Adsorbent compositions, systems, and methods

Abstract

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

Description

[0001] Related Applications

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

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

[0004] Solid adsorbents can be used for a variety of purposes. For example, they are particularly useful in carbon capture adsorbent systems, such as for carbon dioxide (CO 2 ), post-combustion carbon capture (PCC) and direct air capture (DAC). Solid adsorbents for carbon capture offer viable and superior performance to conventional liquid amine-based CO 2 Techno-economic alternatives to capture methods. For example, solid adsorbents tend to have better adsorption capacity, lower regeneration energy requirements, and reduced system complexity and environmental and safety risks compared to active liquid amines.

[0005] There are two types of adsorbent materials based on the underlying adsorption mechanism. The first type is physical adsorbents, which rely on non-covalent interactions (e.g., van der Waals interactions, dipole-dipole interactions, etc.) to adsorb gaseous species such as CO. 2 and H 2O. Examples of physical adsorbents include activated carbon, zeolites, and metal organic frameworks (MOFs). The second type is chemical adsorbents, which adsorb CO through a reversible chemical reaction and by forming ammonium carbamate, carbamic acid, ammonium carbonate, and / or ammonium bicarbonate. 2 Examples of chemical adsorbents include amine-functionalized silica particles, amine-functionalized polymers and resins, amine-functionalized metal organic frameworks (MOFs), and amine-functionalized covalent organic frameworks (COFs).

[0006] Due to chemical bonding, chemical adsorbent materials are generally more resistant to interfering substances such as N than physical adsorbent materials. 2 , methane and CO have better C0 2 Adsorption selectivity. However, the effectiveness of chemical adsorbent systems can be limited by the compositional nature of the functionalized molecules that undergo the chemical adsorption and functionalization processes. Therefore, there is a need for functionalized adsorbents containing chemically and thermally stable molecular species that selectively absorb CO with high capacity and rapid kinetics. 2 .

[0007] Relatedly, at least some known industrial and power generation processes can result in the production of 2 Thus, capture systems can be used to facilitate the removal of pollutants from an exhaust gas stream before it is released into the atmosphere. For example, a carbon capture system can be used to attempt to capture CO 2 and store it underground, reducing the amount of CO released into the atmosphere 2 The amount.

[0008] At least some known carbon capture systems may use adsorption beds to capture and release CO 2 In some known systems, solid adsorbent materials may be used with the adsorbent bed to enhance the adsorption of CO in order to improve the adsorption capacity and efficiency of the system. 2 adsorption and desorption, which is similar to the use of liquid amine-based CO 2 Other known systems for capture methods are the opposite. However, the effectiveness of chemical adsorbent systems is often limited by functionalization as well as detailed operating conditions.

[0009] In order to increase the captured CO 2 At least some known carbon capture systems use water to improve CO 2 Capture efficiency. For example, carbon capture systems can use wet conditions to improve CO 2 However, if too much H 2 O, then from H 2 Interference from O molecules may reduce the CO content of the chemical adsorbent material used in the adsorption bed. 2Adsorption capacity. Therefore, there is a need for capture systems that use functionalized chemical adsorbents in the presence of water to optimize the efficiency and productivity of carbon dioxide adsorption and desorption.

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

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

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

[0013] Relatedly, some power plant systems may include a post-combustion carbon capture system configured to capture carbon dioxide (CO 2 ). PCC systems can be used to capture CO from exhaust gases produced in power plants. 2 , these power plants include, for example, coal-fired systems, gas turbines and / or boilers. Some types of PCC systems use metal organic frameworks to facilitate carbon capture. Metal organic frameworks generally include two main components: an inorganic metal component (often referred to as a secondary building unit or SBU) and an organic component (often referred to as a linker). A variety of different MOFs have been developed and tested for their capture capacity (e.g., how well a particular MOF can capture CO 2 However, there are potentially millions of combinations of metals, linkers, and other functional groups that could be used in a MOF, some of which would yield greater capture capacity and productivity than existing MOFs, and it is not economically feasible to actually create and study every possible combination of ingredients.

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

[0015] The present disclosure addresses these related needs individually and collectively. Summary of the invention

[0016] In one aspect, a functionalized adsorbent is provided. The functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising an aminoorganosilicon group. The adsorbent has an average particle length of ≤3 μm.

[0017] In another aspect, a method for preparing an adsorbent is provided. The method comprises: (I) forming a mixture comprising: an adsorbent precursor; a crystal growth inhibitor; an optional solvent; and an optional non-solvent; and (II) reacting the mixture. The adsorbent has an average particle length of ≤3 μm.

[0018] In another aspect, a method of capturing at least one gas is provided. The method comprises: (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising an amino organosilicon group; and (II) capturing an amount of the at least one gas with the functionalized adsorbent. The adsorbent has an average particle length of ≤3 μm.

[0019] In another aspect, a method of collecting at least one gas is provided. The method comprises: (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising an amino organosilicon group; (II) capturing an amount of the at least one gas with the functionalized adsorbent; and (III) releasing the at least one gas from the functionalized adsorbent. The adsorbent has an average particle length of ≤3 μm. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] These and other features, aspects and advantages of the present disclosure will be better understood when the following detailed description is read with reference to the accompanying drawings, in which like characters refer to like parts throughout the several views, and in which:

[0021] Figure 1 According to the present disclosure, it can be used to capture CO 2 A schematic diagram of an exemplary capture system;

[0022] Figure 2 According to the present disclosure, it can be used to capture CO 2 Schematic diagram of an alternative capture system;

[0023] Figure 3 It shows that according to the present disclosure Figure 2 Exemplary types of moisture adsorption isotherms that a capture system may have;

[0024] Figure 4 According to the present disclosure, Figure 1 and Figure 2 A schematic diagram of an exemplary control system for use with a capture system of

[0025] Figure 5 0.65:0.35) or the second amine hybrid (Hybrid Compound 2, spermine:AEAM=0.32:0.46) functionalized with AEAM, spermidine, the first amine hybrid (Hybrid Compound 1, spermine:AEAM=0.65:0.35) or the second amine hybrid (Hybrid Compound 2, spermine:AEAM=0.32:0.46) measured at 25°C using dynamic vapor sorption (DVS) gravimetric analysis according to the present disclosure is shown. 2 O adsorption capacity;

[0026] Figure 6 0.65:0.35) measured using DVS gravimetric analysis at different temperatures according to the present disclosure. 2 O adsorption capacity varies with H 2 Changes in O partial pressure;

[0027] Figure 7 0.65:0.35) measured using DVS gravimetric analysis at different temperatures according to the present disclosure. 2 Variation of O adsorption capacity with relative humidity;

[0028] Figure 8 : An exemplary potential CO 2 of an adsorbent functionalized with a first amine hybrid (Hybrid Compound 1, spermine:AEAM=0.65:0.35) measured using DVS gravimetric analysis at 40° C. according to the present disclosure is shown. 2 and H 2 Variation of O adsorption capacity with relative humidity;

[0029] Fig. 9 : shows an exemplary potential CO 2 of an adsorbent functionalized with a first amine hybrid (Hybrid Compound 1, spermine:AEAM=0.65:0.35) measured at different temperatures using DVS gravimetric analysis according to the present disclosure. 2 Variation of adsorption capacity with water pressure;

[0030] Fig.10 0.65:0.35) measured using DVS gravimetric analysis at different temperatures according to the present disclosure. 2 Variation of O adsorption capacity with water pressure;

[0031] Fig.11: shows an exemplary potential CO 2 of an adsorbent functionalized with a first amine hybrid (Hybrid Compound 1, spermine:AEAM=0.65:0.35) measured at different temperatures using DVS gravimetric analysis according to the present disclosure. 2 Variation of adsorption capacity with relative humidity;

[0032] Fig. 12A The adsorbent functionalized with the first amine hybrid (Hybrid Compound 1, spermine:AEAM=0.65:0.35) measured using DVS gravimetric analysis at 40°C according to the present disclosure is shown for dry CO 2 and wet CO with a relative humidity of 30% 2 Exemplary potential CO 2 Adsorption isotherms;

[0033] Fig. 12B The use of a single CO according to the present disclosure is shown 2 and H 2 The penetration test apparatus of the O sensor measured the adsorbent functionalized with hybrid compound 3 (spermine:AEAM=0.69:0.23) against CO at 25 °C and 400 ppmv 2 Dry CO at concentration 2 and wet CO with different relative humidity 2 Exemplary CO 2 Adsorption and H 2 O isotherm;

[0034] Fig.13 is a flow chart of an exemplary method according to the present disclosure;

[0035] Fig.14 An exemplary PCC modeling system according to the present disclosure is shown, which can be used to predict the performance of a particular MOF in capturing carbon dioxide (CO2) from the exhaust gas of a coal-fired power plant. 2 )

[0036] Fig.15 is a graph showing CO 2 for an exemplary adsorbent (e.g., an exemplary MOF) 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. 2 Decrease in adsorption productivity;

[0037] FIG. 16A to FIG. 16C is a flow chart illustrating an exemplary method for analyzing the expected performance of an expected sorbent in a post-combustion carbon capture system according to the present disclosure;

[0038] Fig.17 shows an exemplary correlation matrix according to the present disclosure;

[0039] Fig.18The Mg according to the present disclosure is shown 2 (dobpdc) 1 (IPA) 1.92 1H NMR analysis;

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

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

[0042] Fig.21 Depicted is a powder X-ray diffraction (XRD) spectrum of MOF-274 synthesized according to the present disclosure using 4,4′-biphenol as a crystal growth inhibitor, wherein 4,4′-biphenol: 4 The input molar ratio of dobpdc is indicated by arrows;

[0043] Fig. 22 Depicted are SEM images of exemplary MOF-274 prepared in accordance with the present disclosure without (left) and with 9.24 wt % 4,4′-biphenyl diphenol (right);

[0044] Fig.23 Powder XRD patterns of 2,2′-bipyridine-5,5′-dicarboxylic acid (BPYDC), a crystal growth inhibitor according to the present disclosure, and MOF-274 synthesized using BPYDC are depicted, with BPYDC:H shown above each line. 4 input molar ratio of dobpdc;

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

[0046] Fig.25 Powder XRD patterns of 2,2′-bipyridine-5,5′-dimethanol (BPYDM), a crystal growth inhibitor according to the present disclosure, and MOF-274 synthesized using BPYDM are depicted, with BPYDM:H shown above each line. 4 input molar ratio of dobpdc;

