a constant coefficient b0 to generate the final transfer function. This transfer function can then be used with the expected adsorbent and their associated values ​​to determine the expected PCC capacity for that particular adsorbent.

[0183] In some embodiments, the PCC modeling system 1440 can use the model on test data to evaluate how it performs in predictive ability. For example, the PCC modeling system 1440 can generate residual plots of the linear regression model for both the training data and the test data, thereby allowing the analyst 1402 to assess how well the model is performing.

[0184] In one particular example, the regression operation 1660 calculates the isosteric heat of adsorption (Q st ), BET area, pore volume (V pore ) and an example training set starting with three example secondary features "A," "B," and "C." In the first iteration, the BET area p-value is 0.948, which is identified as the highest, and is removed. In the second iteration, the "A" secondary feature p-value is 0.769, which is identified as the highest, and is removed. In the third iteration, the "B" secondary feature p-value is 0.441, which is identified as the highest, and is removed. In the fourth iteration, all remaining current features (e.g., Q st , V pore The p-values ​​for the "Q" secondary feature and the "Q" secondary feature) are less than 0.05, so the regression iterations end 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, and this difference triggers an overfitting analysis. Because there are three remaining features in the final feature set 1684, each combination of those features contributes to the model (e.g., a total of 3!=6 unique combinations, i.e., [Q st ], [Q st , V pore ], [Q st , V pore , "C"], [V pore ], [V pore , "C"], and ["C"]). In this example, just [Q st ] combination yields an r-squared of 0.567 and an adjusted r-squared of 0.560, for a minimum difference of 0.007. Thus, Q stA feature and its associated value are the only features that are related to one remaining feature (e.g., X1=Q st is used to generate the final transfer function with only b1X1+b0=0.0318*Q st -0.4243, and b1=0.0318 is Q st is the final coefficient generated for the model, and b0 = -0.4243 is a constant coefficient. In this particular example, applying the test data to the trained model yielded a test r-squared value of 0.331, while the r-squared for the trained model was 0.567. Therefore, the formula includes only features with p-values ​​less than 0.05. Also, a positive r-squared for the test data indicates a positive correlation between the heat of adsorption (Q st ) can be used to explain about 60% of the capacity.

[0185] The PCC modeling system 1440 may use the generated transfer function to operate the post-combustion carbon capture system, such as by determining one or more expected sorbents to be used by the post-combustion carbon system. For example, the PCC modeling system 1440 may 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.

[0186] FIG. 17 illustrates an exemplary correlation matrix 1608. In some embodiments, the correlation matrix 1608 is generated by the PCC modeling system 1440 and used in the method 1600 described in FIGS. 16B-16C. In the exemplary embodiment, the correlation matrix 1608 is a 9x9 square reflection matrix. There are nine rows 1702 and nine columns 1704, and nine features 1712 that are the subject of this exemplary model. Each of the nine features 1712 has both an associated row 1702 and an associated column 1704. The features 1712 include six primary ("primary") features 1712A and three secondary ("secondary") features 1712B, similar to the example provided in FIGS. 16B-16C. Each cell of the matrix contains a correlation coefficient calculated between the two particular intersecting features in that cell. For example, the correlation coefficient between BET area and PCC capacity is -0.12.

[0187] Further aspects of the invention are provided by the subject matter of the following clauses.

[0188] 1. A power generation system including a capture system used to capture carbon dioxide, a controller configured to operate a photography system, and a modeling system including a processor configured to identify a model training dataset, each instance of the model training dataset identifying a sorbent used by the capture system, a carbon capture performance value of the sorbent, and a plurality of primary feature values ​​associated with a plurality of primary features; 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; and generating a plurality of correlation strengths including correlation strength values ​​between each of the plurality of primary features and each of the one or more secondary features. a power generation system configured to determine a value, identify a first subset of a model training dataset based on the plurality of correlation strength values, determine a statistical significance for each instance of the first subset of the model training dataset, identify a second subset of the model training dataset based on the statistical significance, generate a transfer function based on the second subset of the model training dataset, wherein the statistical significance of each instance of the second subset of the model training dataset is below a predetermined threshold, and use the transfer function to determine one or more expected sorbents to be used by the capture system based on the carbon capture performance values, and a controller causes the capture system to operate using the one or more expected sorbents determined by the modeling system.

[0189] 2. The power generation system of the preceding clause, wherein generating 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.

[0190] 3. The power generation system of any preceding clause, wherein determining the plurality of correlation strength values ​​includes generating a correlation matrix including a plurality of cells, the plurality of cells arranged in a plurality of rows and a plurality of columns for the plurality of primary features and one or more secondary features, each of the plurality of cells including one of the plurality of correlation strength values.

[0191] 4. The power generation system of any of the preceding clauses, wherein the processor of the modeling system is configured to select an initial feature set from a plurality of primary features and one or more secondary features.

[0192] 5. The power generation system of any of the preceding clauses, wherein selecting an initial feature set includes receiving user input from a user indicating a selection of one or more features from the plurality of primary features and one or more secondary features.

[0193] 6. A power generation system as described in any of the preceding clauses, wherein selecting an initial feature set includes selecting one or more features from a plurality of primary features and one or more secondary features, each of the one or more features having a correlation coefficient greater than a predetermined threshold.

[0194] 7. The power generation system of any preceding clause, wherein each of the one or more features has one or more PCC performance data values ​​greater than a predetermined threshold.

[0195] 8. The power generation system of any preceding clause, 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 dataset, determine a difference value 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 identify a third subset of the model training dataset based on the difference value, wherein the difference value for each instance of the third subset of the model training dataset is greater than a predetermined difference value threshold.

[0196] 9. The power generation system of any of the preceding clauses, wherein the difference value for each instance of the third subset of the model training dataset is less than a predetermined difference value threshold.

[0197] 10. The power generation system of any preceding clause, wherein the plurality of primary features includes at least a carbon capture capacity and an isosteric heat of adsorption.

[0198] 11. The power generation system of any 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 heating value.

[0199] 12. A method for selecting one or more promising sorbents for use in operating a capture system to capture carbon dioxide, comprising: identifying a model training dataset, each instance of the model training dataset identifying a sorbent used by the capture system; generating one or more secondary features based on one or more of the plurality of primary features, the secondary features including a carbon capture performance value of the sorbent and a plurality of primary feature values ​​associated with a 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 strength values, the correlation strength values ​​including a correlation strength value between each of the plurality of primary features and each of the one or more secondary features; and generating the model training dataset based on the plurality of correlation strength values. determining a statistical significance of each instance in the first subset of the model training dataset; identifying a second subset of the model training dataset based on the statistical significance, wherein the statistical significance of each instance in the second subset of the model training dataset is below a predetermined threshold; generating a transfer function based on the second subset of the model training dataset; and determining, using the transfer function, one or more prospective sorbents to be used by the capture system based on the carbon capture performance values, wherein the controller operates the capture system using the one or more prospective sorbents determined using the transfer function.

[0200] 13. The method of the preceding clause, wherein generating 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.

[0201] 14. The method of any preceding clause, wherein determining the plurality of correlation strength values ​​includes generating a correlation matrix including a plurality of cells, the plurality of cells arranged in a plurality of rows and a plurality of columns for the plurality of primary features and one or more secondary features, each of the plurality of cells including one of the plurality of correlation strength values.

[0202] 15. The method of any of the preceding clauses, further comprising selecting an initial feature set from a plurality of primary features and one or more secondary features.

[0203] 16. The method of any of the preceding clauses, wherein selecting an initial feature set includes receiving user input from a user indicating a selection of one or more features of the plurality of primary features and one or more secondary features.

[0204] 17. The method of any preceding clause, wherein selecting an initial feature set includes selecting one or more features from a plurality of primary features and one or more secondary features, each of the one or more features having a correlation coefficient greater than a predetermined threshold.

[0205] 18. The method of any preceding clause, 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 value 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 values.

[0206] 19. The method of any preceding clause, wherein identifying the third subset of model training data includes a difference value for each instance in the third subset of model training data sets that is greater than a predetermined difference value threshold.

[0207] 20. The method of any of the preceding clauses, wherein identifying the third subset of model training data includes a difference value for each instance in the third subset of model training data sets that is less than a predetermined difference value threshold.

[0208] Solid Adsorbent Materials In one embodiment, a functionalized adsorbent is provided. The functionalized adsorbent comprises an adsorbent and at least one functionalizing ligand comprising an aminosilicone group. The adsorbent has an average particle length of 3 μm or less. In another embodiment, the adsorbent has an average particle length of ≦2 μm. In another embodiment, the adsorbent has an average particle length of ≦1 μm.

[0209] It has been discovered that one or more of reducing the particle size of the adsorbent, increasing the aspect ratio of the adsorbent, and synthesizing the adsorbent in an aqueous form result in adsorbents with significantly improved CO2 uptake kinetics.

[0210] Generally, the adsorbent can comprise any suitable particle size known in the art that facilitates the functionalized adsorbents described herein. In some embodiments, the adsorbent has an average particle length of 3 μm or less, 2.9 μm or less, 2.8 μm or less, 2.7 μm or less, 2.6 μm or less, 2.5 μm or less, 2.4 μm or less, 2.3 μm or less, 2.2 μm or less, 2.1 μm or less, 2 μm or less, 1.9 μm or less, 1.8 μm or less, 1.7 μm or less, 1.6 μm or less, 1.5 μm or less, 1.4 μm or less, 1.3 μm or less, 1.2 μm or less, 1.1 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, 0.2 μm or less, or 0.1 μm or less. In some embodiments, the sorbent has an average particle length of 3 μm or more, 2.9 μm or more, 2.8 μm or more, 2.7 μm or more, 2.6 μm or more, 2.5 μm or more, 2.4 μm or more, 2.3 μm or more, 2.2 μm or more, 2.1 μm or more, 2 μm or more, 1.9 μm or more, 1.8 μm or more, 1.7 μm or more, 1.6 μm or more, 1.5 μm or more, 1.4 μm or more, 1.3 μm or more, 1.2 μm or more, 1.1 μm or more, 1 μm or more, 0.9 μm or more, 0.8 μm or more, 0.7 μm or more, 0.6 μm or more, 0.5 μm or more, 0.4 μm or more, 0.3 μm or more, 0.2 μm or more, or 0.1 μm or more.

[0211] Generally, the adsorbent can include any suitable aspect ratio known in the art that facilitates the functionalization of the adsorbents described herein. As used herein, aspect ratio is the ratio of the average width of the adsorbent to 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.

[0212] In some embodiments, the particle size is a discrete particle size. Discrete particle size measurements can be made according to any suitable means known in the art, for example, by measuring particle sizes in SEM images.

[0213] In some embodiments, the particle size measurement is an average particle size measurement. 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.

[0214] In general, the particle size of the adsorbent can be controlled, modified, or reduced according to any suitable technique known in the art to facilitate functionalizing adsorbents as described herein. In some embodiments, suitable techniques for controlling, modifying, or reducing particle size include mechanical milling (e.g., mortar and pestle) using a microfluidizer, dry milling, wet milling, chemical size reduction (e.g., incorporation of crystal growth inhibitors), acoustic cavitation, hydrodynamic cavitation, and combinations thereof.

[0215] Generally, the adsorbent may be in any suitable form known in the art that facilitates the functionalized adsorbents described herein, hi some embodiments, the adsorbent is in a form selected from the group consisting of a powder, a pellet, a composite, a composite mixed with a binder, a film, a coating, a packed bed, a column, a monolith, and combinations thereof.

[0216] Exemplary embodiments described herein include a sorbent system. Generally, the sorbent system may be any suitable sorbent system known in the art that facilitates the functionalized sorbents described herein. In some embodiments, the sorbent system includes a functionalized sorbent and, optionally, a binder. In some embodiments, the sorbent system is disposed on a polymer film.