[0047] Fig.26Depicted are SEM images of exemplary MOF-274 prepared according to the present disclosure using BPYDM as a crystal growth inhibitor (1.17 wt%, 3.43 wt%, and 6.80 wt% incorporation levels):

[0048] Fig. 27 depicts the chemical structures of spermine and exemplary aminosilicones according to the present disclosure;

[0049] Fig.28 Depicted is a SEM image of a comparative example (Comparative-3) of an adsorbent (GE115-A259) using MOF-274 (ID#: A21) synthesized according to conventional procedures:

[0050] Fig.29 depicts an SEM image of an inventive embodiment of an adsorbent (GE115-A272) (Invention-4) comprising mortar and ground MOF-274 (ID#A21) according to the present disclosure;

[0051] Fig.30 depicts an SEM image of an inventive embodiment of an adsorbent (GE115-A279)) (Invention-5) comprising mechanically ground MOF-274 according to the present disclosure;

[0052] Fig.31 is a graph depicting the results of a penetration test apparatus according to the present disclosure at 25°C, 50% RH and 400 ppmvCO 2 The CO of adsorbents including pure spermine, pure APAP and mixtures of different ratios was measured under the conditions of 2 Variation of absorption with spermine loading;

[0053] Fig.32 is a graph depicting the DVS gravimetric method at 120°C and 100 mBar CO according to the present disclosure. 2 CO 2 partial pressures of adsorbents including pure spermine, pure APAP, and mixtures of different ratios 2 Variation of absorption with spermine loading;

[0054] Fig.33 is a graph depicting CO2 absorption of adsorbents including pure spermine, pure APAP, and mixtures at different ratios according to the present disclosure. 2 Variation of adsorption working capacity with spermine loading.

[0055] Fig.34 is a flow chart of an exemplary method according to the present disclosure;

[0056] Fig.35 is a flow chart of an exemplary method according to the present disclosure;

[0057] Fig.36is a flow chart of an exemplary method according to the present disclosure; and

[0058] Fig.37 is a flow chart of an exemplary method according to the present disclosure;

[0059] Unless otherwise indicated, the drawings provided herein are intended to illustrate features of the embodiments of the present disclosure. It is believed that these features are applicable to a variety of systems including one or more embodiments of the present disclosure. Therefore, the drawings are not intended to include all conventional features required for practicing the embodiments disclosed herein known to those of ordinary skill in the art. DETAILED DESCRIPTION

[0060] The embodiments of the present disclosure may 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. Therefore, the following embodiments are to be interpreted as illustrative only and do not limit the present disclosure in any manner.

[0061] Carbon dioxide capture system using functionalized adsorbents and water management

[0062] In one aspect, a capture system for capturing carbon dioxide is provided. The capture system includes an adsorption bed, the adsorption bed comprising 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 in the gas stream through the functionalized adsorbent, and discharge an exhaust stream. The capture system also includes: a contactor for dynamically controlling a temperature and a relative humidity of the at least one adsorption module; and a controller configured to adjust the temperature and the relative humidity based on the functionalized adsorbent to facilitate increasing the amount of carbon dioxide captured by the adsorption bed.

[0063] Embodiments described herein relate to systems that use functionalized chemical adsorbents in the presence of water to facilitate optimized adsorption and desorption of carbon dioxide by adsorbent beds. Advantages of the systems described herein include at least: (i) improved efficiency and performance of carbon dioxide adsorption and desorption due to the use of temperature variations of the adsorbent beds; (ii) improved efficiency and performance of carbon dioxide adsorption and desorption due to the use of functionalized adsorbents within the adsorbent beds; (iii) improved efficiency and performance of carbon dioxide adsorption and desorption due to the use of variations in relative humidity of water within the adsorbent beds; and (iv) improved performance of the capture system due to the regulation of temperature and relative humidity of water within one or more adsorption modules within the adsorbent beds based on the functionalized adsorbents within the one or more adsorption modules.

[0064] Figure 1 can be used to capture CO using adsorption bed 102 2Schematic diagram of an exemplary capture system 100 of FIG. 1 . In the exemplary embodiment, the adsorption bed 102 includes at least one adsorption module 104. More specifically, in the exemplary embodiment, the adsorption bed 102 includes four adsorption modules 104a-d. In some embodiments, the capture system 100 may include more or less than four adsorption modules 104. Furthermore, in the exemplary embodiment, the adsorption bed 102 includes an inlet 106 and an outlet 108. The inlet 106 and the outlet 108 are oriented such that during operation, a gas stream 110 received through the inlet 106 is directed to flow through each adsorption module 104 in series toward the outlet 108. As the gas stream 110 is directed through each adsorption module 104, the adsorption bed 102 captures CO from the gas stream 110. 2 , and the exhaust gas flow 112 is discharged through the outlet 108 .

[0065] Adsorption module 104 may include a solid adsorbent to preferentially capture specific components of gas stream 110, such as CO 2 and H 2 In an exemplary embodiment, the adsorption module 104 includes a functionalized adsorbent 114, which includes an adsorbent and a functionalized ligand, the functionalized ligand including at least one amine group, such as but not limited to an amino silicone group, to promote the increase of CO 2 Capture capacity and productivity. Generally, the functionalized adsorbent 114 can be in any form known in the art to facilitate the systems described herein. For example, the functionalized adsorbent 114 can be in the form of a powder, a composite mixed with a binder, a film or coating, a packed bed, and / or a column.

[0066] In this exemplary embodiment, after being received by the inlet 106, the gas stream 110 is directed through the first module 104a of the adsorption modules 104. Each adsorption module 104 includes a functionalized adsorbent 114 to adsorb CO contained in the gas stream 110. 2 In some embodiments, the functionalized adsorbent 114 of each adsorption module 104 can be the same. In other embodiments, the functionalized adsorbent 114 within at least one adsorption module 104 can be different.

[0067] Generally, gas stream 110 can be any suitable gas known in the art to facilitate the systems described herein. For example, gas stream 110 can be air, flue gas, post-combustion gas, natural gas, and / or combinations thereof. In this exemplary embodiment, gas stream 110 includes CO 2 and H 2 In some embodiments, CO 2 can be present in the gas stream 110 in the range of about 1 v% to about 10 v%. In other embodiments, CO 2The CO may be present in the gas stream 110 in an amount less than 1% by volume, such as about or less than 300 ppm to 500 ppm by volume. 2 The H may be present in gas stream 110 in an amount greater than 10 v%. In some embodiments, H 2 O may be present in the gas stream 110 in the range of about 0.01 v% to about 20 v%. In other embodiments, H 2 O may be present in the air stream 110 in an amount less than 7 v% such as about 2 v% to 7 v% in the air during hot and humid summer months, or less than 2 v% in the air during cold winter months. In other embodiments, H 2 O may be present in the gas stream 110 in an amount greater than 5 v%., such as in post-combustion gases.

[0068] In this exemplary embodiment, when gas stream 110 enters inlet 106, CO 2 The concentration is usually highest. 2 When adsorbed by the functionalized adsorbent 114 of each subsequent adsorption module 104, the CO in the gas stream 110 2 The concentration of CO decreases as the gas stream 110 is directed through the adsorption modules 104a-d toward the outlet 108. In this exemplary embodiment, during a given adsorption cycle, the CO in the gas stream 110 flowing through the adsorption modules 104a-d is 2 The concentration is lowest at outlet 108 .

[0069] In this exemplary embodiment, the capture system 100 also includes a controller 116 that dynamically adjusts the operation of the capture system 100. For example, as further described herein, the controller 116 may dynamically adjust the operation of the capture system 100 by changing the temperature of one or more adsorption modules 104 and / or changing the H within one or more adsorption modules 104. 2 O content to promote maximum CO 2 of capture.

[0070] The controller 116 regulates the operating conditions of the capture system 100 by dynamically adjusting the temperature of each adsorption module 104a-d. In this exemplary embodiment, the adsorption module 104 includes a contactor 118. The contactor 118 includes a contactor inlet 120 and a contactor outlet 121. In this exemplary embodiment, the first stream 122 received through the contactor inlet 118 regulates the temperature of the adsorption module 104 by 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 may include a fluid circuit (not shown) defined between the contactor inlet 120 and the contactor outlet 121 and extending from the contactor inlet 120 to the contactor outlet 121, so that indirect heat transfer occurs between the first stream 122 flowing in the fluid circuit (not shown) and the functionalized adsorbent 114 in the adsorption module 104. In addition, for example, the contactor 118 may be in direct flow communication with the adsorption module 104, wherein direct heat transfer occurs between the first stream 122 and the functionalized adsorbent 114 in the adsorption module 104. In some embodiments, the contactors 118 of one or more adsorption modules 104a - d may be coupled in series and / or in parallel.

[0071] The controller 116 may adjust the temperature of one or more adsorption modules 104 while monitoring the conditioned temperature T of the first stream 122. reg 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 within one or more adsorption modules 104 helps control the temperature of the functionalized adsorbent 114. The controller 116 may use a contactor sensor 130 ( Figure 4 ) monitors the regulated temperature T of the first flow 122 reg In addition, the controller 116 may use the module sensor 134 ( Figure 4 ) monitors the control temperature T of at least one adsorption module 104 cntl In which the control temperature T of at least one adsorption module 104 cntl Under operating conditions below a desired value, the controller 124 may selectively increase the regulated temperature T of the first stream 122. reg , thereby increasing the temperature of at least one adsorption module 104. Alternatively, in which the control temperature T of at least one adsorption module 104 cntl Under operating conditions higher than the desired value, the controller 124 may selectively reduce the regulated temperature T of the first stream 122. reg , thereby reducing the temperature of at least one adsorption module 104.

[0072] Typically, the regulated temperature T of the first stream 122 is regand thus the temperature of the adsorption module 104 may be as known in the art to facilitate CO capture by the system described herein. 2 In some embodiments, the regulated temperature T of the first stream 122 is reg The adjusted temperature T of the first stream 122 may be in the range of about 0°C to about 150°C. reg The conditioned temperature T of the first stream 122 may be in the range of about 60° C. to about 250° C. In an exemplary embodiment, the conditioned temperature T of the first stream 122 is monitored within each adsorption module 104a-d. reg In some embodiments, the regulated temperature T of the first stream 122 is reg The adjusted temperature T of the first stream 122 may be substantially the same in each adsorption module 104. reg This may vary among the different adsorption modules 104a-d.

[0073] Additionally, the controller 116 may vary the conditioning temperature T of the first stream 122 within any of the adsorption modules 104a-d. reg For example, one or more adsorption modules 104a-d may include more than one module sensor 134 ( Figure 4 ). Thus, the controller 116 may generate a temperature profile that includes an adjusted temperature T of the first stream 122 within any or all of the adsorption modules 104a-d. reg In some embodiments, the adjustment temperature T of the first stream 122 is reg The change in value of can form a gradient temperature distribution in any or all adsorption modules 104a-d. In other embodiments, the adjustment temperature T of the first stream 122 is reg Varying values ​​of may create discrete temperature profiles within any or all of the adsorption modules 104a-d.

[0074] Figure 2 can be used to capture CO using adsorption bed 102 2 Schematic diagram of an exemplary capture system 200. Figure 2 The implementation shown in is similar to Figure 1 The embodiments shown in , with the differences noted herein, therefore, Figure 2 The reference numerals used in Figure 1 The controller 116 adjusts the H in each adsorption module 104a-d. 2 O content to dynamically adjust H 2O relative humidity, thereby helping to adjust the operating conditions of the capture system 200. In this exemplary embodiment, the adsorption module 104 includes an ejector 202, which includes an ejector inlet 204. The second stream 206 received through the ejector inlet 204 helps to adjust the H within the adsorption module 104. 2 O content to adjust H 2 In this exemplary embodiment, the second stream 206 includes H 2 O. The second stream 206 may include H in liquid form (e.g., water) or in gaseous form (e.g., water vapor). 2 O. In some embodiments, H 2 O may be present in the second stream 206 in the range of about 0.1 v% to about 20 v%. In other embodiments, H 2 O may be present in the second stream 206 in the range of about 4 v% to about 15 v%. In other embodiments, H 2 O may be present in the second stream 206 in a range of about 0.5 v% to about 4 v%, such as typically occurs in ambient air.

[0075] The controller 116 may adjust the H in one or more adsorption modules 104 by adjusting the flow rate of the second stream 206 entering the one or more adsorption modules 104. 2 O content. For example, the controller 116 may use the module sensor 134 ( Figure 4 (shown) monitors the H of the adsorption module 104 2 O concentration C relative humidity level. 2 O concentration C H 2 Under operating conditions where the relative humidity level is below a desired level in at least one adsorption module 104, the controller 116 may selectively increase the flow rate of the second stream 206 to transfer additional H 2 O is injected into the at least one adsorption module 104. 2 When the relative humidity level is higher than the desired level in the at least one adsorption module 104, the controller 116 can selectively reduce the flow rate of the second stream 206, thereby reducing the additional H injected into the at least one adsorption module 104. 2 In another embodiment, at the beginning of the adsorption cycle, the controller 116 can selectively increase the flow rate of the second stream 206 to add additional H 2 O is injected into the at least one adsorption module 104 to increase the relative humidity to above the desired relative humidity level, thereby allowing rapid H 2 O adsorption. Then, at a later stage of the adsorption cycle, the controller 116 may selectively reduce or stop the flow of the second stream 206 to reduce the relative humidity level of the at least one adsorption module 104.

[0076] The controller 116 may also monitor the regulated temperature T of the first stream 122 of one or more absorption modules 104. reg To adjust the H in one or more adsorption modules 104 2 O relative humidity. 2 Under operating conditions where the relative humidity level is higher than the desired level in at least one adsorption module 104, the controller 116 may selectively increase the conditioned temperature T of the first stream 122. reg , thereby increasing the temperature of at least one adsorption module 104, and due to the increase in saturated vapor pressure at an increased temperature, H 2 O relative humidity decreases. 2 Under operating conditions where the relative humidity is lower than a desired value in at least one adsorption module 104, the controller 116 may selectively reduce the conditioned temperature T of the first stream 122. reg , thereby reducing the temperature of at least one adsorption module 104 and causing H 2 The relative humidity increases. The regulated temperature T of the first flow 122 reg Any of the systems described herein may be used for raising or lowering.

[0077] The controller 116 regulates the operating conditions of the capture system 200 to promote optimal CO 2 removal by maintaining the relative humidity of each adsorption module 104a-d. 2 The relative humidity of each adsorption module 104a-d can be based on the regulated temperature T of the first stream 122. reg and H of the adsorption module 104 2 O concentration C. In this exemplary embodiment, the controller 116 adjusts the H concentration of the functionalized adsorbent 114 in the adsorption module 104 based on the H 2 O adsorption isotherm to adjust the adjustment temperature T of the first flow 122 reg and H of the adsorption module 104 2 O concentration C, to promote the passage of H 2 O monolayer adsorption to optimize CO 2 adsorption and desorption.

[0078] In general, the capture system 200 may have features that facilitate the capture of CO by the system described herein. 2 There are six types of water adsorption isotherms defined by IUPAC, and their shapes depend on relative humidity and temperature ( Figure 3 Of the six types, Type II, Type IV, and Type VI each show a flat region (e.g., a “turning point”) until an inflection point, typically corresponding to monolayer coverage and H 2 O adsorption ( Figure 3In this exemplary embodiment, the controller 116 adjusts the operating conditions of the capture system 200 to achieve a monolayer coverage of the functionalized adsorbent 114 and H 2 O adsorption, thereby promoting the optimization of CO 2 For example, the capture system 200 may have a Type II, Type IV, or Type VI adsorption isotherm ( Figure 3 ), which is particularly useful for ensuring single layer coverage and H 2 O adsorption, thereby increasing the CO 2 Adsorption capacity.

[0079] In addition to being dependent on relative humidity and temperature, the adsorption isotherm also depends on the adsorbent material. In many embodiments, the functionalized adsorbent 114 can be a material that facilitates the capture of CO by the systems described herein. 2 In an exemplary embodiment, the functionalized adsorbent 114 includes an adsorbent and at least one functionalized ligand, the at least one functionalized ligand comprising an amino organosilicon group to optimize the relative H 2 O adsorption of CO 2 Capture capacity and production rate.

[0080] In general, the 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 specific embodiment disclosed herein.

[0081] In some embodiments, the functionalized adsorbent includes a first type of functionalized ligand, wherein the first type of functionalized ligand includes at least one functionalized ligand comprising an aminoorganosilicon group. Generally, the at least one functionalized ligand comprising an aminoorganosilicon group can include any such suitable ligand that promotes the functionalized adsorbent described herein. The at least one functionalized ligand comprising an aminoorganosilicon group can include only one functionalized ligand comprising an aminoorganosilicon group, or include two or more functionalized ligands each comprising an aminoorganosilicon group.

[0082] Generally, the adsorbent can be any suitable adsorbent known in the art to promote the functionalized adsorbent described herein. In some embodiments, the adsorbent is selected from the group consisting of coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCP), covalent organic framework (COF) compounds, zeolitic imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open frameworks, network chemistry, silica particles, zeolites, silicon-aluminum-phosphates (SAPO), aluminum-phosphates (AlPO), polyaromatic frameworks (PAF), activated carbon, molecular organic solids, and combinations thereof.

[0083] As used herein, MOF compounds are compounds that include metal ions or clusters coordinated with organic ligands to form one-dimensional, two-dimensional or three-dimensional structures. The metal ions or clusters act as connectors and are bound by multi-directional organic ligands, which act as connectors in the network structure. MOF compounds have modular properties that allow synthetic tunability, which provide fine chemicals and structural control. Properties such as porosity, stability, particle morphology and conductivity can be customized for specific applications.

[0084] In many embodiments, the adsorbent is a MOF compound including a MOF metal or a metal-containing cluster and a MOF linker.

[0085] In some embodiments, the MOF metal can be any suitable MOF metal known in the art to promote the functionalized adsorbents described herein. In other embodiments, the MOF metal is a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, their ions, their hydrates, their salts, their halides, their fluorides, their chlorides, their bromides, their iodides, their nitrates, their acetates, their sulfates, their phosphates, their carbonates, their oxides, their formates, their carboxylates, and combinations thereof. In some embodiments, the MOF metal includes Mg.

[0086] In some embodiments, the MOF metal-containing cluster can be any suitable MOF metal-containing cluster known in the art to promote the functionalized adsorbent described herein. In some embodiments, the MOF metal-containing cluster includes a MOF metal node and a linker pillar, wherein the MOF metal and the linker are each defined as described herein. In other embodiments, the MOF metal-containing cluster includes a MOF metal-oxygen cluster.

[0087] In some embodiments, the MOF linker can be any suitable MOF linker known in the art to facilitate the functionalized adsorbents described herein. Generally, the geometry and connectivity of the linker contribute to the structure of the resulting MOF compound. Adjusting the linker geometry, length, ratio, and functional groups can adjust the size, shape, and internal surface properties of the MOF compound for targeted applications.

[0088] In at least some embodiments, the MOF linker is a linker selected from the group consisting of a polytopic linker, a dihedral linker, a trihedral linker, a tetrahedral linker, a pentahedral linker, a hexahedral linker, a heptahedral linker, an octahedral linker, a mixed linker, an asymmetric linker, a metal linker, an N-heterocyclic linker, and combinations thereof.

[0089] In at least some embodiments, the MOF linker is a linker selected from the group consisting of: a polyhedral linker, 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H 4 dobpdc), 4,4′-dioxybiphenyl-3,3′-dicarboxylate (dobpdc 4 -), 4,4"-dioxo-[1,1':4',1"-terphenyl]-3,3"-dicarboxylate (dotpdc 4 -), 2,5-dioxybenzene-1,4-dicarboxylate (dobdc 4 -), 4,6-dihydroxyisophthalic acid (m-dobdc 4 -), 3,3′-dioxo-biphenyl-4,4′-dicarboxylate (p-carboxylate-dobpdc 4 -), 4,4′-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H 4 ODA), 4,4′-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H 4 TDA), 4,4′-dihydroxyazobenzene-3,3′-dicarboxylic acid (H 4 OSA), their protonated, partially and completely deprotonated forms, and combinations thereof. As another example, in at least some embodiments, the MOF linker is a linker selected from the group consisting of dicarboxylates (e.g., terephthalic acid), tricarboxylates (e.g., 1,3,5-benzenetricarboxylic acid), azolates, tetrazoles, and combinations thereof.