[0217] In some embodiments, the adsorbent system includes at least one contactor. In some embodiments, the adsorbent system includes two or more contactors. In some embodiments, the adsorbent system includes a contactor configured for an adsorption cycle and a contactor configured for a desorption cycle. The contactor may be any suitable contactor known in the art that facilitates the functionalized adsorbents described herein. In some embodiments, the adsorbent is incorporated into at least one channel of the contactor. In some embodiments, the contactor is fabricated from the adsorbent itself. In some embodiments, the contactor is coated with an adsorbent system. In some embodiments, the contactor includes two or more adsorbent coatings, and at least one adsorbent coating is an adsorbent system.

[0218] In some embodiments, the adsorbent system includes a frame. The frame may be any suitable frame known in the art that facilitates the functionalized adsorbents described herein. The frame may be included in a contactor or between two contactors. The frame may be comprised of one piece or may be comprised of two or more pieces. In some embodiments, the frame is an air frame. In some embodiments, the frame is in a configuration selected from the group consisting of a polygonal configuration, a rectangular configuration, a square configuration, a circular configuration, an asymmetric configuration, and combinations thereof. In some embodiments, the adsorbent system is mounted on the frame.

[0219] In some embodiments, the adsorbent system includes at least one concentrator. The concentrator may be any suitable concentrator known in the art that facilitates the functionalized adsorbents described herein. The concentrator may be a passive or active concentrator.

[0220] In some embodiments, the sorbent system includes at least one component configured to drive fluid flow. The component configured to drive fluid flow may be any suitable component configured to drive fluid flow known in the art to facilitate the functionalized sorbents described herein. In some embodiments, the component configured to drive fluid flow is selected from the group consisting of a pump, a fan, and combinations thereof.

[0221] In some embodiments, the sorbent system includes at least one component configured to alter temperature. The component configured to alter temperature can be any suitable component configured to alter temperature known in the art to facilitate functionalized sorbents described herein. In some embodiments, the component configured to alter temperature is selected from the group consisting of a heater, a cooler, and combinations thereof.

[0222] In some embodiments, the sorbent system includes at least one component configured to convey a fluid. The component configured to convey a fluid may be any suitable component configured to convey a fluid known in the art that facilitates the functionalized sorbents described herein. In some embodiments, the component configured to convey a fluid is selected from the group consisting of tubing, perforated tubing, plastic perforated tubing, polymer perforated tubing, metal perforated tubing, composite perforated tubing, and combinations thereof.

[0223] In general, the functionalized sorbents can be used according to any suitable purpose known in the art that facilitates the use of the functionalized sorbents described herein. In some embodiments, the functionalized sorbents are used in sorbent systems. In some embodiments, the functionalized sorbents are used in carbon capture sorbent systems. In some embodiments, the functionalized sorbents are used in moisture sorbent systems. In some embodiments, the functionalized sorbents are used in carbon capture sorbent systems in the presence of water. In some embodiments, the functionalized sorbents are used to capture gases. In some embodiments, the functionalized sorbents are used in post-combustion capture of CO and / or direct air capture of CO.

[0224] Exemplary embodiments described herein include methods of making the adsorbent systems. Generally, the functionalized adsorbents can be made according to any suitable synthetic method known in the art that facilitates the functionalized adsorbents described herein.

[0225] In many embodiments, a method of making a sorbent system includes making a sorbent having an average particle length of ≦3 μm and, optionally, functionalizing the sorbent with at least one functionalizing ligand comprising an aminosilicone group. In some embodiments, a method of making a sorbent system includes making a sorbent having an average particle length of ≦2 μm and, optionally, functionalizing the sorbent with at least one functionalizing ligand comprising an aminosilicone group. In some embodiments, a method of making a sorbent system includes making a sorbent having an average particle length of ≦1 μm and, optionally, functionalizing the sorbent with at least one functionalizing ligand comprising an aminosilicone group.

[0226] In some embodiments, the method of making a sorbent system includes functionalizing a sorbent with at least one functionalizing ligand that includes an aminosilicone group. In some embodiments, the method of making a sorbent system includes functionalizing a sorbent with at least two functionalizing ligands that each include an aminosilicone group, where the aminosilicone groups are different from each other. In some embodiments, the method of making a sorbent system further includes functionalizing the sorbent with at least one functionalizing ligand that does not include an aminosilicone group. In some embodiments, the method of making a sorbent system includes controlling the ratio between the at least one functionalizing ligand that includes an aminosilicone group and the at least one functionalizing ligand that does not include an aminosilicone group.

[0227] In some embodiments, the method of making the adsorbent system further comprises annealing the functionalized adsorbent. Annealing the adsorbent system can remove excess ligand. In some embodiments, annealing the functionalized adsorbent comprises annealing the functionalized adsorbent at an elevated temperature. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 50°C to about 400°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 100°C to about 300°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 150°C to about 250°C.

[0228] 34 is an exemplary method flowchart 3410. In this exemplary embodiment, method flowchart 3410 illustrates exemplary steps of method embodiments described herein and is not intended to limit method embodiments. In the exemplary embodiment, the method includes step 3412 of forming a mixture including an adsorbent precursor; a crystal growth inhibitor; optionally a solvent; and optionally a non-solvent. The method also includes step 3414 of reacting the mixture. In some embodiments, the adsorbent has an average particle length of 3 μm or less. In some embodiments, the adsorbent has an average particle length of 2 μm or less. In some embodiments, the adsorbent has an average particle length of 1 μm or less.

[0229] Forming the mixture 3412 may be done by any suitable means known in the art. In some embodiments, all of the ingredients are added at the same time. In some embodiments, at least one ingredient is added at a different time than the other ingredients.

[0230] In some embodiments, the sorbent precursor comprises a MOF linker and a MOF metal or metal-containing cluster. The sorbent precursor may be formed before the mixture is formed 3412, added as a single component to the mixture, or may be formed in situ in the mixture during the formation of the mixture 3412. For example, the MOF linker can be separately deprotonated and then added or deprotonated in situ. Similarly, the MOF metal or metal-containing cluster can be preformed and then added or formed in situ.

[0231] In some embodiments, the solvent comprises an aqueous solvent. In some embodiments, the solvent comprises water. The use of an aqueous solvent offers several advantages. In particular, the use of an aqueous solvent exhibits scalability, safety, cost, and waste disposal advantages compared to at least some known methods of preparing MOF compounds. Furthermore, MOF compounds prepared using an aqueous solvent are generally easier to purify, for example, via solvent washing, than the same MOF compounds prepared according to known methods. This improved purification results from the relative ease of removing solvent molecules (e.g., water) from the MOF compounds described herein compared to the removal of strongly bound solvent molecules (e.g., dimethylformamide (DMF)) utilized to prepare the same MOF compounds according to known methods. Furthermore, the purified MOF compounds are free of strongly bound solvent molecules that reduce gas uptake, surface area, and / or overall pore volume. Finally, purification is improved by requiring less toxic purification methods.

[0232] 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.

[0233] 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.

[0234] 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.

[0235] 35 is an exemplary method flowchart 3510. In this exemplary embodiment, method flowchart 3510 illustrates exemplary steps of method embodiments described herein and is not intended to limit the method embodiments. In the exemplary embodiment, the method includes step 3512 of forming a mixture comprising: an adsorbent; at least one functionalized ligand comprising an aminosilicone group; optionally, at least one functionalized ligand not comprising an aminosilicone group; optionally, a solvent, and optionally, a non-solvent. The method also includes functionalizing 3514 the adsorbent.

[0236] In some embodiments, step 3514 of functionalizing the adsorbent includes agitating the mixture.

[0237] In some embodiments, functionalizing 3514 the adsorbent includes functionalizing 3514 the adsorbent in the presence of an inert gas.

[0238] In some embodiments, functionalizing 3514 the adsorbent comprises functionalizing 3514 the adsorbent at a temperature ranging from about 0° C. to about 100° C. In some embodiments, functionalizing 3514 the adsorbent comprises functionalizing 3514 the adsorbent at a temperature ranging from about 20° C. to about 80° C. In some embodiments, functionalizing 3514 the adsorbent comprises functionalizing 3514 the adsorbent at a temperature ranging from about 20° C. to about 60° C.

[0239] In some embodiments, functionalizing 3514 the adsorbent comprises functionalizing 3514 the adsorbent for a time ranging from about 1 minute to about 7 days. In some embodiments, functionalizing 3514 the adsorbent comprises functionalizing 3514 the adsorbent for a time ranging from about 1 hour to about 3 days.

[0240] In some embodiments, the adsorbent is desolvated before functionalization 3514. In some embodiments, the adsorbent is dried before functionalization.

[0241] In some embodiments, the adsorbent is annealed after functionalization 3514. 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 ranging from about 50°C to about 400°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 100°C to about 300°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 150°C to about 250°C.

[0242] 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.

[0243] 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.

[0244] In some embodiments, the non-solvent aids in functionalization. In some embodiments, the selectivity of functionalization is controlled by relative solubility. For example, one or more 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 may introduce limiting reactions and / or reagents.

[0245] In many embodiments, the methods can also include any additional suitable processing steps known in the art that facilitate the success of the methods described herein. Such processing steps include, but are not limited to, washing, drying, filtering, purifying, separating, centrifugation, and any combination thereof. In some embodiments, the methods further include washing the functionalized adsorbent. In some embodiments, the methods further include purifying the functionalized adsorbent. In some embodiments, the purification includes distillation, vacuum distillation, and / or the use of heat.

[0246] SUMMARY OF THE INVENTION Exemplary embodiments described herein include methods for capturing at least one gas.

[0247] FIG. 36 is an exemplary method flowchart 3610. In an exemplary embodiment, the method flowchart 3610 illustrates exemplary method steps of method embodiments described herein and is not intended to limit the method embodiments. The method includes receiving 3612 a gas source containing at least one gas with a functionalized adsorbent, the functionalized adsorbent including an adsorbent; and at least one functionalized ligand including an aminosilicone group. In some embodiments, the functionalized adsorbent includes at least two functionalized ligands, each including an aminosilicone group, and the aminosilicone groups are different from one another. In some embodiments, the functionalized adsorbent further includes at least one functionalized ligand that does not include an aminosilicone group. The method also includes capturing 3614 a quantity of at least one gas with the functionalized adsorbent. The adsorbent has an average particle length of 3 μm or less.

[0248] In some embodiments, the method includes (I) receiving 3612 a gas source comprising at least one gas with a functionalized adsorbent, the functionalized adsorbent comprising an adsorbent and at least one functionalized ligand comprising an aminosilicone group; and (II) capturing 3614 a quantity of the at least one gas with the functionalized adsorbent.

[0249] Generally, the gas source may be any suitable gas source known in the art that facilitates the methods described herein. In some embodiments, the gas source is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0250] Generally, the at least one gas may 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, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0251] In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 100% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 40% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 15% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v). In some embodiments, at least one gas is present in the feed gas in an amount greater than 10% (v / v).

[0252] In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 100 ppmv to about 1000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 200 ppmv to about 1000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 300 ppmv to about 5000 ppmv.

[0253] In some embodiments, the at least one gas does not include water vapor.

[0254] In some embodiments, at least one gas comprises water vapor. In some embodiments, at least one gas comprises water vapor in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, at least one gas comprises water vapor in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, at least one gas comprises water vapor in an amount ranging from about 0.5% (v / v) to about 15% (v / v). In some embodiments, at least one gas comprises water vapor in an amount ranging from about 0.5% (v / v) to about 4% (v / v). In some embodiments, at least one gas comprises water vapor in an amount ranging from about 4% (v / v) to about 15% (v / v).

[0255] In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v) and in the presence of water vapor. In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v) and in the presence of water vapor. In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v) and in the presence of water vapor. In some embodiments, at least one gas is present in the source gas in an amount greater than about 10% (v / v) and in the presence of water vapor. In some embodiments, water vapor is present in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.5% (v / v) to about 10% (v / v).

[0256] In some embodiments, capturing a quantity of at least one gas with the functionalized adsorbent step 3614 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 the functionalized adsorbent step 3614 comprises adsorbing a quantity of the at least one gas with the functionalized adsorbent in the presence of water vapor.

[0257] In some embodiments, the amount of at least one gas 3614 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 feed gas. In some embodiments, the amount of at least one gas 3614 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 feed gas. In some embodiments, the amount of at least one gas 3614 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 feed gas. In some embodiments, the amount of at least one gas 3614 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 feed gas. In some embodiments, the amount of at least one gas 3614 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 feed gas.