[0090] As another example, in at least some embodiments, the MOF linker is a dicarboxylic acid linker selected from the group consisting of 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylene dicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, terephthalic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline quinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, flower-3,9-dicarboxylic acid, flower dicarboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquine 1,4-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,8-naphthalene-1,2-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2′-biquinoline-4,4′-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenonedicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diaminodiphenyl ether imide dicarboxylic acid, 4,4'-diaminodiphenylmethane imide dicarboxylic acid, 4,4'-diaminodiphenyl sulfone imide dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 8-methoxy-2,3-naphthalene dicarboxylic acid, 8-nitro-2,3-naphthalene dicarboxylic acid, 8-sulfo-2,3-naphthalene dicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2′-3′-diphenyl-4,4"-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromic acid 1,3-benzenedicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, trihexadecanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4′-dihydroxy Diphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorescein ring-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-phthalic acid, 2,6-pyridinedicarboxylic acid Acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid and combinations thereof.

[0091] 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.

[0092] As another example, in at least some embodiments, the MOF linker is a tetracarboxylic acid linker selected from the group consisting of 1,1-dioxide-pyrene[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, pyrene-3,4,9,10-tetracarboxylic acid, pyrene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7, 10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid and combinations thereof.

[0093] In this exemplary embodiment, the MOF linker is 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H 4 dobpdc) and / or 4,4′-dioxybiphenyl-3,3′-dicarboxylate (dobpdc 4 In some embodiments, dobpdc includes 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid, its monocarboxylate form, its dicarboxylate form, its monophenolate form, its diphenolate form, and combinations thereof.

[0094] In some embodiments, the MOF linker is one or more of the following linkers:

[0095]

[0096]

[0097]

[0098] 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 Mg 2 (dobpdc).

[0099] In some embodiments, the functionalized adsorbent is a functionalized MOF compound of formula (AI)

[0100]

[0101] in:

[0102] M is the MOF metal or metal-containing cluster;

[0103] L is a MOF linker;

[0104] F A is at least one functionalized ligand comprising an amino organosilicon group;

[0105] F B is at least one functionalized ligand that does not contain an amino organosilicon group;

[0106] x is a value in the range of 1 to 6;

[0107] y is a value in the range of 1 to 6;

[0108] a is a value greater than 0 and less than or equal to 2; and

[0109] b is a value in the range of 0 to 2.

[0110] In some embodiments, the functionalized adsorbent includes a second type of functionalized ligand, wherein the second type of functionalized ligand includes at least one functionalized ligand that does not contain an aminoorganosilicon group. In some embodiments, the functionalized adsorbent also includes at least one functionalized ligand that does not contain an aminoorganosilicon group. Generally, the at least one functionalized ligand that does not contain an aminoorganosilicon group can include any such suitable ligand that promotes the functionalized adsorbent described herein. The at least one functionalized ligand that does not contain an aminoorganosilicon group can include only one functionalized ligand that does not contain an aminoorganosilicon group, or include two or more functionalized ligands that each do not contain an aminoorganosilicon group.

[0111] In some embodiments, the at least one functionalized ligand that does not contain an amino silicone group is selected from the group consisting of: amine ligands, monoamine ligands, diamine ligands, triamine ligands, tetraamine ligands, pentamine ligands, hexamine ligands, polyamine ligands, alkylamine ligands, and amino alcohol ligands. Exemplary ligands include, but are not limited to, ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, di(N-methyl)ethylenediamine, N-isopropylethylenediamine, N,N-dimethyl-N-methylethylenediamine, di(N,N-dimethyl)ethylenediamine, N,N-diisopropylethylenediamine, 2,2-dimethyl-1,3-diaminopropane, 1,3-diaminopentane, diethylenetriamine, N-(2-aminoethyl) -1,3-propylenediamine, bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane (spermidine), triethylenetetramine, N,N′-bis(2-aminoethyl)-1,3-propylenediamine, 1,2-bis(3-aminopropylamino)ethane, N,N′-bis(3-aminopropyl)-1,3-propylenediamine, N,N′-bis(3-aminopropyl)-1,4-diaminobutane (spermidine), tetraethylenepentamine and / or combinations thereof.

[0112] Typically, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group may be present in any suitable ratio known in the art to promote the functionalized adsorbent described herein. In some embodiments, the ratio is selected from the group consisting of a molar ratio, a weight ratio, and a volume ratio. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 10:1 to about 1:10. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 9:1 to about 1:9. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 8:1 to about 1:8. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 7:1 to about 1:7. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 6:1 to about 1:6. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 5:1 to about 1:5. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 4:1 to about 1:4. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 3:1 to about 1:3. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio ranging from about 2: 1 to about 1: 2. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group and the at least one functionalized ligand not comprising an aminoorganosilicon group are present in a ratio of about 1: 1.

[0113] In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group is present in an amount less than the at least one functionalized ligand not comprising an aminoorganosilicon group.

[0114] 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.

[0115] In many embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group can be any suitable at least one functionalized ligand comprising an aminoorganosilicon group known in the art to promote the functionalized adsorbents described herein.

[0116] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group comprises at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof. In some embodiments, the at least one functionalized ligand comprising an aminosilicone group comprises at least one primary amine or at least one secondary amine.

[0117] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentamines, hexamines, polyamines, and combinations thereof.

[0118] 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.

[0119] In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group comprises a symmetrical structure. In some embodiments, the at least one functionalized ligand comprising an aminoorganosilicon group comprises an asymmetrical structure.

[0120] In some embodiments, when the at least one functionalized ligand comprising an aminoorganosilicon group comprises a disiloxane group, the at least one functionalized ligand comprising an aminoorganosilicon group comprises the same amine on both sides of the disiloxane group. In some embodiments, when the at least one functionalized ligand comprising an aminoorganosilicon group comprises a disiloxane group, the at least one functionalized ligand comprising an aminoorganosilicon group comprises different amines on either side of the disiloxane group.

[0121] 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).

[0122]

[0123]

[0124] in:

[0125] R 1 , R 2 , R 3 , R 4 , R 9 , R 10 , R 13 , R 14 and R 18 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0126] R 5 , R 6 , R 11 , R 15 and R 17 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 alkyl,

[0127] R 7 , R 8 , R 12 and R 16 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl group, and a substituent of formula (A-VIII)

[0128]

[0129] in:

[0130] The wavy bond indicates the bonding position to formula (A-II) or formula (A-III) or formula (A-IV) or formula (AV) or formula (A-VI) or formula (A-VII);

[0131] R 19 , R 20 , R 21 , R 22 , R 23 and R 24 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C 1 -C 6 Straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0132] R 25 and R 26 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl and substituted or unsubstituted C 4 -C 6Cycloalkyl, or when taken together, R 25 and R 26 forming a monocyclic ring selected from the group consisting of heterocycloalkyl and heteroaryl;

[0133] R 27 , R 28 and R 29 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, ether, -OCH 2 CH 2 -、-OCH 2 CH 2 CH 2 -、-OCH 2 CH 2 CH 2 CH 2 -、-NHCH 2 CH 2 -、-NHCH 2 CH 2 CH 2 - and -NHCH 2 CH 2 CH 2 CH 2 -;

[0134] R 30 Selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 4 -C 6 Cycloalkyl, heterocycloalkyl, and heteroaryl;

[0135] j is an integer ranging from 0 to 20;

[0136] k is an integer ranging from 0 to 20;

[0137] m is an integer in the range of 0 to 20; and

[0138] n is an integer ranging from 0 to 20.

[0139] In some embodiments, the at least one functionalized ligand comprising an aminosilicone group is selected from the group consisting of:

[0140]

[0141]

[0142]

[0143]

[0144]

[0145] as well as

[0146]

[0147] Figure 4 is a schematic diagram of an exemplary control system 400 that may be used to capture CO using a capture system. 2 , such as capture system 100 ( Figure 1 ) and / or capture system 200 ( Figure 2 4. In the exemplary embodiment, the controller 116 includes a memory 402 and a processor 404. The controller 116 may be configured to control the temperature of the first stream 122 based on data received from the contactor sensor 130 by the control system 400, such as, but not limited to, the regulated temperature T of the first stream 122. reg , to adjust the temperature of one or more adsorption modules 104a-d. The controller 116 may adjust the temperature of one or more adsorption modules 104a-d based on a comparison with data stored in the memory 402, such as the adjustment temperature T reg desired range, instructions stored in memory 402 and / or data analyzed by processor 404.

[0148] Additionally, the controller 116 may control the temperature T within one or more of the adsorption modules 104a-d based on data received by the control system 400 from the module sensors 134, such as, but not limited to, the control temperature T cntl and / or H 2O relative humidity to adjust the temperature of one or more adsorption modules 104a-d. The controller 116 may adjust the temperature of one or more adsorption modules 104a-d based on a comparison with data stored in the memory 402, such as the control temperature T cnt1 and / or H 2 O desired range of relative humidity, instructions stored in memory 402 and / or data analyzed by processor 404.

[0149] Described herein is an exemplary system for using functionalized chemical adsorbents in the presence of water to facilitate optimization of the adsorption and desorption of carbon dioxide by an adsorbent bed. The exemplary system as described herein provides several advantages over conventional designs and methods, including at least: improved efficiency and performance of carbon dioxide adsorption and desorption due to the use of temperature variation of the adsorbent bed; improved efficiency and performance of carbon dioxide adsorption and desorption due to the use of functionalized adsorbents within the adsorbent bed; improved efficiency and performance of carbon dioxide adsorption and desorption due to the use of water relative humidity variation within the adsorbent bed; and improved performance of the capture system due to adjusting the temperature and water relative humidity within one or more adsorption modules within the adsorbent bed based on the functionalized adsorbent within the one or more adsorption modules.

[0150] Further aspects of the invention are provided by the subject matter of the following clauses:

[0151] 1. A capture system for capturing carbon dioxide, the capture system comprising: an adsorption bed, the adsorption bed comprising 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 through the functionalized adsorbent; and discharge an exhaust stream; a contactor, the contactor being used to dynamically control the temperature and relative humidity of the at least one adsorption module; and a controller, the controller being configured to adjust the temperature and the relative humidity based on the functionalized adsorbent to facilitate increasing the amount of carbon dioxide captured by the adsorption bed.

[0152] 2. The capture system according to any of the preceding clauses, wherein the contactor is oriented to receive a conditioning fluid for dynamically controlling the temperature of the at least one adsorption module.

[0153] 3. The capture system according to any of the preceding clauses, further comprising at least one ejector oriented to discharge a water stream to control the water relative humidity of the at least one adsorption module.

[0154] 4. The capture system of any of the preceding clauses, wherein the controller is further configured to reduce the fluid temperature of the conditioning fluid received by the contactor to facilitate increasing the water relative humidity.

[0155] 5. The capture system according to any of the preceding clauses, 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 adsorption bed.

[0156] 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 facilitate increasing the amount of carbon dioxide adsorbed by the functionalized adsorbent.

[0157] 7. The capture system of any of the preceding clauses, wherein the controller is further configured to increase the pressure of the water stream discharged from the ejector to facilitate increasing the water relative humidity of the at least one adsorption module.

[0158] 8. The capture system according to 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 a moisture adsorption isotherm of the functionalized adsorbent.

[0159] 9. The capture system according to any of the preceding clauses, wherein the temperature and water relative humidity of the at least one adsorption module are based on the relative humidity at the inflection point of the water adsorption isotherm of the functionalized adsorbent.

[0160] 10. The capture system according to any of the preceding clauses, wherein the at least one adsorption module comprises a plurality of adsorption modules coupled in a series flow arrangement.

[0161] 11. The capture system of any of the preceding clauses, wherein the at least one ejector comprises an ejector coupled to each of the plurality of adsorption modules.

[0162] 12. The capture system according to any of the preceding clauses, wherein the controller is further configured to adjust the temperature and water relative humidity of each of the plurality of adsorption modules.

[0163] 13. The capture system according to any of the preceding clauses, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising an amine group.

[0164] 14. The 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.

[0165] 15. The 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, pentamines, hexamines, polyamines, and combinations thereof.

[0166] 16. The capture system according to any of the preceding clauses, wherein the functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising aminoorganosilicon groups.

[0167] 17. The capture system according to any one of the preceding clauses, wherein the functionalized adsorbent is a functionalized MOF compound of formula (AI)

[0168]

[0169] in:

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

[0171] L is a MOF linker;

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

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

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

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

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

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

[0178] 18. A capture system according to 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, their ions, their hydrates, their salts, their halides, their fluorides, their chlorides, their bromides, their iodides, their nitrates, their acetates, their sulfates, their phosphates, their carbonates, their oxides, their formates, their carboxylates and combinations thereof.

[0179] 19. The capture system according to any of the preceding clauses, wherein the MOF linker comprises at least one or more linkers selected from the group consisting of: a polyhedral linker, 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H 4 dobpdc), 4,4′-dioxybiphenyl-3,3′-dicarboxylate (dobpdc 4 -), 4,4"-dioxo-[1,1':4',1"-terphenyl]-3,3"-dicarboxylate (dotpdc 4 -), 2,5-dioxybenzene-1,4-dicarboxylate (dobdc 4- )、4,6-dihydroxyisophthalic acid (m-dobdc 4 -), 3,3′-dioxo-biphenyl-4,4′-dicarboxylate (p-carboxylate-DOBPDC 4- ), 4,4′-[oxalylbis(imino)]bis(2-hydroxybenzoic acid)(H 4 ODA), 4,4′-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H 4 TDA), 4,4′-dihydroxyazobenzene-3,3′-dicarboxylic acid (H 4OSA), dicarboxylates, terephthalic acid, tricarboxylates, 1,3,5-benzenetricarboxylic acid, nitrogen azoles, tetrazoles, 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, terephthalic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline -3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, floret-3,9-dicarboxylic acid, floret dicarboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquine 1,4-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2′-biquinoline-4,4′-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenonedicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E 400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diaminodiphenyl ether imide dicarboxylic acid, 4,4'-diaminodiphenylmethane imide dicarboxylic acid, 4,4'-diaminodiphenyl sulfone imide dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 8-methoxy-2,3-naphthalene dicarboxylic acid, 8-nitro-2,3-naphthalene dicarboxylic acid, 8-sulfo-2,3-naphthalene dicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2′-3′-diphenyl-4,4″-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4 (1H)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, trihexadecanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosene dicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorescein ring-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-phthalic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4 -dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1 , 2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurinetricarboxylic acid, 1,1-dioxide-pyrene [1,12-BCD] thiophene-3,4,9,10-tetracarboxylic acid, pyrene tetracarboxylic acid, pyrene-3,4,9,10-tetracarboxylic acid, pyrene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, meso-1,2,3,4-butane tetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzene tetracarboxylic acid Acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, polyhedral linkers, dihedral linkers, trihedral linkers, tetrahedral linkers, pentahedral linkers, hexahedral linkers, heptahedral linkers, octahedral linkers, mixed linkers, asymmetric linkers, metal linkers, N-heterocyclic linkers, their protonated, partially or completely deprotonated forms, and combinations thereof.

[0180] 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.

[0181] Synthesis of Aminoalkyl Substituted Disiloxanes .

[0182] In one aspect, a method for preparing an aminoalkyl-substituted disiloxane is provided. The method comprises: I) forming a mixture comprising: a diamine or polyamine containing at least one primary amine group; and a silane; II) reacting the mixture in a first reaction; III) adding a hydrolyzing agent to the mixture; and IV) reacting the mixture in a second reaction to form an aminoalkyl-substituted disiloxane.

[0183] In another aspect, an aminoalkyl-substituted disiloxane of formula (BI) is provided. The formula is:

[0184]

[0185] in:

[0186] R 12 , R 13 , R 14 , R 15 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0187] R 16 and R 17 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 Alkyl; and

[0188] R 18 and R 19 Each independently selected from the substituents of formula (B-IV)

[0189]

[0190] in:

[0191] The wavy bond indicates the bonding position to formula (BI);

[0192] 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 linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C 1 -C 6 Straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0193] R 31 and R 32 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl and substituted or unsubstituted C 4 -C 6 Cycloalkyl, or when taken together, R 31 and R 32forming a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl;

[0194] R 33 , R 34 and R 35 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, ether, -OCH 2 CH 2 -、-OCH 2 CH 2 CH 2 -、-OCH 2 CH 2 CH 2 CH 2 -、-NHCH 2 CH 2 -、-NHCH 2 CH 2 CH 2 - and -NHCH 2 CH 2 CH 2 CH 2 -;

[0195] R 36 Selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 4 -C 6 Cycloalkyl, heterocycloalkyl, and heteroaryl; and

[0196] m is an integer ranging from 0 to 20;

[0197] Provided that the aminoalkyl-substituted disiloxane is not

[0198]

[0199] Embodiments described herein overcome at least some of the disadvantages of known methods for preparing aminoalkyl-substituted disiloxanes and known aminoalkyl-substituted disiloxanes. Exemplary embodiments described herein include methods for preparing aminoalkyl-substituted disiloxanes, wherein the methods include: I) forming a mixture comprising: a diamine or polyamine containing at least one primary amine group; and a silane; II) reacting the mixture in a first reaction; III) adding a hydrolyzing agent to the mixture; and IV) reacting the mixture in a second reaction to form an aminoalkyl-substituted disiloxane. Compared to known methods for preparing aminoalkyl-substituted disiloxanes, exemplary embodiments described herein avoid side reactions and / or produce desired products with higher productivity and purity with fewer steps.

[0200] In many embodiments, the method is a one-pot synthesis. As used herein, a one-pot synthesis is a synthesis performed in a single reaction vessel. There is no need to remove intermediates from the reaction vessel for separation and / or purification. The one-pot synthesis may include one reaction or more than one reaction. The one-pot synthesis is particularly advantageous in reducing reaction complexity and avoiding lengthy and expensive separation and purification.

[0201] In many embodiments, the aminoalkyl-substituted disiloxane is an amino-C 1 -C 6 Alkyl substituted disiloxanes. Compared to other compounds including larger aminoalkyl substituents or alternative substituents, including C 1 -C 6 Embodiments with alkyl groups are thermodynamically more favorable to formation. In some embodiments, the aminoalkyl-substituted disiloxane is an aminomethyl-substituted disiloxane.

[0202] Fig.13 13 is an exemplary process flow diagram 1310. In this exemplary embodiment, process flow diagram 1310 depicts the basic process steps of the exemplary embodiments described herein and is not intended to limit the process embodiments. First, a mixture 1312 is formed, which includes: a diamine or polyamine containing at least one primary amine group; and a silane. The mixture is reacted in a first reaction 1314, and a hydrolyzing agent is added to the mixture 1316. The mixture is then reacted in a second reaction 1318 to form an aminoalkyl-substituted disiloxane.

[0203] 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):

[0204]

[0205] in:

[0206] R 12 , R 13 , R 14 , R 15 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0207] R 16 and R 17 are each independently selected from a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 Alkyl, preferably C 1 -C 6 Straight chain alkyl, even more preferably C 1 alkyl;

[0208] R 18 and R 19 Each independently selected from the substituents of formula (B-IV)

[0209]

[0210] in:

[0211] The wavy bond indicates the bonding position to formula (BI);

[0212] 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 linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C3 -C 6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C 1 -C 6 Straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0213] R 31 and R 32 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl and substituted or unsubstituted C 4 -C 6 Cycloalkyl, or when taken together, R 31 and R 32 forming a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl;

[0214] R 33 , R 34 and R 35 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, ether, -OCH 2 CH 2 -、-OCH 2 CH 2 CH 2 -、-OCH 2 CH 2 CH 2 CH 2 -、-NHCH 2 CH 2-、-NHCH 2 CH 2 CH 2 - and -NHCH 2 CH 2 CH 2 CH 2 -;

[0215] R 36 Selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 4 -C 6 Cycloalkyl, heterocycloalkyl, and heteroaryl; and

[0216] m is an integer in the range of 0 to 20, preferably an integer in the range of 0 to 10, even more preferably an integer in the range of 0 to 3;

[0217] Provided that the aminoalkyl-substituted disiloxane is not

[0218]

[0219] In some embodiments, the aminoalkyl-substituted disiloxane is selected from the group consisting of:

[0220]

[0221] as well as

[0222] In some embodiments, the diamine or polyamine containing at least one primary amine group can be any suitable diamine or polyamine containing at least one primary amine group known in the art to promote the methods described herein. In other embodiments, the diamine or polyamine containing at least one primary amine group is a compound of formula (B-II):

[0223]

[0224] in:

[0225] R 1 , R 2 , R 3, R 4 , R 5 and R 6 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0226] R 7 and R 8 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl and substituted or unsubstituted C 4 -C 6 Cycloalkyl, or when taken together, R 7 and R 8 forming a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl;

[0227] R 9 , R 10 and R 11 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, ether, -OCH 2 CH 2 -、-OCH 2 CH 2 CH 2-、-OCH 2 CH 2 CH 2 CH 2 -、-NHCH 2 CH 2 -、-NHCH 2 CH 2 CH 2 - and -NHCH 2 CH 2 CH 2 CH 2 -;as well as

[0228] n is an integer in the range of 0-20, preferably an integer in the range of 0-10, and even more preferably an integer in the range of 0-3.