[0258] In some embodiments, the amount of at least one gas 3614 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 feed gas. In some embodiments, the amount of at least one gas 3614 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 feed gas. In some embodiments, the amount of at least one gas 3614 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 feed gas. In some embodiments, the amount of at least one gas 3614 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 feed gas. In some embodiments, the amount of at least one gas 3614 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 feed gas.

[0259] In some embodiments, the amount of at least one gas 3614 captured by the functionalized adsorbent ranges from about 80% (v / v) to about 100% (v / v) of the at least one gas present in the feed gas. In some embodiments, the amount of at least one gas 3614 captured by the functionalized adsorbent ranges from about 85% (v / v) to about 100% (v / v) of the at least one gas present in the feed gas. In some embodiments, the amount of at least one gas 3614 captured by the functionalized adsorbent ranges from about 90% (v / v) to about 100% (v / v) of the at least one gas present in the feed gas. In some embodiments, the amount of at least one gas 3614 captured by the functionalized adsorbent ranges from about 95% (v / v) to about 100% (v / v) of the at least one gas present in the feed gas.

[0260] In some embodiments, the feed gas is reformed to vary the amount of water vapor. In some embodiments, varying the amount of water vapor comprises increasing the amount of water vapor. In some embodiments, varying the amount of water vapor comprises decreasing the amount of water vapor. In some embodiments, increasing the amount of water vapor comprises adding or injecting water vapor into the source gas. In some embodiments, decreasing the amount of water vapor comprises removing water vapor from the feed gas by evaporation, condensation, and / or pre-adsorption. In some embodiments, varying the amount of water vapor comprises exhaust gas recirculation (EGR) and / or blending.

[0261] In many embodiments, the functionalized adsorbent, the feed gas, the at least one gas, or a combination thereof, is at a particular temperature. Each temperature can be varied to facilitate the methods described herein. Each temperature can have a uniform temperature profile, a gradient temperature profile, a discrete temperature profile, or a combination thereof.

[0262] In some embodiments, the method includes an adsorption cycle. In some embodiments, the method includes a desorption cycle. In some embodiments, at least one of the functionalized adsorbent, the feed gas, the at least one gas, or a combination thereof is at a temperature ranging from about 0° C. to about 150° C. during the gas adsorption cycle. In some embodiments, at least one of the functionalized adsorbent, the feed gas, the at least one gas, or a combination thereof is at a temperature ranging from about 60° C. to about 250° C. during the gas desorption cycle.

[0263] In some embodiments, the method includes controlling the temperature. The temperature can be controlled for the functionalized adsorbent, the feed gas, the at least one gas, or a combination thereof.

[0264] SUMMARY OF THE INVENTION Exemplary embodiments described herein include a method for recovering at least one gas from a gas source.

[0265] FIG. 37 illustrates an exemplary method flowchart 3710. In this exemplary embodiment, the method flowchart 3710 illustrates exemplary method steps of method embodiments described herein and is not intended to limit the method embodiments. The method includes receiving 3712 a gas source containing at least one gas with a functionalized adsorbent, the functionalized adsorbent including an adsorbent; and at least one functionalized ligand including an aminosilicone group. In some embodiments, the functionalized adsorbent includes at least two functionalized ligands, each including an aminosilicone group, and the aminosilicone groups are different from one another. In some embodiments, the functionalized adsorbent further includes at least one functionalized ligand that does not include an aminosilicone group. The method also includes step 3714 of capturing a quantity of at least one gas with the functionalized adsorbent. The method also includes step 3716 of releasing the at least one gas from the functionalized adsorbent. The adsorbent has an average particle length of 3 μm or less.

[0266] In some embodiments, the method includes (I) receiving 3712 a gas source comprising at least one gas with a functionalized adsorbent, the functionalized adsorbent comprising an adsorbent and at least one functionalized ligand comprising an aminosilicone group; (II) capturing 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.

[0267] In some embodiments, releasing 3716 the at least one gas from the functionalized adsorbent comprises purging the at least one gas from the functionalized adsorbent with a purge gas. In some embodiments, releasing 3716 the at least one gas from the functionalized adsorbent comprises subjecting the functionalized adsorbent to a change in temperature or pressure.

[0268] In some embodiments, at least one gas is released from the functionalized adsorbent into a receiving gas 3716. In some embodiments, the receiving gas is selected from the group consisting of air, N2, steam, and combinations thereof. In some embodiments, the receiving gas is removed from the presence of the functionalized adsorbent after receiving the at least one gas. In some embodiments, the receiving gas has an increased concentration of the at least one gas compared to the source gas.

[0269] Further aspects of the present disclosure are provided by the subject matter of the following clauses.

[0270] 1. A functionalized adsorbent comprising: an adsorbent; at least one functionalized ligand comprising an aminosilicone group; wherein the adsorbent has an average particle length of 3 μm or less.

[0271] 2. The functionalized adsorbent of the preceding embodiment, further comprising at least one functionalizing ligand that does not comprise an aminosilicone group.

[0272] 3. The functionalized adsorbent of any of the preceding embodiments, wherein the at least one functionalized ligand comprising an aminosilicone group and the at least one functionalized ligand not comprising an aminosilicone group are present in a ratio ranging from about 10:1 to about 1:10.

[0273] 4. The functionalized adsorbent is a functionalized MOF compound of formula (AI),

number

[0274] 5. A functionalized adsorbent according to any 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, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof.

[0275] 6. The MOF linker is a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4" -dioxide-[1,1':4',1"-terphenyl]-3,3"-dicarboxylate (dotpdc 4- ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-DOBDC 4- ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4-), 4,4'-[oxalylbis(imino)bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), dicarboxylate, terephthalic acid, tricarboxylate, 1,3,5-benzotricarboxylic acid, azolate, tetrazolate, 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butanedicarboxylic acid Diene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimidedicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol 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-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxo Imidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cisdicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenone dicarboxylic acid, Pluriol 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'-Diaminodiphenyldiimidecarboxylic acid, 4,4'-Diaminodiphenylmethanedicarboxylic acid, 4,4'-Diaminodiphenylsulfonediimidedicarboxylic acid, 2,6-Naphthalenedicarboxylic acid, 1,3-Adamantanedicarboxylic acid, 1,8-Naphthalenedicarboxylic acid, 2,3-Naphthalenedicarboxylic acid, 8-Methoxy-2,3-naphthalenedicarboxylic acid, 8-Nitro-2,3-naphthalenedicarboxylic acid, 8-Sulfo-2,3-naphthalenedicarboxylic acid anthracene-2,3-dicarboxylic acid, 2'-3'-diphenyl-p-terphenyl-4,4"-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-Dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosene dicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorine-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-dehydrobornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, 2-hydroxy-1,2,3-propanedicarboxylic acid 1,2,4-Benzenetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene- 1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurintricarboxylic acid, 1,1-dioxide-perillo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-Hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclo A functionalized sorbent according to any of the preceding embodiments, comprising a linker selected from the group consisting of pentane-1,2,3,4-tetracarboxylic acid, a polytopic linker, a ditopic linker, a tritopic linker, a tetratopic linker, a pentatopic linker, a hexatopic linker, a heptatopic linker, an octatopic linker, a mixed linker, a demetallated linker, a metallo linker, an N-heterocyclic linker, protonated, partially and fully deprotonated forms, and combinations thereof.

[0276] 7. The functionalized adsorbent of any of the preceding embodiments, wherein the adsorbent has an aspect ratio >0.2.

[0277] 8. The functionalized adsorbent of any of the preceding embodiments, wherein the adsorbent has an average particle length of less than 1 μm.

[0278] 9. At least one functionalized ligand containing an aminosilicone group is an amino-substituted siloxane of formula (A-II), (A-III), (A-IV), (AV), (A-VI) or (A-VII), [ka] JPEG2026501066000047.jpg241150In formula, R1, R2, R3, R4, R9, R 10 , R 13 , R 14 and R 18are 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 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; R5, R6, R 11 , R 15 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 alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; 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 alkyl, a C1 alkyl, a C2 alkyl, a C3 alkyl, a C4 alkyl, a C5 alkyl, a C6 alkyl, and a substituent of formula (A-VIII); [ka] During the ceremony, the wavy bond indicates the position of attachment to formula (A-II) or formula (A-III) or formula (A-IV) or formula (AV) or formula (A-VI) or formula (A-VII), R 19 , R 20 , R 21 , R 22 , R 23 and R 24 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted 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 C1-C6 straight chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R25 and 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 alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, and substituted or unsubstituted C4-C6 cycloalkyl, or R 25 and R 26 are taken together to form a monocyclic ring selected from the group consisting of heterocycloalkyl and heteroaryl; R 27 , R 28 and R 29 are each independently selected from the group consisting of a direct bond, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-; R 30 is selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C1-C3 straight chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl, and heteroaryl; j is an integer ranging from 0 to 20, k is an integer ranging from 0 to 20; m is an integer ranging from 0 to 20, and n is an integer ranging from 0 to 20; The functionalized adsorbent of any of the preceding embodiments.

[0279] 10. At least one functionalized ligand containing an aminosilicone group is selected from the group consisting of: [ka] JPEG2026501066000050.jpg232148JPEG2026501066000051.jpg243148JPEG2026501066000052.jpg212137JPEG2026501066000053.jpg213119 and [ka] The functionalized adsorbent of any of the preceding embodiments, wherein the functionalized adsorbent is selected from the group consisting of:

[0280] 11. A sorbent system comprising the functionalized sorbent of any of the preceding embodiments.

[0281] 12. A method for producing an adsorbent, comprising: (I) Adsorbent precursors; Crystal growth inhibitors; optionally a solvent; and Optionally a non-solvent forming a mixture comprising: (II) reacting the mixture; Including, The adsorbent has an average particle length of 3 μm or less; A method for producing an adsorbent.

[0282] 13. The method of the preceding embodiment, wherein the sorbent precursor comprises a MOF linker and a MOF metal or metal-containing cluster.

[0283] 14. The method of any of the preceding embodiments, wherein the solvent comprises an aqueous solvent.

[0284] 15. The method of any of the preceding 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.

[0285] 16. A method for producing a functionalized adsorbent, comprising: (I) An adsorbent prepared according to any of the preceding embodiments; at least one functionalized ligand comprising an aminosilicone group; Optionally, at least one functionalized ligand that does not include an aminosilicone group; optionally a solvent; and optionally a non-solvent; and forming a mixture; (II) functionalizing the adsorbent; A method for producing a functionalized adsorbent, comprising:

[0286] 17. A method for capturing at least one gas, comprising: (I) receiving a gas source comprising at least one gas with a functionalized adsorbent, the functionalized adsorbent comprising: Adsorbents with an average particle length ≤ 3 μm; at least one functionalized ligand containing an aminosilicone group and (II) capturing a quantity of at least one gas using a functionalized adsorbent; 1. A method for capturing at least one gas, comprising:

[0287] 18. The method of the preceding 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 gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0288] 19. The method of any of the preceding 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 gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0289] 20. A method for recovering at least one gas from a gas source, comprising: capturing at least one gas according to the method of any of the preceding embodiments; (III) releasing at least one gas from the functionalized adsorbent; and 1. A method for recovering at least one gas from a gas source, comprising:

[0290] Solid adsorbent materials functionalized with polyamines having cyclic units.

[0291] Described herein are solid adsorbent materials functionalized with polyamines having at least one cyclic ring-shaped unit containing alicyclic units, aromatic units, or a combination of both. As an example, magnesium-based metal-organic framework 274 (MOF-274) is functionalized with several polyamines containing cyclic units. The adsorbent materials developed in this disclosure exhibit high adsorption capacities and low desorption residues for carbon dioxide under mild desorption conditions.

[0292] In general, functionalized adsorbents according to the present disclosure can be used with compositions according to the present disclosure, systems according to the present disclosure, and methods according to the present disclosure. The functionalized adsorbents are not limited to any particular embodiment disclosed herein.