[0229] In some embodiments, the silane can be any suitable silane known in the art to facilitate 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):

[0230]

[0231] in:

[0232] R 20 selected from the group consisting of halide, fluoride, chloride, bromide and iodide;

[0233] R 21 and R 22 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0234] R 23 and R 24 are each independently selected from the group consisting of: 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, C6 Alkyl, aryl and phenyl.

[0235] In some embodiments, R 23 and R 24 are each independently selected from the group consisting of: 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, preferably C 1 -C 6 Straight chain alkyl.

[0236] In some embodiments, R 23 It is C 1 alkyl.

[0237] In some embodiments, R 24 It is C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, aryl or phenyl.

[0238] In some embodiments, the silane is In some embodiments, the silane is

[0239] In many embodiments, reacting the mixture in a first reaction 1314 can be performed under any suitable reaction conditions known in the art to facilitate the methods described herein. In some embodiments, reacting the mixture in a first reaction 1314 includes stirring the mixture.

[0240] In many embodiments, the mixture is allowed to react 1314 in the first reaction for any suitable amount of time known in the art to facilitate the methods described herein. In some embodiments, the elapsed time for the mixture to react 1314 in the first reaction is in the range of about 1 second to about 12 hours. In some embodiments, the elapsed time for the mixture to react 1314 in the first reaction is in the range of about 1 second to about 6 hours. In some embodiments, the elapsed time for the mixture to react 1314 in the first reaction is in the range of about 1 second to about 3 hours. In some embodiments, the elapsed time for the mixture to react 1314 in the first reaction is in the range of about 1 hour to about 3 hours. In some embodiments, the elapsed time for the mixture to react 1314 in the first reaction is in the range of about 2 hours to about 3 hours.

[0241] In some embodiments, reacting the mixture 1314 in a first reaction includes adding a silane (e.g., chloromethyldimethylethoxysilane) dropwise to a neat diamine or polyamine containing at least one primary amine group over about 1 hour. The reaction temperature is allowed to rise to about 90° C. due to the reaction exotherm and maintained at that temperature for the duration of the reaction (about 2-3 hours total). During this period, the HCl salt of the amine is formed and may precipitate to varying degrees depending on the amine.

[0242] In some embodiments, the hydrolyzing agent is added dropwise 1316 to the mixture. In some embodiments, the hydrolyzing agent is added to the mixture over a period of time. In some embodiments, the hydrolyzing agent is added to the mixture 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 under exothermic conditions 1316 and allowed to cool to room temperature before the mixture is reacted 1318 in a second reaction.

[0243] In some embodiments, the hydrolyzing agent 1316 is added over 30 minutes and under exothermic conditions before reacting the mixture in a second reaction 1318. In these embodiments, the reaction 1318 is completed before the reaction mixture is cooled to room temperature.

[0244] In many embodiments, the hydrolyzing agent can be any suitable hydrolyzing agent known in the art to facilitate the methods described herein. In some embodiments, the hydrolyzing agent is an aqueous solution. In some embodiments, the hydrolyzing agent is water.

[0245] In many embodiments, reacting the mixture in a second reaction 1318 can be performed under any suitable reaction conditions known in the art to facilitate the methods described herein. In some embodiments, reacting the mixture in a second reaction 1318 includes adjusting the temperature of the mixture. In some embodiments, reacting the mixture in a second reaction 1318 includes cooling the mixture.

[0246] In some embodiments, the aminoalkyl-substituted disiloxane is further extracted from the reaction mixture. In some embodiments, the aminoalkyl-substituted disiloxane is further extracted from the reaction mixture with an organic solvent.

[0247] 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 separated, the aqueous layer is back-extracted with a minimal amount of organic solvent, and the combined organic layers are concentrated under vacuum, triturated once with an organic solvent, and then dried under vacuum.

[0248] In some embodiments, the aminoalkyl-substituted disiloxane is further purified. In some embodiments, the further purification comprises using distillation, vacuum distillation and / or heating. In some embodiments, the further purification comprises using vacuum distillation to remove impurities and by-products. In these embodiments, the remaining material in the distillation tank is a higher purity product relative to the product before purification.

[0249] In many embodiments, the mixture is reacted 1318 in the second reaction for any suitable amount of time known in the art to facilitate the methods described herein. In some embodiments, the elapsed time for the mixture to react 1318 in the second reaction is in the range of about 1 second to about 12 hours. In some embodiments, the elapsed time for the mixture to react 1318 in the second reaction is in the range of about 1 second to about 6 hours. In some embodiments, the elapsed time for the mixture to react 1318 in the second reaction is in the range of about 1 second to about 3 hours. In some embodiments, the elapsed time for the mixture to react 1318 in the second reaction is in the range of about 1 hour to about 3 hours. In some embodiments, the elapsed time for the mixture to react 1318 in the second reaction is in the range of about 2 hours to about 3 hours.

[0250] In many embodiments, the method may also include any other suitable processing steps known in the art that promote the success of the methods described herein. Such processing steps may include, but are not limited to, only washing, drying, filtering, purifying, separating, centrifuging, and any combination thereof. In some embodiments, the method also includes washing the aminoalkyl-substituted disiloxane compound. In some embodiments, the method also includes purifying the aminoalkyl-substituted disiloxane compound. In some embodiments, purification includes using distillation, vacuum distillation, and / or heating. In some embodiments, the method also includes removing volatile reaction byproducts.

[0251] In some embodiments, the method includes: I) forming a mixture comprising: a diamine or polyamine containing at least one primary amine group; and chloromethyldimethylalkoxysilane; II) reacting the mixture in a first reaction by a controlled exothermic nature; III) adding a hydrolyzing agent to the mixture; IV) reacting the mixture in a second reaction to form an aminoalkyl-substituted disiloxane; (V) extracting the aminoalkyl-substituted disiloxane; and (VI) purifying the aminoalkyl-substituted disiloxane.

[0252] In many embodiments, the aminoalkyl-substituted disiloxanes can be used for 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.

[0253] Other aspects of the disclosure are provided by the subject matter of the following clauses:

[0254] 1. A method for preparing an aminoalkyl-substituted disiloxane, the method comprising: I) forming a mixture, the mixture comprising: a diamine or polyamine containing at least one primary amine group; and a silane; II) reacting the mixture in a first reaction; III) adding a hydrolyzing agent to the mixture; and IV) reacting the mixture in a second reaction to form the aminoalkyl-substituted disiloxane.

[0255] 2. The method according to the preceding clause, wherein the aminoalkyl-substituted disiloxane is a compound of formula (BI)

[0256]

[0257] in:

[0258] R 12 , R 13 , R 14 , R 15 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0259] R 16 and R 17 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1-C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 alkyl;

[0260] R 18 and R 19 Each independently selected from the substituents of formula (B-IV)

[0261]

[0262] in:

[0263] The wavy bond indicates the bonding position to formula (BI);

[0264] 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 linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C 1 -C 6 Straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0265] R 31 and R 32 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6Cycloalkyl and substituted or unsubstituted C 4 -C 6 Cycloalkyl, or when taken together, R 31 and R 32 forming a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl;

[0266] R 33 , R 34 and R 35 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, ether, -OCH 2 CH 2 -、-OCH 2 CH 2 CH 2 -、-OCH 2 CH 2 CH 2 CH 2 -、-NHCH 2 CH 2 -、-NHCH 2 CH 2 CH 2 - and -NHCH 2 CH 2 CH 2 CH 2 -;

[0267] R 36 Selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 4 -C 6 Cycloalkyl, heterocycloalkyl, and heteroaryl; and

[0268] m is an integer ranging from 0 to 20.

[0269] 3. The method according to any one of the preceding clauses, wherein the aminoalkyl-substituted disiloxane is a compound selected from the group consisting of:

[0270]

[0271] as well as

[0272] 4. A method according to any one of the preceding clauses, wherein the diamine or polyamine containing at least one primary amine group is a compound of formula (B-II)

[0273]

[0274] in:

[0275] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0276] R 7 and R 8 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl and substituted or unsubstituted C4 -C 6 Cycloalkyl, or when taken together, R 7 and R 8 forming a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl;

[0277] R 9 , R 10 and R 11 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, ether, -OCH 2 CH 2 -、-OCH 2 CH 2 CH 2 -、-OCH 2 CH 2 CH 2 CH 2 -、-NHCH 2 CH 2 -、-NHCH 2 CH 2 CH 2 - and -NHCH 2 CH 2 CH 2 CH 2 -;as well as

[0278] n is an integer ranging from 0 to 20.

[0279] 5. A method according to any one of the preceding clauses, wherein the silane is a compound of formula (B-III)

[0280]

[0281] in:

[0282] R 20 selected from the group consisting of halide, fluoride, chloride, bromide and iodide;

[0283] R 21 and R 22 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0284] R 23 and R 24 are each independently selected from the group consisting of: substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, aryl and phenyl.

[0285] 6. A method according to any one of the preceding clauses, wherein the silane is

[0286]

[0287] 7. The method according to any of the preceding clauses, wherein reacting the mixture in a first reaction comprises stirring the mixture.

[0288] 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.

[0289] 9. A method according to any of the preceding clauses, wherein the first time period is a time in the range of about 1 second to about 12 hours.

[0290] 10. A method according to any of the preceding clauses, wherein the hydrolyzing agent is an aqueous solution.

[0291] 11. A method according to any of the preceding clauses, wherein the hydrolysis agent is water.

[0292] 12. A method according to any of the preceding clauses, wherein the hydrolyzing agent is added to the mixture during a second period of time.

[0293] 13. A method according to any of the preceding clauses, wherein the second time period is a time in the range of about 1 second to about 12 hours.

[0294] 14. A method according to any of the preceding clauses, wherein the hydrolyzing agent is added dropwise to the mixture.

[0295] 15. The method according to any of the preceding clauses, wherein the method further comprises purifying the aminoalkyl-substituted disiloxane.

[0296] 16. The method according to any of the preceding clauses, wherein at least one method step comprises adjusting the temperature of the mixture.

[0297] 17. The method according to any of the preceding clauses, wherein reacting the mixture in a second reaction comprises adjusting the temperature of the mixture.

[0298] 18. The method according to any of the preceding clauses, wherein reacting the mixture in a second reaction comprises cooling the mixture.

[0299] 19. A method according to any one of the preceding clauses, wherein the method is a one-pot synthesis.

[0300] 20. An aminoalkyl-substituted disiloxane prepared by a process according to any one of the preceding clauses.

[0301] 21. An aminoalkyl-substituted disiloxane of formula (BI)

[0302]

[0303] in:

[0304] R 12 , R 13 , R 14 , R 15 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0305] R 16 and R 17 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 alkyl;

[0306] R 18 and R 19 Each independently selected from the substituents of formula (B-IV)

[0307]

[0308] in:

[0309] The wavy bond indicates the bonding position to formula (BI);

[0310] 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 linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C 1 -C 6 Straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0311] R 31 and R 32 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl and substituted or unsubstituted C 4 -C 6 Cycloalkyl, or when taken together, R 31 and R 32forming a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl;

[0312] R 33 , R 34 and R 35 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, ether, -OCH 2 CH 2 -、-OCH 2 CH 2 CH 2 -、-OCH 2 CH 2 CH 2 CH 2 -、-NHCH 2 CH 2 -、-NHCH 2 CH 2 CH 2 - and -NHCH 2 CH 2 CH 2 CH 2 -;

[0313] R 36 Selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 4 -C 6 Cycloalkyl, heterocycloalkyl, and heteroaryl; and

[0314] m is an integer ranging from 0 to 20;

[0315] Provided that the aminoalkyl-substituted disiloxane is not

[0316]

[0317] 22. The aminoalkyl-substituted disiloxane according to the preceding clause, wherein the aminoalkyl-substituted disiloxane is a compound selected from the group consisting of:

[0318]

[0319] as well as

[0320] Machine learning model incorporating physical characteristics of sorbents for post-combustion carbon capture

[0321] In one aspect, a power generation system is provided. The power generation system includes a capture system for capturing carbon dioxide, a controller configured to operate the capture system, and a modeling system including a processor. The processor is configured to identify a model training data set, each instance of which identifies an adsorbent used by the capture system, a carbon capture performance value of the adsorbent, and a plurality of primary feature values ​​associated with a plurality of primary features. The processor is 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 determine a plurality of correlation amplitude values, the plurality of correlation amplitude values ​​including correlation amplitude values ​​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 data set based on the plurality of correlation amplitude values, determine the statistical significance of each instance of the first subset of the model training data set, and identify a second subset of the model training data set based on the statistical significance, wherein the statistical significance of each instance of the second subset of the model training data set is below a predetermined threshold. The processor is further configured to generate a transfer function based on a second subset of the model training data set 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 value. The controller operates the capture system using the one or more expected sorbents determined by the modeling system.

[0322] In another aspect, a method for selecting one or more prospective adsorbents for operating a capture system to capture carbon dioxide. The method includes identifying a model training data set, each instance of the model training data set identifying an adsorbent used by the capture system, a carbon capture performance value of the adsorbent, and a plurality of primary feature values ​​associated with a plurality of primary features. 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 magnitude values, the plurality of correlation magnitude values ​​including correlation magnitude values ​​between each of the plurality of primary features and each of the one or more secondary features; and identifying a first subset of the model training data set based on the plurality of correlation magnitude values. The method also includes determining a statistical significance of each instance of the first subset of the model training data set; identifying a second subset of the model training data set based on the statistical significance, wherein the statistical significance of each instance of the second subset of the model training data set is below a predetermined threshold; and generating a transfer function based on the second subset of the model training data set. The method further includes determining one or more anticipated sorbents to be used by the capture system based on the carbon capture performance value using the transfer function, wherein the controller operates the capture system using the one or more anticipated sorbents determined based on the transfer function.

[0323] In one embodiment, a computer program is provided and embodied on a computer readable medium. In an exemplary embodiment, the system is executed on a single computer system without requiring connection to a server computer. In another embodiment, the system is executed on a single computer system. In another embodiment, the system is operated in a mainframe environment and UNIX is a registered trademark of X / Open Company Limited, located in Reading, Berkshire, United Kingdom. In another embodiment, the system is In another embodiment, the system runs on a Mac (Mac OS is a registered trademark of Apple Inc. located in Cupertino, CA). In another embodiment, the system In another embodiment, the system runs on an Android OS (Android is a registered trademark of Google, Inc., located in Mountain View, CA). The system may be implemented in a manner that allows the user to use a computer program that is executable by a computer. The system may be implemented in a manner that allows the user to use a computer program that is executable by a computer. The system may be implemented in a manner that allows the user to use a computer program that is executable by a computer. The system may be implemented in a manner that allows the user to use a computer program that is executable by a computer. The system may be implemented in a manner that allows the user to use a computer program that is executable by a computer.

[0324] 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 specifically to metal organic framework (MOF) based compositions and their effects on carbon dioxide (CO 2 ) capture capacity. In an exemplary embodiment, the modeling system is configured to train a model based on the performance characteristics of known metal organic frameworks (MOFs) and their associated components. The model can then be used to evaluate the expected performance of other MOFs based on their specific components. Such modeling can help scientists and engineers evaluate different MOFs without physically testing each candidate, thereby more quickly developing products that can be used in CO 2 capture. 2 MOFs with improved performance in terms of capture capacity.

[0325] Fig.14 An exemplary PCC modeling system 1440 is shown that can be used to predict the performance of a particular MOF in capturing carbon dioxide (CO 2 ) from exhaust gas 1416 of a coal-fired power plant 1410. 2 ). In the exemplary embodiment, power plant 1410 generates electricity 1412 that is distributed via transmission and distribution grid 1414. Power plant 1410 also includes a post-combustion carbon capture (PCC) system 1420 that is configured to remove CO from exhaust gas 1416. 2, and then releasing the treated exhaust gas into the environment. The exemplary PCC system 1420 includes a metal organic framework (MOF) 1422, which performs the capture function of the PCC system 1420. The MOF 1422 is composed of three main components, namely a metal 1424, an organic linker 1426, and one or more functional groups 1428. During operation, the PCC system 1420 produces certain performance results, which for the purposes of discussion are generally represented here as "capture performance" 1430 (e.g., PCC capacity). The PCC modeling system 1440 is configured to estimate how a particular MOF (e.g., a particular combination of components and various associated physical characteristics) will perform when implemented in the PCC system 1420 (e.g., performance predictions in a "real world" environment).

[0326] In this exemplary embodiment, the PCC modeling system 1440 includes a data collection and preparation module 1442, which is configured to identify and store data to be used to train a machine learning model (e.g., a supervised predictive model). The preparation module 1442 stores historical records of various adsorbents (e.g., MOFs 1422) and their associated characteristics and known properties. Each historical record may include, for example, adsorbent data, such as the composition of a particular adsorbent (e.g., information about the metals 1424 used in the secondary structural units or SBUs, information about the organic linker 1426, and / or information about any functional groups 1428 or amines associated with a particular MOF 1422), various physical characteristics of the adsorbent (e.g., pore size, pore volume, pore size distribution, surface area, etc.), and known performance data of the adsorbent (e.g., isosteric heat of adsorption (Q) at a particular pressure and / or temperature). ST ), Henry's law constant, selectivity ratio, mmol CO adsorbed per gram of adsorbent 2 The adsorption capacity is expressed in millimoles of CO adsorbed per gram of adsorbent per unit time. 2 Each of these historical records may be stored as model data 1460 (e.g., in a database) and may include other data described herein. Some of these records may be collected from published literature, where other records may include data collected from laboratory measurements or operational performance data of the PCC system 1420 (e.g., data collected during operation).

[0327] The PCC modeling system 1440 also includes an exploratory data analysis module 1444, which is configured to help the analyst 1402 perform univariate data analysis on various aspects of historical data. In an exemplary embodiment, the exploratory data analysis module 1444 is configured to generate a chart showing a single component of a known MOF for a single feature, thereby allowing the analyst 1402 to see the trend of the feature of various MOFs. For example, the analysis module 1444 can generate a graph of two types of MOFs, chemical adsorbents and physical adsorbents, and how they perform in terms of Henry's constant, selectivity ratio, adsorption heat, PCC capacity and PCC productivity (e.g., as a composite material across these two types of MOFs). In another example, the analysis module 1444 can generate a graph of various metal types and their respective adsorption heats (e.g., the range of values, average values, etc. of each metal type) in physical adsorbents or chemical adsorbents MOF. These graphs can be compiled and generated from the historical records identified in the model data 1460, and displayed to the analyst 1402 via the display of the computing device 1404. Based on this data, the analyst 1402 can further identify one or more second-order features, which can be a combination of two or more of the first-order features, as discussed further below. Such second-order features can be used for subsequent model training and analysis.

[0328] In this exemplary embodiment, the PCC modeling system 1440 also includes a correlation and bivariate analysis module 1446, which is configured to analyze the model data 1460 for positive or negative correlations between various feature pairs of historical records. For example, the analysis module 1446 can identify a set of first-order features and possibly one or more second-order features, and perform a correlation analysis between the associated features. For each specific 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 the two features are related to each other (e.g., where a positive coefficient indicates a positive correlation between the two features, and where a negative coefficient indicates a negative correlation between the two features). These correlation coefficients can be, for example, Pearson correlation coefficients, etc. These correlation coefficients can be displayed to the analyst 1402 in a matrix format, allowing the analyst 1402 to view the strength of correlation between various feature pairs. In some examples, the matrix can be a heat map that displays each correlation coefficient, for example, in a color spectrum, with one color at one end of the spectrum (e.g., dark blue) indicating a strong positive correlation and another color at the opposite end of the spectrum (e.g., dark red) indicating a strong negative correlation, with coloring along the spectrum based on the magnitude of the correlation coefficient. In some examples, the analysis module 1446 can generate a pair graph for each of the feature pairs, allowing the analyst 1402 to assess what type of relationship the two features have (e.g., linear, nonlinear, etc.).