[0293] In some embodiments, the functionalized adsorbent comprises a first type of functionalized ligand, wherein the first type of functionalized ligand comprises at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit. Generally, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit can comprise any such suitable ligand that facilitates the functionalized adsorbent described herein. The at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit can comprise only one functionalized ligand comprising a polyamine comprising at least one cyclic unit, or two or more functionalized ligands, each comprising a polyamine comprising at least one cyclic unit.

[0294] Generally, the adsorbent can be any suitable adsorbent known in the art that facilitates the functionalized adsorbents described herein. Suitable adsorbents are described in detail above.

[0295] Further, in some embodiments, the functionalized adsorbent comprises a metal-organic framework (MOF), wherein a first amine of the polyamine binds to a first metal site of the MOF, and optionally, a second amine of the polyamine binds to a second metal site of the MOF.

[0296] In some embodiments, the functionalized adsorbent is a functionalized MOF compound of formula (CV):

number

[0297] In some embodiments, the functionalized adsorbent comprises a second type of functionalizing ligand, wherein the second type of functionalizing ligand comprises at least one functionalizing ligand that does not comprise a polyamine containing at least one cyclic unit. In some embodiments, the functionalized adsorbent also comprises at least one functionalizing ligand that does not comprise a polyamine containing at least one cyclic unit. Generally, the at least one functionalizing ligand that does not comprise a polyamine containing at least one cyclic unit can comprise any suitable ligand that facilitates the functionalized adsorbent described herein. The at least one functionalizing ligand that does not comprise a polyamine containing at least one cyclic unit can comprise only one functionalizing ligand that does not comprise a polyamine containing at least one cyclic unit, or two or more functionalizing ligands that each do not comprise a polyamine containing at least one cyclic unit.

[0298] In some embodiments, the at least one functionalized ligand that does not include a polyamine containing at least one cyclic unit is selected from the group consisting of aminosilicone 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 ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, di(N-methyl)ethylenediamine, N-isopropylethylenediamine, N,N-dimethyl-N-methylethylenediamine, di(N,N-dimethyl)ethylenediamine, N,N-diisopropylethylenediamine, 2,2-dimethyl-1,3-diaminopropane, 1,3-diaminopentane, diethylenetriamine, N-(2-aminoethyl)-1,3 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.

[0299] In some embodiments, the at least one functionalized ligand comprising a polyamine that does not contain at least one cyclic unit comprises at least one aminosilicone selected from the group consisting of linear aminosilicones, cyclic aminosilicones, branched aminosilicones, amino-substituted siloxanes, linear amino-substituted disiloxanes, cyclic amino-substituted disiloxanes, linear amino-substituted trisiloxanes, cyclic amino-substituted trisiloxanes, linear amino-substituted tetrasiloxanes, cyclic amino-substituted tetrasiloxanes, linear amino-substituted polysiloxanes, cyclic amino-substituted polysiloxanes, silsesquioxanes, polyoctahedral silsesquioxanes, and combinations thereof.

[0300] Generally, the at least one functionalized ligand comprising a polyamine containing at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine containing at least one cyclic unit may be present in any suitable ratio known in the art to facilitate the functionalized sorbents described herein. In some embodiments, the ratio is selected from the group consisting of molar ratio, weight ratio, and volume ratio. In some embodiments, the at least one functionalized ligand comprising a polyamine containing at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine containing at least one cyclic unit are present in a ratio ranging from about 10:1 to about 1:10. In some embodiments, the at least one functionalized ligand comprising a polyamine containing at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine containing at least one cyclic unit are present in a ratio ranging from about 9:1 to about 1:9. In some embodiments, the at least one functionalized ligand comprising a polyamine containing at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine containing at least one cyclic unit are present in a ratio ranging from about 8:1 to about 1:8. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio ranging from about 7:1 to about 1:7. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio ranging from about 6:1 to about 1:6. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio ranging from about 5:1 to about 1:5. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio ranging from 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 ranging from about 3:1 to about 1:3. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit are present in a ratio ranging from about 2:1 to about 1:2. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one 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.

[0301] In some embodiments, the at least one functionalized ligand that includes a polyamine that includes at least one cyclic unit is present in an amount that is less than the at least one functionalized ligand that does not include a polyamine that includes at least one cyclic unit.

[0302] In some embodiments, the at least one functionalized ligand that includes a polyamine that includes at least one cyclic unit and the at least one functionalized ligand that does not include a polyamine that includes 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.

[0303] In many embodiments, the at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit can be any suitable at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit known in the art to facilitate the functionalized sorbents described herein.

[0304] In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises at least one amine selected from the group consisting of a primary amine, a secondary amine, a tertiary amine, and combinations thereof. In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises at least one primary amine or at least one secondary amine.

[0305] In some embodiments, the at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentaamines, hexaamines, polyamines, and combinations thereof.

[0306] In some embodiments, at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises a symmetric structure. In some embodiments, at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit comprises an asymmetric structure.

[0307] In some embodiments, the at least one cyclic unit is selected from the group consisting of an alicyclic unit, an aromatic unit, and combinations thereof.

[0308] In many embodiments, polyamines comprising at least one cyclic unit are described herein. In some embodiments, the polyamines comprising at least one cyclic unit are functionalized ligands. In some embodiments, the polyamines comprising at least one cyclic unit are functionalized ligands for functionalizing adsorbents.

[0309] In many embodiments, the polyamine-containing functionalized ligand has the formula (CI): [ka] and wherein the ring unit is at least one ring unit according to During the ceremony, B, C, and D each individually contain at least one amine group; x, y, and z are each independently 0 or 1; A comprises an aromatic ring structure according to formula (C-II) or an alicyclic structure according to formula (C-III), [ka] During the ceremony, n is an integer ranging from about 3 to about 8; m is an integer ranging from about 3 to about 5, and A 1 , A 2 , A 3 , and A 4 each independently contains at least one of carbon, oxygen, and silicon.

[0310] In some embodiments, A 1 , A 2 , A 3 , and A 4 are respectively, 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 linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; and combinations of these is selected from the group consisting of:

[0311] In some embodiments, B, C, and D each independently represent formula (C-IV): [ka] wherein: t, u, v, and w are each independently an integer ranging from about 0 to about 10; E, F, G and H are each individually Substituted or unsubstituted C1 to C6 straight chain alkyl, substituted or unsubstituted C3 to C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; R1 and R2 are each independently selected from the group consisting of substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; NH2, NHR1, and NR1R 2;並びに combinations of these is selected from the group consisting of:

[0312] In some embodiments, the polyamine comprises at least two cyclic units, and the polyamine comprises a polycyclic structure connected by at least one connecting group selected from the group consisting of substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl.

[0313] In some embodiments, the polyamine comprises at least one bicyclic unit.

[0314] In some embodiments, the polyamine comprises at least two cyclic units, and the polyamine comprises a bridged polycyclic structure comprising at least one bridging group selected from the group consisting of substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl.

[0315] In some embodiments, the polyamine comprises at least one bridged cyclic unit.

[0316] In some embodiments, t, u, v, and w are each independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0317] In some embodiments, n is 3, 4, 5, 6, 7, or 8.

[0318] In some embodiments, m is 3, 4, or 5.

[0319] In some embodiments, at least one of x, y, and z is 1. In some embodiments, at least two of x, y, and z are 1. In some embodiments, x, y, and z are each 1.

[0320] In general, each of B, C, and D may be attached to any suitable atom of A that facilitates a functionalized adsorbent according to the present disclosure. In many embodiments, each of B, C, and D is attached to a separate atom of a cyclic unit of A. In some embodiments, each of B, C, and D is attached to a separate atom of a cyclic unit of A. 1 , A 2 , A 3 , and A 4 are bonded to separate atoms of

[0321] In some embodiments, the polyamine comprises at least one substituent at a substituent position selected from the group consisting of 1, 2 (ortho) positions, 1, 3 (meta) positions, 1, 4 (para) positions, and combinations thereof.

[0322] In some embodiments, at least two of B, C, and D are located at ortho positions of a cyclic unit of A. In some embodiments, at least two of B, C, and D are located at meta positions of a cyclic unit of A. In some embodiments, at least two of B, C, and D are located at para positions of a cyclic unit of A.

[0323] In some embodiments, the polyamine comprises an isomer selected from the group consisting of a cis-isomer, a trans-isomer, an R-enantiomer, an S-enantiomer, and combinations thereof.

[0324] In some embodiments, at least two of B, C, and D are different. In some embodiments, B, C, and D are different.

[0325] In some embodiments, at least two of B, C, and D are the same. In some embodiments, B, C, and D are the same.

[0326] In some embodiments, the polyamine comprises at least one heteroalicyclic ring unit. In some embodiments, the polyamine comprises at least one heteroalicyclic ring unit that does not contain a nitrogen atom. In some embodiments, the polyamine comprises at least one heteroalicyclic ring unit, and the heteroatom is not nitrogen.

[0327] Generally, the polyamine can contain any number of amine groups known in the art to be suitable for facilitating a functionalized sorbent. In some embodiments, the polyamine contains a total number of amine groups ranging from about 2 to about 10. In some embodiments, the polyamine contains a total number of amine groups ranging from about 2 to about 6. In some embodiments, the polyamine contains a total number of amine groups ranging from about 2 to about 4. In some embodiments, the polyamine contains 2, 3, 4, 5, 6, 7, 8, 9, or 10 amine groups.

[0328] In some embodiments, the polyamine is [ka] JPEG2026501066000060.jpg24355JPEG2026501066000061.jpg251124JPEG2026501066000062.jpg21366JPEG2026501066000063.jpg17866JPEG2026501066000064.jpg19899 and and combinations thereof.

[0329] The following exemplary polyamines have cyclic units according to the present disclosure:

[0330] Aliphatic cyclic (hexacyclic) amines: GE201 (mixture of cis and trans); GE182 (trans); GE200 (cis); 1,4-cyclohexanediamine (p-CHD) (mw: 114; bp = 197°C). [ka]

[0331] GE181; GE187 (mixture of cis and trans); GE199 (cis); 1,3-cyclohexanediamine (m-CHD) (mw: 114; bp = 194°C). [ka]

[0332] GE202 (mixture of cis and trans); GE203 (cis); GE209 (trans); 1,2-cyclohexanediamine (o-CHD) (mw: 114; bp = 194°C) [ka]

[0333] Di / tri / tetraamines: GE221-A2109; 1,3,5-cyclohexanetriyltrimethanamine (CHTM) (mw=171.316; bp=309°C) [ka]

[0334] GE254;GE255(BPDCH) [ka]

[0335] 3-Ring-3 [ka]

[0336] Primary / Secondary / Tertiary Amines: N,N-dimethylcyclohexanediamine (NMCHD) (mw: 142.24; bp = 80°C at 18 mmHg) [ka]

[0337] Cis or trans isomers and chirality: (R,R)-1,2-Cyclohexanediamine(trans) [ka]

[0338] (S,S)-Cyclohexanediamine(trans) [ka]

[0339] (R,S)-Cyclohexanediamine(cis) [ka]

[0340] Different lengths: GE193 (mixture of isomers); 1,4-bis-(aminomethyl)-cyclohexane (BAMCH) (mw: 142.24; bp = 239°C) [ka]

[0341] GE206 (mixture of isomers); 1,3-bis-(aminomethyl)-cyclohexane (mBAMCH) (mw: 142.24; bp = 240°C) [ka]

[0342] GE248;GE249(BEDCH) [ka]

[0343] Structures with multiple cyclic units: GE216; 4,4'-methylenebis(2-methylcyclohexylamine) (mixture of isomers) (MCHA) [ka]

[0344] Asymmetrical structure: GE205 (mixture of isomers); 4-(aminomethyl)cyclohexanamine (AMCHA) [ka]

[0345] GE240; 4-(2-aminoethyl)cyclohexylamine (cis- and trans-mixture) (ACHEA) [ka]

[0346] GE256; N-(3-aminopropyl)cyclohexylamine (BPDCH) [ka]

[0347] Mixed amines: GE234; GE235; a mixture of 1,4-bis-(aminomethyl)-cyclohexane (BAMCH) and spermine [ka]

[0348] GE236; GE237; a mixture of 1,4-bis-(aminomethyl)-cyclohexane (BAMCH) and spermidine [ka]

[0349] GE285; GE291; BEDCH and spermine mixture [ka]

[0350] Replace with: GE208: Isophoronediamine (IPRDA) (mw: 170.3; bp = 252.9°C) [ka]

[0351] Bridged bicyclic structure: GE214 Bis(aminomethyl)norbornane (BAMNB) (mixture of isomers) (mw: 154.25; bp = 259°C) [ka]

[0352] Heterocyclic amines: GE204; [(2S,5R)-5-(aminomethyl)oxolan-2-yl]methanamine; tetrahydrofuran-2,5-diamine (AMTHF) (mw: 130.18) [ka]

[0353] Aromatic (6) amines / substituted GE183, GE184: meta-xylylenediamine (m-XYD) (mw: 136; bp = 265°C) [ka]

[0354] GE185; GE186; GE189; paraxylylenediamine (p-XYD) (mw: 136; bp = 230°C) [ka]

[0355] Primary / Secondary / Tertiary Amines: GE225; N-methyl-1-[4-(methylaminomethyl)phenyl]methanamine (Me-p-XYD) (mw: 164.20) [ka]

[0356] Mixed amines: GE226; GE227; Mixture of paraxylylenediamine (p-XYD) and 1,3,5 benzenetriyltrimethanamine (BTM) [ka]

[0357] GE247; GE251; paraxylylenediamine (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) mixture (APAP) [ka]

[0358] Heteroaromatic amines: GE195: 2,5-bis(aminomethyl)furan (mw: 126.16 g / mol, bp = 230°C). [ka]

[0359] GE217; Tetrafluoro-p-xylylenediamine (TF-p-XYD) (mw: 2018.16) [ka]

[0360] Di / tri / tetra / penta / hexaamine GE220-A2107; 1,3,5 Benzenetriyltrimethanamine (BTM) (mw: 165.24; bp = 329°C) [ka]

[0361] GE222;GE223(Ph-3-ED) [ka]

[0362] GE252;GE253(Ph-3-PD) [ka]

[0363] In some embodiments, the polyamine is [ka] JPEG2026501066000099.jpg150113Cyclohexanediamine, and and combinations thereof.

[0364] It has been discovered that one or more of reducing the particle size of the adsorbent, increasing the aspect ratio of the adsorbent, and synthesizing the adsorbent in an aqueous form result in adsorbents with significantly improved CO2 uptake kinetics.

[0365] Generally, the adsorbent can comprise any suitable particle size known in the art that facilitates the functionalized adsorbents described herein. In some embodiments, the adsorbent has an average particle length of 3 μm or less, 2.9 μm or less, 2.8 μm or less, 2.7 μm or less, 2.6 μm or less, 2.5 μm or less, 2.4 μm or less, 2.3 μm or less, 2.2 μm or less, 2.1 μm or less, 2 μm or less, 1.9 μm or less, 1.8 μm or less, 1.7 μm or less, 1.6 μm or less, 1.5 μm or less, 1.4 μm or less, 1.3 μm or less, 1.2 μm or less, 1.1 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, 0.2 μm or less, or 0.1 μm or less. In some embodiments, the sorbent has an average particle length of 3 μm or more, 2.9 μm or more, 2.8 μm or more, 2.7 μm or more, 2.6 μm or more, 2.5 μm or more, 2.4 μm or more, 2.3 μm or more, 2.2 μm or more, 2.1 μm or more, 2 μm or more, 1.9 μm or more, 1.8 μm or more, 1.7 μm or more, 1.6 μm or more, 1.5 μm or more, 1.4 μm or more, 1.3 μm or more, 1.2 μm or more, 1.1 μm or more, 1 μm or more, 0.9 μm or more, 0.8 μm or more, 0.7 μm or more, 0.6 μm or more, 0.5 μm or more, 0.4 μm or more, 0.3 μm or more, 0.2 μm or more, or 0.1 μm or more.

[0366] Generally, the adsorbent can include any suitable aspect ratio known in the art that facilitates the functionalization of the adsorbents described herein. As used herein, aspect ratio is the ratio of the average width of the adsorbent to 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.

[0367] In some embodiments, the particle size is a discrete particle size. Discrete particle size measurements can be made according to any suitable means known in the art, for example, by measuring particle sizes in SEM images.

[0368] In some embodiments, the particle size measurement is an average particle size measurement. 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.

[0369] In general, the particle size of the adsorbent can be controlled, modified, or reduced according to any suitable technique known in the art to facilitate functionalizing adsorbents as described herein. In some embodiments, suitable techniques for controlling, modifying, or reducing particle size include mechanical milling (e.g., mortar and pestle) using a microfluidizer, dry milling, wet milling, chemical size reduction (e.g., incorporation of crystal growth inhibitors), acoustic cavitation, hydrodynamic cavitation, and combinations thereof.

[0370] Generally, the adsorbent may be in any suitable form known in the art that facilitates the functionalized adsorbents described herein, hi some embodiments, the adsorbent is in a form selected from the group consisting of a powder, a pellet, a composite, a composite mixed with a binder, a film, a coating, a packed bed, a column, a monolith, and combinations thereof.

[0371] Exemplary embodiments described herein include a sorbent system. Generally, the sorbent system may be any suitable sorbent system known in the art that facilitates the functionalized sorbents described herein. In some embodiments, the sorbent system includes a functionalized sorbent and, optionally, a binder. In some embodiments, the sorbent system is disposed on a polymer film.

[0372] In some embodiments, the adsorbent system includes at least one contactor. In some embodiments, the adsorbent system includes two or more contactors. In some embodiments, the adsorbent system includes a contactor configured for an adsorption cycle and a contactor configured for a desorption cycle. The contactor may be any suitable contactor known in the art that facilitates the functionalized adsorbents described herein. In some embodiments, the adsorbent is incorporated into at least one channel of the contactor. In some embodiments, the contactor is fabricated from the adsorbent itself. In some embodiments, the contactor is coated with an adsorbent system. In some embodiments, the contactor includes two or more adsorbent coatings, and at least one adsorbent coating is an adsorbent system.

[0373] In some embodiments, the adsorbent system includes a frame. The frame may be any suitable frame known in the art that facilitates the functionalized adsorbents described herein. The frame may be included in a contactor or between two contactors. The frame may be comprised of one piece or may be comprised of two or more pieces. In some embodiments, the frame is an air frame. In some embodiments, the frame is in a configuration selected from the group consisting of a polygonal configuration, a rectangular configuration, a square configuration, a circular configuration, an asymmetric configuration, and combinations thereof. In some embodiments, the adsorbent system is mounted on the frame.

[0374] In some embodiments, the adsorbent system includes at least one concentrator. The concentrator may be any suitable concentrator known in the art that facilitates the functionalized adsorbents described herein. The concentrator may be a passive or active concentrator.

[0375] In some embodiments, the sorbent system includes at least one component configured to drive fluid flow. The component configured to drive fluid flow may be any suitable component configured to drive fluid flow known in the art to facilitate the functionalized sorbents described herein. In some embodiments, the component configured to drive fluid flow is selected from the group consisting of a pump, a fan, and combinations thereof.

[0376] In some embodiments, the sorbent system includes at least one component configured to alter temperature. The component configured to alter temperature can be any suitable component configured to alter temperature known in the art to facilitate functionalized sorbents described herein. In some embodiments, the component configured to alter temperature is selected from the group consisting of a heater, a cooler, and combinations thereof.

[0377] In some embodiments, the sorbent system includes at least one component configured to convey a fluid. The component configured to convey a fluid may be any suitable component configured to convey a fluid known in the art that facilitates the functionalized sorbents described herein. In some embodiments, the component configured to convey a fluid is selected from the group consisting of tubing, perforated tubing, plastic perforated tubing, polymer perforated tubing, metal perforated tubing, composite perforated tubing, and combinations thereof.

[0378] In general, the functionalized sorbents can be used according to any suitable purpose known in the art that facilitates the use of the functionalized sorbents described herein. In some embodiments, the functionalized sorbents are used in sorbent systems. In some embodiments, the functionalized sorbents are used in carbon capture sorbent systems. In some embodiments, the functionalized sorbents are used in moisture sorbent systems. In some embodiments, the functionalized sorbents are used in carbon capture sorbent systems in the presence of water. In some embodiments, the functionalized sorbents are used to capture gases. In some embodiments, the functionalized sorbents are used in post-combustion capture of CO and / or direct air capture of CO.

[0379] Exemplary embodiments described herein include methods of making the adsorbent systems. Generally, the functionalized adsorbents can be made according to any suitable synthetic method known in the art that facilitates the functionalized adsorbents described herein.

[0380] In many embodiments, a method of making a sorbent system includes making a sorbent, wherein the sorbent has an average particle length of 3 μm or less, and optionally functionalizing the sorbent with at least one functionalizing ligand comprising a polyamine containing at least one cyclic unit.

[0381] In some embodiments, the method of making the sorbent system includes functionalizing the sorbent with at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit. In some embodiments, the method of making the sorbent system includes functionalizing the sorbent 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, the method of making the sorbent system further includes functionalizing the sorbent with at least one functionalizing ligand that does not comprise a polyamine comprising at least one cyclic unit. In some embodiments, the method of making the sorbent system includes controlling the ratio between the at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalizing ligand that does not comprise a polyamine comprising at least one cyclic unit.

[0382] In some embodiments, the method of making the adsorbent system further comprises annealing the functionalized adsorbent. Annealing the adsorbent system can remove excess ligand. In some embodiments, annealing the functionalized adsorbent comprises annealing the functionalized adsorbent at an elevated temperature. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 50°C to about 400°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 100°C to about 300°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 150°C to about 250°C.

[0383] 87 is an exemplary method flowchart 8710. In this exemplary embodiment, method flowchart 8710 illustrates exemplary steps of method embodiments described herein and is not intended to limit method embodiments. In the exemplary embodiment, the method includes step 8712 of forming a mixture including the following: an adsorbent precursor; a crystal growth inhibitor; optionally a solvent; and optionally a non-solvent. The method also includes step 8714 of reacting the mixture. The adsorbent has an average particle length of 3 μm or less.

[0384] Forming the mixture 8712 may be done by any suitable means known in the art. In some embodiments, all of the ingredients are added at the same time. In some embodiments, at least one ingredient is added at a different time than the other ingredients.

[0385] In some embodiments, the sorbent precursor comprises a MOF linker and a MOF metal or metal-containing cluster. The sorbent precursor may be formed before the mixture is formed 8712, added as a single component to the mixture, or formed in situ in the mixture during the formation of the mixture 8712. For example, the MOF linker can be separately deprotonated and then added or deprotonated in situ. Similarly, the MOF metal or metal-containing cluster can be preformed and then added or formed in situ.

[0386] In some embodiments, the solvent comprises an aqueous solvent. In some embodiments, the solvent comprises water. The use of an aqueous solvent offers several advantages. In particular, the use of an aqueous solvent exhibits scalability, safety, cost, and waste disposal advantages compared to at least some known methods of preparing MOF compounds. Furthermore, MOF compounds prepared using an aqueous solvent are generally easier to purify, for example, via solvent washing, than the same MOF compounds prepared according to known methods. This improved purification results from the relative ease of removing solvent molecules (e.g., water) from the MOF compounds described herein compared to the removal of strongly bound solvent molecules (e.g., DMF) utilized to prepare the same MOF compounds according to known methods. Furthermore, the purified MOF compounds are free of strongly bound solvent molecules that reduce gas uptake, surface area, and / or overall pore volume. Finally, purification is improved by requiring less toxic purification methods.

[0387] 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.

[0388] 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.

[0389] 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.

[0390] In some embodiments, the method of making the sorbent system includes functionalizing the sorbent with at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit. In some embodiments, the method of making the sorbent system includes functionalizing the sorbent with at least two functionalizing ligands, each comprising a polyamine comprising at least one cyclic unit, wherein the aminosilicone groups are different from each other. In some embodiments, the method of making the sorbent system further includes functionalizing the sorbent with at least one functionalizing ligand that does not comprise a polyamine comprising at least one cyclic unit. In some embodiments, the method of making the sorbent system includes controlling the ratio between the at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit and the at least one functionalizing ligand that does not comprise a polyamine comprising at least one cyclic unit.

[0391] In some embodiments, the method of making the adsorbent system further comprises annealing the functionalized adsorbent. Annealing the adsorbent system can remove excess ligand. In some embodiments, annealing the functionalized adsorbent comprises annealing the functionalized adsorbent at an elevated temperature. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 50°C to about 400°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 100°C to about 300°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 150°C to about 250°C.

[0392] 88 is an exemplary method flowchart 8810. In this exemplary embodiment, method flowchart 8810 illustrates exemplary steps of method embodiments described herein and is not intended to limit method embodiments. In the exemplary embodiment, the method includes step 8812 of forming a mixture including: an adsorbent; at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit; optionally, at least one functionalized ligand not comprising a polyamine comprising at least one cyclic unit; optionally, a solvent, and optionally, a non-solvent. The method also includes step 8814 of functionalizing the adsorbent.

[0393] In some embodiments, step 8814 of functionalizing the adsorbent includes agitating the mixture.

[0394] In some embodiments, functionalizing the adsorbent 8814 comprises functionalizing the adsorbent 8814 in the presence of an inert gas.

[0395] In some embodiments, functionalizing the adsorbent 8814 comprises functionalizing 3514 the adsorbent at a temperature ranging from about 0° C. to about 100° C. In some embodiments, functionalizing 8814 the adsorbent comprises functionalizing 3514 the adsorbent at a temperature ranging from about 20° C. to about 80° C. In some embodiments, functionalizing 8814 the adsorbent comprises functionalizing 3514 the adsorbent at a temperature ranging from about 20° C. to about 60° C.

[0396] In some embodiments, functionalizing the adsorbent 8814 comprises functionalizing the adsorbent for a time ranging from about 1 minute to about 7 days 8814. In some embodiments, functionalizing the adsorbent 8814 comprises functionalizing the adsorbent for a time ranging from about 1 hour to about 3 days 8814.

[0397] In some embodiments, the adsorbent is desolvated before functionalization 8814. In some embodiments, the adsorbent is dried before functionalization.

[0398] In some embodiments, the adsorbent is annealed after functionalization 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 ranging from about 50°C to about 400°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 100°C to about 300°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature ranging from about 150°C to about 250°C.

[0399] 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.

[0400] 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.

[0401] In some embodiments, the non-solvent aids in functionalization. In some embodiments, the selectivity of functionalization is controlled by relative solubility. For example, one or more 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 may introduce limiting reactions and / or reagents.

[0402] In many embodiments, the methods can also include any additional suitable processing steps known in the art that facilitate the success of the methods described herein. Such processing steps include, but are not limited to, washing, drying, filtering, purifying, separating, centrifugation, and any combination thereof. In some embodiments, the methods further include washing the functionalized adsorbent. In some embodiments, the methods further include purifying the functionalized adsorbent. In some embodiments, the purification includes distillation, vacuum distillation, and / or the use of heat.

[0403] SUMMARY OF THE INVENTION Exemplary embodiments described herein include methods for capturing at least one gas.

[0404] FIG. 89 is an exemplary method flowchart 8910. In an exemplary embodiment, method flowchart 8910 illustrates exemplary method steps of method embodiments described herein and is not intended to limit method embodiments. The method includes step 8912 of receiving a gas source containing at least one gas with a functionalized adsorbent, the functionalized adsorbent comprising an adsorbent; and at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit. In some embodiments, the functionalized adsorbent includes 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, the functionalized adsorbent further includes at least one functionalizing ligand that does not comprise a polyamine comprising at least one cyclic unit. The method also includes step 8914 of capturing a quantity of at least one gas with the functionalized adsorbent. The adsorbent may have an average particle length of 3 μm or less.

[0405] In some embodiments, the method includes (I) receiving 8912 a gas source comprising at least one gas with a functionalized adsorbent, the functionalized adsorbent comprising an adsorbent and at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit; and (II) capturing 8914 a quantity of the at least one gas with the functionalized adsorbent.

[0406] Generally, the gas source may be any suitable gas source known in the art that facilitates the methods described herein. In some embodiments, the gas source is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0407] Generally, the at least one gas may 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, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0408] In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 100% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 40% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 15% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v). In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v). In some embodiments, at least one gas is present in the feed gas in an amount greater than 10% (v / v).

[0409] In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 100 ppmv to about 1000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 200 ppmv to about 1000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 300 ppmv to about 5000 ppmv.

[0410] In some embodiments, the at least one gas does not include water vapor.

[0411] In some embodiments, at least one gas comprises water vapor. In some embodiments, at least one gas comprises water vapor in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, at least one gas comprises water vapor in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, at least one gas comprises water vapor in an amount ranging from about 0.5% (v / v) to about 15% (v / v). In some embodiments, at least one gas comprises water vapor in an amount ranging from about 0.5% (v / v) to about 4% (v / v). In some embodiments, at least one gas comprises water vapor in an amount ranging from about 4% (v / v) to about 15% (v / v).

[0412] In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v) and in the presence of water vapor. In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v) and in the presence of water vapor. In some embodiments, at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v) and in the presence of water vapor. In some embodiments, at least one gas is present in the source gas in an amount greater than about 10% (v / v) and in the presence of water vapor. In some embodiments, water vapor is present in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.5% (v / v) to about 10% (v / v).

[0413] In some embodiments, capturing a quantity of at least one gas with the functionalized adsorbent 8814 comprises adsorbing a quantity of the at least one gas with the functionalized adsorbent, hi some embodiments, capturing a quantity of the at least one gas with the functionalized adsorbent 8814 comprises adsorbing a quantity of the at least one gas with the functionalized adsorbent in the presence of water vapor.

[0414] In some embodiments, the amount of at least one gas 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 feed gas. In some embodiments, the amount of at least one gas 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 feed gas. In some embodiments, the amount of at least one gas 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 feed gas. In some embodiments, the amount of at least one gas 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 feed gas. In some embodiments, the amount of at least one gas 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 feed gas.

[0415] In some embodiments, the amount of at least one gas 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 feed gas. In some embodiments, the amount of at least one gas 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 feed gas. In some embodiments, the amount of at least one gas 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 feed gas. In some embodiments, the amount of at least one gas 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 feed gas. In some embodiments, the amount of at least one gas 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 feed gas.

[0416] In some embodiments, the amount of at least one gas 8814 captured by the functionalized adsorbent ranges from about 80% (v / v) to about 100% (v / v) of the at least one gas present in the feed gas. In some embodiments, the amount of at least one gas 8814 captured by the functionalized adsorbent ranges from about 85% (v / v) to about 100% (v / v) of the at least one gas present in the feed gas. In some embodiments, the amount of at least one gas 8814 captured by the functionalized adsorbent ranges from about 90% (v / v) to about 100% (v / v) of the at least one gas present in the feed gas. In some embodiments, the amount of at least one gas 8814 captured by the functionalized adsorbent ranges from about 95% (v / v) to about 100% (v / v) of the at least one gas present in the feed gas.

[0417] In some embodiments, the feed gas is reformed to vary the amount of water vapor. In some embodiments, varying the amount of water vapor comprises increasing the amount of water vapor. In some embodiments, varying the amount of water vapor comprises decreasing the amount of water vapor. In some embodiments, increasing the amount of water vapor comprises adding or injecting water vapor into the source gas. In some embodiments, decreasing the amount of water vapor comprises removing water vapor from the feed gas by evaporation, condensation, and / or pre-adsorption. In some embodiments, varying the amount of water vapor comprises exhaust gas recirculation (EGR) and / or blending.

[0418] In many embodiments, the functionalized adsorbent, the feed gas, the at least one gas, or a combination thereof, is at a particular temperature. Each temperature can be varied to facilitate the methods described herein. Each temperature can have a uniform temperature profile, a gradient temperature profile, a discrete temperature profile, or a combination thereof.

[0419] In some embodiments, the method includes an adsorption cycle. In some embodiments, the method includes a desorption cycle. In some embodiments, at least one of the functionalized adsorbent, the feed gas, the at least one gas, or a combination thereof is at a temperature ranging from about 0° C. to about 150° C. during the gas adsorption cycle. In some embodiments, at least one of the functionalized adsorbent, the feed gas, the at least one gas, or a combination thereof is at a temperature ranging from about 60° C. to about 250° C. during the gas desorption cycle.

[0420] In some embodiments, the method includes controlling the temperature. The temperature can be controlled for the functionalized adsorbent, the feed gas, the at least one gas, or a combination thereof.

[0421] SUMMARY OF THE INVENTION Exemplary embodiments described herein include a method for recovering at least one gas from a gas source.

[0422] FIG. 90 is an exemplary method flowchart 9010. In this exemplary embodiment, the method flowchart 9010 illustrates exemplary method steps of method embodiments described herein and is not intended to limit the method embodiments. The method includes step 9012 of receiving a gas source containing at least one gas with a functionalized adsorbent, the functionalized adsorbent comprising an adsorbent; and at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit. In some embodiments, the functionalized adsorbent includes 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, the functionalized adsorbent further includes at least one functionalizing ligand that does not comprise a polyamine comprising at least one cyclic unit. The method also includes step 9014 of capturing a quantity of at least one gas with the functionalized adsorbent. The method also includes step 9016 of releasing the at least one gas from the functionalized adsorbent. The adsorbent may have an average particle length of 3 μm or less.

[0423] In some embodiments, the method includes (I) step 9012 of receiving a gas source comprising at least one gas with a functionalized adsorbent, the functionalized adsorbent comprising an adsorbent and at least one functionalizing ligand comprising a polyamine comprising at least one cyclic unit; (II) step 9014 of capturing a quantity of the at least one gas with the functionalized adsorbent; and (III) step 9016 of releasing the at least one gas from the functionalized adsorbent.

[0424] In some embodiments, releasing 9016 the at least one gas from the functionalized adsorbent comprises purging the at least one gas from the functionalized adsorbent with a purge gas, hi some embodiments, releasing 9016 the at least one gas from the functionalized adsorbent comprises subjecting the functionalized adsorbent to a change in temperature or pressure.

[0425] In some embodiments, at least one gas is released from the functionalized adsorbent into a receiving gas 9016. In some embodiments, the receiving gas is selected from the group consisting of air, N2, steam, and combinations thereof. In some embodiments, the receiving gas is removed from the presence of the functionalized adsorbent after receiving the at least one gas. In some embodiments, the receiving gas has an increased concentration of the at least one gas compared to the feed gas.

[0426] Further aspects of the present disclosure are provided by the subject matter of the following clauses.

[0427] 1. A functionalized adsorbent comprising: Adsorbents; and at least one functionalized ligand comprising a polyamine containing at least one cyclic unit; A functionalized adsorbent comprising:

[0428] 2. The functionalized adsorbent of the preceding clause, wherein the adsorbent comprises a metal-organic framework (MOF).

[0429] 3. The functionalized adsorbent of the preceding clause, wherein a first amine of the polyamine binds to a first metal site of the MOF and, optionally, a second amine of the polyamine binds to a second metal site of the MOF.

[0430] 4. The functionalized sorbent of any of the preceding clauses, wherein at least one cyclic unit is selected from the group consisting of an alicyclic unit, an aromatic unit, and combinations thereof.

[0431] 5. The functionalized sorbent of any of the preceding clauses, comprising at least one functionalizing ligand that does not comprise a polyamine containing at least one cyclic unit.

[0432] 6. The functionalized sorbent of any of the preceding clauses, wherein the polyamine comprises at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof.

[0433] 7. The functionalized adsorbent of any preceding clause, wherein the adsorbent has an aspect ratio of ≥ 0.2.

[0434] 8. A functionalized adsorbent according to any preceding clause, wherein the adsorbent has an average particle length of 3 μm or less.

[0435] 9. The polyamine has the formula (CI): [ka] and comprising at least one cyclic unit of During the ceremony, B, C, and D each individually contain at least one amine group; x, y, and z are each independently 0 or 1; A is an aromatic ring structure according to formula (C-II) or an alicyclic structure according to formula (C-III): [ka] Including, During the ceremony, n is an integer ranging from about 3 to about 8; m is an integer ranging from about 3 to about 5; A 1 , A 2 , A 3 , and A 4 each independently contains at least one of carbon, oxygen, and silicon; The functionalized adsorbent of any of the preceding clauses.

[0436] 10.A 1 , A 2 , A 3 , and A 4 are respectively, 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 linear alkyl, substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; and combinations of these The functionalized adsorbent of the preceding clause, selected from the group consisting of:

[0437] 11. B, C, and D each independently represent a group of formula (C-IV): [ka] wherein: t, u, v, and w are each independently an integer ranging from about 0 to about 10; E, F, G and H are each individually Substituted or unsubstituted C1 to C6 straight chain alkyl, substituted or unsubstituted C3 to C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; R1 and R2 are each independently selected from the group consisting of substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; NH2, NHR1, and NR1R 2;並びに combinations of these The functionalized adsorbent of the preceding clause, selected from the group consisting of:

[0438] 12. The polyamine contains at least two cyclic units; the polyamine comprises a polycyclic structure linked by at least one linking group selected from the group consisting of substituted or unsubstituted C1 to C6 straight chain alkyl, substituted or unsubstituted C3 to C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl; or The functionalized sorbent of the preceding clause, wherein the polyamine comprises a bridged polycyclic structure comprising at least one bridging group selected from the group consisting of substituted or unsubstituted C1-C6 linear alkyl, substituted or unsubstituted C3-C6 branched alkyl, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl.

[0439] 13. Polyamines are: [ka] JPEG2026501066000104.jpg24955JPEG2026501066000105.jpg246124JPEG2026501066000106.jpg23866JPEG2026501066000107.jpg23366JPEG2026501066000108.jpg19899 and The functionalized adsorbent of any of the preceding clauses, which is a compound selected from the group consisting of:

[0440] 14. An adsorbent system comprising the functionalized adsorbent of any of the preceding clauses.

[0441] 15. A method of making a functionalized adsorbent, comprising: (I) Adsorbents; at least one functionalized ligand comprising a polyamine containing at least one cyclic unit; Optionally, at least one functionalized ligand that does not comprise a polyamine comprising at least one cyclic unit; optionally a solvent; and Optionally a non-solvent forming a mixture comprising: (II) functionalizing the adsorbent; A method of making a functionalized adsorbent comprising:

[0442] 16. The method of the preceding clause, wherein the adsorbent has an average particle length of 1 μm or less.

[0443] 17. A method for capturing at least one gas, comprising: (I) receiving a gas source comprising at least one gas with a functionalized adsorbent, the functionalized adsorbent comprising: Adsorbents; at least one functionalized ligand comprising a polyamine containing at least one cyclic unit; and (II) capturing a quantity of at least one gas using a functionalized adsorbent; 1. A method for capturing at least one gas, comprising:

[0444] 18. The method of the preceding clause, wherein the gas source is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0445] 19. The method of any preceding clause, wherein the at least one gas is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0446] 20. A method for recovering at least one gas from a gas source, comprising: capturing at least one gas according to the method of any preceding clause; (III) releasing at least one gas from the functionalized adsorbent; and 1. A method for recovering at least one gas from a gas source, comprising: [Example]

[0447] Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. Therefore, the following examples should be construed as merely illustrative and in no way limiting of the present disclosure. The starting materials in the following examples may not necessarily have been prepared by the specific preparation procedures described in other examples. Furthermore, any numerical range recited herein is understood to include all values ​​from the lower value to the upper value. For example, if a range is stated as 10 to 50, it is intended that values ​​such as 12 to 30, 20 to 40, or 30 to 50 are expressly recited herein. These are merely examples of what is specifically intended, and all possible combinations of numerical values ​​between the lowest and highest recited values ​​should be considered to be expressly stated in this application.

[0448] Systems for carbon dioxide capture using functionalized sorbents and water management

[0449] Example A1. Comparative Moisture Isotherms. Figure 5 shows the HO adsorption capacities of adsorbents functionalized with AEAM, spermidine, and spermine hybrids (AEAM: 0.65:0.35) ("Hybrid Compound 1") and spermine hybrids (AEAM: 0.32:0.46) ("Hybrid Compound 2") as a function of relative humidity at 25 °C, as measured using DVS gravimetric analysis. This figure demonstrates that the moisture adsorption isotherms, and therefore the relative humidity at which the knee-point for monolayer adsorption of HO occurs, change with changes in the chemical structure of the functionalized adsorbents. As shown in Figure 5, all adsorbents except AEAM have moisture adsorption isotherm shapes most similar to Type IV, which include a flattened region leading to the knee-point corresponding to monolayer coverage and approximately 30% relative humidity for the two hybrid compounds and approximately 35% HO adsorption for spermidine.

[0450] Example A2. Water sorption isotherm of hybrid compound 1. The HO adsorption capacity of hybrid compound 1 (spermine:AEAM = 0.65:0.35) as a function of relative humidity at various temperatures, measured using DVS gravimetry, is shown in Figure 6. The HO adsorption capacity of hybrid compound 1 (spermine:AEAM = 0.65:0.35) as a function of HO partial pressure (kPa) at various temperatures, measured using DVS gravimetry, is shown in Figure 7. These figures show that although the absolute HO partial pressure changes, the shape of the moisture isotherm, and therefore the relative humidity at which the knee point occurs for monolayer adsorption of HO, remains nearly the same as the temperature changes.

[0451] Example A3. Adsorption performance of hybrid compound 1. Figure 8 shows the CO2 and HO adsorption performance of hybrid compound 1 (spermine:AEAM = 0.65:0.35) as a function of relative humidity at 40 °C under 4.5 v% CO2, as measured using DVS gravimetry. This figure suggests that CO2 adsorption is sensitive to relative humidity. As shown for hybrid compound 1 in Figure 5, the knee point for monolayer adsorption of HO appears to be a critical threshold. Because DVS gravimetry is based on measuring the change in accumulated mass, it cannot accurately calculate the amount of individual CO2 adsorption versus HO adsorption due to the lack of distinction between individual components in a binary system (e.g., CO2 and HO in this case). However, a breakthrough test rig and analytical equipment equipped with individual sensors designated for CO2 and HO should be used to quantitatively assess individual CO2 and HO adsorption.

[0452] Example A4. Adsorption performance of hybrid compound 1 as a function of temperature, water content and relative humidity.

[0453] The CO adsorption performance of hybrid compound 1 (spermine:AEAM = 0.65:0.35) under 4.5 v% CO as a function of water pressure (kPa) at various temperatures, measured using DVS gravimetry, is shown in Figure 9. The HO adsorption capacity of hybrid compound 1 (spermine:AEAM = 0.65:0.35) as a function of water pressure (kPa) at various temperatures, measured using DVS gravimetry, is shown in Figure 10. The CO adsorption performance of hybrid compound 1 (spermine:AEAM = 0.65:0.35) as a function of relative humidity at various temperatures, measured using DVS gravimetry, is shown in Figure 11. These figures show that the adsorption performance of hybrid compound 1 varies with temperature and water pressure, but high performance can be maintained by adjusting the relative humidity by adjusting the temperature and water content. These figures further suggest that CO adsorption is sensitive to relative humidity. As shown for hybrid compound 1 in Figure 5, the knee point for monolayer adsorption of HO appears to be a critical threshold. Similarly, separate CO2 and H2O adsorption should be quantitatively assessed using a breakthrough test rig and analytical equipment equipped with individual sensors designated for CO2 and H2O.

[0454] Example A5. Comparative Adsorption Capacity. The CO2 adsorption isotherms of hybrid compound 1 (spermine:AEAM=0.65:0.35) for dry and wet CO2 with 30% relative humidity at 40 °C measured using DVS gravimetry are shown in Figure 12A. This figure shows that the adsorption capacity of hybrid compound 1 increases under wet conditions with 30% relative humidity compared to the dry condition.

[0455] Figure 12B shows the CO adsorption of hybrid compound 3 (spermine:AEAM = 0.69:0.23) for dry and wet CO at various relative humidities under DAC-relevant conditions of 25 °C and a CO concentration of 400 ppmv, as measured using a breakthrough test rig with individual CO and HO sensors. Figure 12B also shows the pure HO adsorption isotherm for hybrid compound 3. This figure quantitatively demonstrates that, at least for the test conditions relevant to DAC applications, (1) wet CO results in increased CO adsorption relative to dry CO, i.e., at 0% relative humidity, aligned with the knee point for monolayer adsorption of HO, as shown for hybrid compound 3 in Figure 12B; (2) the amount of CO adsorption is sensitive to the actual relative humidity; and (3) CO adsorption appears to plateau once a minimum relative humidity is reached, as shown for hybrid compound 3 in Figure 12B.

[0456] Described herein are exemplary systems for using functionalized chemical sorbents in the presence of water to facilitate optimization of carbon dioxide adsorption and desorption by adsorbent beds. The exemplary systems described herein offer several advantages over conventional designs and processes, including at least improving carbon dioxide adsorption and desorption efficiency and performance through the use of temperature and / or water relative humidity variations within the adsorbent bed, varying the functionalized adsorbent within the adsorbent bed, and / or improving capture system performance through adjustment of temperature and water relative humidity within one or more adsorption modules within an adsorbent bed based on the functionalized adsorbent within one or more adsorption modules.

[0457] Synthesis of aminoalkyl-substituted disiloxanes. Example B1. Synthesis of the aminomethyl-substituted disiloxane 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane with 4 equivalents of ethylenediamine.

[0458] Ethylenediamine (396 mL, 5.93 mol) was added to a 2 L, 3-neck, round-bottom flask equipped with an addition funnel and a reflux condenser. The flask was placed in an ice-water bath and the headspace was purged with N2. Chloromethyldimethylethoxysilane (240 mL, 1.48 mol) was added to the addition funnel and added dropwise to the ethylenediamine over 1 h as the reaction exothermed to 90-100 °C. After an additional 1 h, 1 The reaction was judged complete by H NMR, at which point 300 mL of water was added dropwise to the reaction mixture over 30 minutes, resulting in an 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 vigorously stirred for 1 hour, after which the organic layer was isolated 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 was collected at 40-80°C and 380 mTorr, containing primarily cyclic by-products and some product. The remaining material (167 g, 81% yield) was 1 It was deemed >75% pure by 1 H NMR spectroscopy. 1 H 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).

[0459] Example B2. Synthesis of the aminomethyl-substituted disiloxane 1,3-bis(3-aminopropylaminomethyl)tetramethyldisiloxane. The same procedure was followed for Example B1, but using 1,3-propanediamine (52 mL, 0.62 mol), chloromethyldimethylethoxysilane (25 mL, 0.15 mol), 40 mL of water, and 40 mL of chloroform in a 250 mL three-neck flask. The resulting material was then purified by vacuum distillation. The first fraction, containing mainly cyclic by-products and some product, was collected over a temperature range of 40-65°C. The remaining material (17.6 g, 74% yield) was 1 It was deemed >95% pure by 1 H NMR spectroscopy. 1 H NMR(CDCl3)δ:2.75(t,4H,H2NCH2CH2CH2),2.65(t,4H,H2NCH2),2.05(s,4H,SiCH2),1.60(mult,4H,H2NCH2CH2),1.30(br s,6H,NH&NH2),0.12(s,12H,SiCH3).

[0460] Example B3. Synthesis of the aminomethyl-substituted disiloxane 1,3-bis(2-methyl-3-aminopropylaminomethyl)tetramethyldisiloxane. The same procedure was followed for Example B1, but using 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 in a 15 mL flask. The resulting material was then purified by vacuum distillation. The first fraction, containing by-products and some product, was collected at 110° C. The remaining material (0.60 g, 51% yield) was 1 It was deemed >95% pure by 1 H NMR spectroscopy. 1 H NMR(CDCl3)δ:2.8-2.5(overlapping mult,8H,H2NCH2CH(CH3)CH2),2.05(mult,4H,SiCH2),1.75(mult,2H,H2NCH2CH),1.95(br s,6H,NH&NH2),0.90(d,6H,H2NCH2CHCH3)0.12(s,12H,SiCH3).

[0461] Example B4. Synthesis of the aminomethyl-substituted disiloxane 1,3-bis(2,2-dimethyl-3-aminopropylaminomethyl)tetramethyldisiloxane. The same procedure was followed for Example B1, except that 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 product, was collected at 80-90°C. The remaining material (0.95 g, 74% yield) was 1 It was deemed >95% pure by 1 H NMR spectroscopy. 1 H 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).

[0462] Example B5. Synthesis of the aminomethyl-substituted disiloxane 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane with 8 equivalents of ethylenediamine. Ethylenediamine (793 mL, 11.9 mol) was added to a 2 L, 3-neck, round-bottom flask equipped with an addition funnel and a reflux condenser. The flask was placed in an ice-water bath and the headspace was purged with N2. Chloromethyldimethylethoxysilane (240 mL, 1.48 mol) was added to the addition funnel and added dropwise to the ethylenediamine over 1 h as the reaction exothermed to 90-100 °C. After an additional 1 h, 1The reaction was judged complete by H NMR, at which point 300 mL of water was added dropwise to the reaction mixture over 30 minutes, resulting in an 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 vigorously stirred for 1 hour, after which the organic layer was isolated 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 was collected at 40-80°C and 380 mTorr, containing primarily cyclic by-products and some product. The remaining material (326 g, 79% yield) was 1 It was deemed >90% pure by 1 H NMR spectroscopy. 1 H 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).

[0463] Example B6. Synthesis of the aminomethyl-substituted disiloxane 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane with 10 equivalents of ethylenediamine. Ethylenediamine (400 mL, 5.99 mol) was added to a 2 L, 3-neck, round-bottom flask equipped with an addition funnel and a reflux condenser. The flask was placed in an ice-water bath and the headspace was purged with N2. Chloromethyldimethylethoxysilane (97 mL, 0.59 mol) was added to the addition funnel and added dropwise to the ethylenediamine over 1 h as the reaction exothermed to 90-100 °C. After an additional 1 h, 1 The reaction was judged complete by H NMR, at which point 300 mL of water was added dropwise to the reaction mixture over 30 minutes, resulting in an 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 vigorously stirred for 1 hour, after which the organic layer was isolated 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 was collected at 40-80°C and 380 mTorr, containing primarily cyclic by-products and some product. The remaining material (117 g, 70% yield) was1 It was deemed >95% pure by 1 H NMR spectroscopy. 1 H 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).

[0464] Comparative Example B1. Attempted synthesis of the aminomethyl-substituted disiloxane 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane from 1,3-bis(chloromethyl)tetramethyldisiloxane. Ethylenediamine (13 g, 0.216 mol, 10 equivalents) was added to a 50 mL three-neck round-bottom flask equipped with a nitrogen blanket, magnetic stir bar, condenser, and addition funnel. This was then heated in an oil bath set at 110°C. Once the temperature in the oil bath had stabilized, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane (5 g, 0.0216 mol) was added dropwise over 2 hours. The reaction was stirred at room temperature overnight. The reaction was cooled and 1 H NMR analysis confirmed the reaction was complete. The reaction mixture was then poured into a 250 ml separatory funnel and partitioned between chloroform and 10% NaOH, washed three times with DI water and once with saturated sodium chloride, and then dried over anhydrous potassium chloride. After filtration, the chloroform was stripped on a rotary evaporator to yield a clear, colorless, viscous liquid. 1 H NMR analysis showed a mixture of products containing the cyclic by-product 2,2,6,6-tetramethyl-1-oxa-4-aza-2,6-disilacyclohexane-4-ethanamine. The desired 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane was not formed.

[0465] Comparative Example B2. Attempted synthesis of the aminomethyl-substituted disiloxane 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane from 1,3-bis(iodomethyl)tetramethyldisiloxane. Ethylenediamine (13 g, 0.216 mol, 10 equiv.) was added to a 50 mL three-neck round-bottom flask equipped with a nitrogen blanket, a magnetic stir bar, a condenser, and an addition funnel. 1,3-Bis(iodomethyl)-1,1,3,3-tetramethyldisiloxane (10.16 g, 0.0216 mol) was added dropwise over 2 hours. The reaction was stirred at room temperature overnight. 1 H NMR analysis confirmed the reaction was complete. The reaction mixture was then poured into a 250 ml separatory funnel and partitioned between chloroform and 10% NaOH, washed three times with DI water and once with saturated sodium chloride, and then dried over anhydrous potassium chloride. After filtration, the chloroform was stripped on a rotary evaporator to yield a clear, colorless, viscous liquid. 1 H NMR analysis showed clean formation of the cyclic by-product 2,2,6,6-tetramethyl-1-oxa-4-aza-2,6-disilacyclohexane-4-ethanamine. The desired 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane was not formed. 1 H NMR(CDCl3), δ:2.70(t,2H,CH2),2.40(t,2H,CH2),1.75(overlapping s,4H+2H,SiCH2NCH2Si+H2N),0.10(s,12H,SiCH3)

[0466] Solid Adsorbent Materials This example uses MOF-274 [Mg2(dobpdc)] as an illustration, however, this example is not limited to MOF-274 and is broadly applicable to any other materials or methods according to this disclosure.

[0467] Characterization techniques. particle size Scanning electron microscopy (SEM) is used to characterize the average particle shape and size, with the aspect ratio defined as the ratio of the average length to the average length.

[0468] Dynamic Vapor Sorption Analyzer (DVS) gravimetric CO2 and H2O uptake.

[0469] A dynamic vapor sorption analyzer (DVS) was used to study the performance of CO2 and H2O adsorption. In the experiments presented in this work, the gases used were CO2 and water, respectively. The DVS vacuum analyzer is designed to accurately measure the mass change of a sample as it adsorbs precisely controlled concentrations of water and / or gas molecules. The sample is placed in a sample pan suspended from a microbalance (an empty pan is usually suspended on the other side of the microbalance as a "reference"). The DVS vacuum simultaneously controls and measures the inflow and outflow of sorbent while recording the change in sample mass. The primary instrument, the microbalance (UltraBalance™), is housed in a precisely controlled temperature-controlled enclosure (called an incubator). This ensures a highly stable instrument baseline and accurate vapor generation control at the experimental temperature.

[0470] A two-cycle sequential adsorption test protocol is developed as follows: At the start of each test, the adsorbent material of interest is added to the 10 -5 The sample is subjected to an activation (or regeneration) step at 120 °C for 30 to...

Claims

1. an adsorbent; at least one functionalized ligand comprising a polyamine comprising at least one cyclic unit; A functionalized adsorbent (114) comprising:

2. 10. The functionalized adsorbent (114) of claim 1, wherein the adsorbent comprises a metal organic framework (MOF (1422)).

3. 3. The functionalized adsorbent (114) of claim 2, wherein a first amine of the polyamine binds to a first metal site of the MOF (1422), and optionally a second amine of the polyamine binds to a second metal site of the MOF (1422).

4. 10. The functionalized adsorbent (114) of 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. 10. The functionalized adsorbent (114) of claim 1, comprising at least one functionalizing ligand that does not include a polyamine containing at least one cyclic unit.

6. 10. The functionalized adsorbent (114) of claim 1, wherein the polyamine comprises at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof.

7. The functionalized adsorbent (114) of claim 1, wherein the adsorbent has an aspect ratio of 0.2 or greater.

8. The functionalized adsorbent (114) of claim 1, wherein the adsorbent has an average particle length of 3 μm or less.

9. The polyamine has the formula (CI): 【Chemistry 1】 and wherein the ring unit is at least one ring unit according to During the ceremony, B, C, and D each independently contain at least one amine group; x, y, and z are each independently 0 or 1; A is an aromatic ring structure according to formula (C-II) or an alicyclic structure according to formula (C-III): 【Chemistry 2】 Including, During the ceremony, n is an integer ranging from about 3 to about 8; m is an integer ranging from about 3 to about 5; A １ , A ２ , A ３ , and A ４ each independently contain at least one of carbon, oxygen, and silicon; The functionalized adsorbent (114) of claim 1.

10. A １ , A ２ , A ３ , and A ４ are each individually, Hydrogen, B, C, D, substituted or unsubstituted linear alkyl, substituted or unsubstituted C １ ~C ６ Straight-chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C ３ ~C ６ a carbon substituted with at least one substituent selected from the group consisting of 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; Hydrogen, B, C, D, substituted or unsubstituted linear alkyl, substituted or unsubstituted C １ ~C ６ Straight-chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C ３ ~C ６ Silicon substituted with at least one substituent selected from the group consisting of branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; and combinations of these The functionalized adsorbent (114) of claim 9 selected from the group consisting of:

11. B, C, and D each independently represent a group represented by formula (C-IV): 【Transformation 3】 wherein: t, u, v, and w are each independently an integer ranging from about 0 to about 10; E, F, G and H are each individually Substituted or unsubstituted C １ ~C ６ Straight chain alkyl, substituted or unsubstituted C ３ ~C ６ Branched alkyl, C １ Alkyl, C ２ Alkyl, C ３ Alkyl, C ４ Alkyl, C ５ Alkyl, and C ６ Alkyl; R １ and R ２ are each independently substituted or unsubstituted C １ ~C ６ Straight chain alkyl, substituted or unsubstituted C ３ ~C ６ Branched alkyl, C １ Alkyl, C ２ Alkyl, C ３ Alkyl, C ４ Alkyl, C ５ Alkyl, and C ６ alkyl, NH ２ , N.H.R. １ and NR １ R ２ ;and combinations of these The functionalized adsorbent (114) of claim 9 selected from the group consisting of:

12. the polyamine comprises at least two cyclic units; The polyamine is a substituted or unsubstituted C １ ~C ６ Straight chain alkyl, substituted or unsubstituted C ３ ~C ６ Branched alkyl, C １ Alkyl, C ２ Alkyl, C ３ Alkyl, C ４ Alkyl, C ５ Alkyl and C ６ comprising a polycyclic structure linked by at least one linking group selected from the group consisting of alkyl; The polyamine is a substituted or unsubstituted C １ ~C ６ Straight chain alkyl, substituted or unsubstituted C ３ ~C ６ Branched alkyl, C １ Alkyl, C ２ Alkyl, C ３ Alkyl, C ４ Alkyl, C ５ Alkyl and C ６ a bridged polycyclic structure containing at least one bridging group selected from the group consisting of alkyl; The functionalized adsorbent (114) of claim 1.

13. The polyamine is 【Chemistry 4】 【change】 【change】 【change】 【change】 【change】 and combinations of these 10. The functionalized adsorbent (114) of claim 1, wherein the functionalized adsorbent is a compound selected from the group consisting of:

14. An adsorbent system comprising the functionalized adsorbent (114) of claim 1.

15. A method of making a functionalized adsorbent (114), comprising: (I) an adsorbent; at least one functionalized ligand comprising a polyamine containing at least one cyclic unit; Optionally, at least one functionalized ligand that does not include a polyamine comprising at least one cyclic unit; optionally, a solvent; and Optionally, a non-solvent forming a mixture comprising: (II) functionalizing the adsorbent; A method of making a functionalized adsorbent (114), comprising:

16. 16. The method of claim 15, wherein the adsorbent has an average particle length of 3 μm or less.

17. 1. A method for capturing at least one gas, comprising: (I) receiving a gas source containing said at least one gas with a functionalized adsorbent (114), said functionalized adsorbent (114) comprising: adsorbent; at least one functionalized ligand comprising a polyamine containing at least one cyclic unit; and (II) capturing a quantity of said at least one gas by said functionalized adsorbent (114); 1. A method for capturing at least one gas, comprising:

18. 18. The method of 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 gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

19. 18. The method of 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, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gases, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

20. 1. A method for recovering at least one gas from a gas source, comprising: Trapping the at least one gas according to the method of claim 17; (III) releasing the at least one gas from the functionalized adsorbent (114); and 1. A method for recovering at least one gas from a gas source, comprising:

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