[0329] The PCC modeling system 1440 also includes a regression analysis module 1448, which is configured to perform regression analysis using the model data 1460. In an exemplary embodiment, the regression analysis module 1448 identifies one or more features of interest for regression analysis. In some embodiments, the analyst 1402 may check the above-mentioned correlation matrix and / or pairing diagram, and may select a subset of features of interest. In some embodiments, the regression analysis module 1448 may automatically identify one or more features of interest for regression analysis (e.g., matrix-based correlation coefficients). For example, the regression analysis module 1448 may select all features with a positive correlation coefficient (e.g., a strong positive correlation) with PCC capacity that is higher than a specific threshold. In some embodiments, the regression analysis module 1448 may also select all features with a negative correlation coefficient (e.g., a strong negative correlation) with PCC capacity that is lower than a specific threshold. In some embodiments, the features used to start regression analysis are selected manually by the user.

[0330] Once the feature subset is identified, the regression analysis module 1448 performs a regression analysis process starting from the feature subset. In some embodiments, a portion of the model data 1460 may be automatically or manually identified as training data (e.g., for the regression analysis process), and the remainder of the model data 1460 may be retained 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 of which includes performing 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 analysis stages, leaving another subset of the features selected downward for the next analysis stage until a specific stopping criterion is reached. In this final stage, the regression analysis module 148 generates a transfer function using the last remaining downwardly selected features (e.g., PCC capacity as a function of a specific downwardly selected feature). Therefore, the transfer function can be applied to a new MOF and its associated feature values ​​to predict how the new MOF will perform in terms of PCC capacity, productivity, etc.

[0331] Figure 16 and Fig.17 Additional details and related functions performed by the PCC modeling system 1440 are described in greater detail.

[0332] Fig.15 is a graph 1500 showing CO 2 for an exemplary adsorbent (e.g., an exemplary MOF) from a synthesized powder measured under equilibrium conditions to a final film coating on a substrate measured under dynamic conditions. 2 In this exemplary embodiment, Y-axis 1502 of graph 1500 is in kilograms of CO 2 (kgCO 2) / kg of adsorbent (kg) / hour (h) of the MOF. The X-axis shows several stages 1504 of PCC productivity: from the equilibrium powder productivity of the initial stage 1504A, to the kinetic time effect stage 1504B, the membrane mass transfer effect stage 1504C, the thermodynamic effect (working capacity between adsorption and desorption) stage 1504D, and then to the final coating work productivity stage 1504E. In this embodiment, in the initial stage 1504A, the adsorbent exhibits about 0.58 kgCO in the synthesized powder measured under equilibrium conditions. 2 / kg / h production rate. At each of the stages 1504A-1504E, the adsorbent will experience various reductions in production rate based on the various effects described above. For example, during the kinetic time effect stage 1504B, the adsorbent will experience a production reduction 1512 of about 0.2, down to a total of about 0.35 kgCO 2 / kg / h. In addition, for example, during the membrane mass transfer effect stage 1504C, the adsorbent will experience a second production decrease 1514 of about 0.05, with the total amount dropping to slightly less than about 0.3 kgCO 2 / kg / h. In addition, for example, during the thermodynamic effect working capacity stage 1504D, the adsorbent may experience a third production decrease 1516 of about 0.1, down to about 0.2 kgCO 2 / kg / h final coating work production rate 1520. Therefore, in this example, the adsorbent will experience about 0.38kgCO 2 The overall productivity of 1522 / kg / h was reduced by 1522, or about a 65% reduction (eg, about a 35% utilization). This knock-down effect is specific to each adsorbent, membrane coating, and cycle time operation.

[0333] Fig.15 The decrease in PCC productivity exhibited by the exemplary adsorbents of is generally coating type and measurement type specific and may be due to a combination of factors such as adsorption cycle time kinetics not allowing equilibrium to be reached, coating mass transfer resistance, and isosteric heat of adsorption heating the adsorbent and reducing performance capacity. Fig.14 In the case of the PCC modeling system 1440, all of these factors are typically determined experimentally in order to understand the ultimate productivity of a given adsorbent.

[0334] For initial adsorption at low concentrations, the Henry's law constant determines the equilibrium capacity of the adsorbent. The adsorbent capacity N of adsorbent i i is Henry's law constant H i Multiply by the gas phase concentration of the adsorbent C i Function: N i =H i C iThe larger the value of Henry's constant, the steeper the initial slope of the isotherm. This means that in the low concentration linear region of the isotherm, the higher the H i The adsorbent has a larger sorption capacity. Maximizing H i The productivity of the adsorbent at low gas phase sorbate concentrations is also improved. Therefore, the PCC modeling system 1440 will seek to find the optimal solution for CO by analyzing how the various MOF components vary independently with the Henry constant. 2 Since the Henry's constant is a thermodynamic term (e.g., not a kinetic term), the kinetics of the adsorbent can also be evaluated to determine the adsorbent productivity. These measurements are not typically reported in the literature for known MOFs, so the PCC modeling system 1440 can first look at the Henry's constant to identify the adsorbents that are most likely to adsorb at the lowest CO. 2 The highest CO concentration in the gas phase 2 Capacity potential of MOF components. Where kinetic uptake data were available, they were used as data input for the PCC modeling system.

[0335] FIG. 16A to FIG. 16C is a flow chart illustrating an exemplary method 1600 for analyzing the expected performance of a prospective sorbent in a post-combustion carbon capture system. In some embodiments, the method 1600 may be performed by the PCC modeling system 1440, and the identified sorbent may be installed in a Fig.14 The PCC system 1420 of FIG. 1420 is a PCC system of FIG. 1420. In an exemplary embodiment, the method 1600 includes collecting or otherwise identifying model training data for known adsorbents (eg, MOFs for which known performance data exists) at operation 1610.

[0336] In an exemplary embodiment, the identified model training data includes instances of individual adsorbents and their specific compositions and known performance data (e.g., various variables of specific known adsorbents) stored in a database such as a model database. Each adsorbent may include information about the composition of the specific adsorbent instance (e.g., specific metal elements, organic linkers and / or functional groups or functions), various physical characteristics of the adsorbent instance (e.g., pore size, pore volume, isosteric heat of adsorption, Henry's law constant, selectivity ratio, Langmuir / BET area, absorption rate, etc.), known performance data of the adsorbent instance (e.g., PCC capacity and productivity), and possibly other information about the adsorbent instance, such as a unique identifier or other adsorbent data (e.g., physical adsorbent or chemical adsorbent classification). Metals may include, for example, nickel, chromium, magnesium, copper, manganese, zirconium, zinc, cobalt, indium, iron, aluminum, dysprosium, titanium, potassium, etc., or some combination or alloy. The organic linker may include, for example, 1,4-dioxo-2,5-phthalate (DOBDC), 1,4-phthalate (BDC), 4,4′-oxo-1,1′-biphenyl-3,3′-diacarboxylate (DOBPDC), 1,3,5-tris(1H-1,2,3-triazol-4-yl)benzene (BTTri), 1,3,5-benzenetricarboxylate (BTC), 1H,5H-benzo(1,2-d:4,5-d′)bistriazole (BBTA), 1,1′-biphenyl-4,4′-diacarboxylate (BPDC), 1,1′-biphenyl-3,3′,5, 5′-tetracarboxylate (BPTC), 1,5-dioxo-2,6-naphthalene dicarboxylate (DONDC), 1,2,4,5-benzene tetracarboxylate (BTEC), 1,4-bis(1H-pyrazol-4-ylethynyl)benzene (BPEP), 2,5-bis(1H-1,2,4-triazol-1-yl)terephthalate (BTTA), 2,4,6-tris(3,5-dicarboxyphenylamino)-1,3,5-triazine (TDPAT), 2,3,5,6-tetrachloroterephthalate (TCDC), 4,4′-dibenzoic acid-2,2′sulfone (SBPDC), etc. The functionality may 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 cases, such adsorbent model training data may be manually collected (e.g., by analyst 1402) and recorded in a model data database. In some embodiments, PCC modeling system 1440 may be configured to collect such data (e.g., via other online databases, from performance or test data captured via PCC system 1420, etc.).

[0337] In an exemplary embodiment, the adsorbent data is used by the PCC modeling system 1440 as model training data for training a machine learning model to analyze the desired performance of prospective adsorbents (e.g., novel combinations of metals, linkers, and functionalities that have not yet been studied and tested under real-world conditions). The model training data can be used as labeled training data in model building (e.g., instances of model training data with specific "inputs" of known outcomes or "labels"). In some embodiments, a subset of the model training data may be identified for the purpose of training the model, and another subset may be identified for the purpose of testing the model (e.g., 60% of the adsorbents are identified for training and 40% are identified for testing, 70% are identified for training and 30% are identified for testing, etc.). In some embodiments, the analyst 1402 may manually identify the adsorbents for training and testing (e.g., by specific rows of a database). In some embodiments, the PCC modeling system 1440 may automatically identify the training subset and the test subset (e.g., using preconfigured percentages, random selection, etc.).

[0338] In some embodiments, method 1600 also includes performing aspects of univariate data analysis on the model training data at operation 1620. Such data analysis includes evaluating a particular single adsorbent variable (e.g., a particular component or feature) relative to other variables (e.g., another component, feature, or property value) across the entire body of training data. This analysis can be used to identify high-level trends relative to a particular component or feature.

[0339] In this exemplary embodiment, the PCC modeling system 1440 may provide the analyst 1402 with a graphical user interface that displays a graph of a particular feature relative to other target features of interest, thereby allowing the analyst 1402 to investigate trends and relationships between these particular features. The interface may 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 may then calculate the average / mean / median and / or value range of a bar chart, forest plot, etc. (e.g., for a domain variable with discrete values ​​and a continuous secondary variable) in all training data with these variables, or may generate a scatter plot, etc. (e.g., for continuous primary and secondary variables). For example, the PCC modeling system 1440 may generate a graph of an organic linker relative to isosteric heat of adsorption or Henry's law constant or average pore size, and may identify a physical adsorbent or a chemical adsorbent, respectively (e.g., via different colors or shading). In another example, the PCC modeling system 1440 may generate a graph of metals identified in the training data relative to isosteric heat of adsorption or selectivity ratios.

[0340] At operation 1630, in an exemplary embodiment, the PCC modeling system 1440 generates secondary features 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., a pre-existing primary effect parameter of a historical 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 that involves an interaction between the two primary features (e.g., an interaction parameter). In some embodiments, the analyst 1402 may manually create a secondary feature within the PCC modeling system 1440 by specifying two or more primary features and combining them as a new secondary feature for the model. In one example, a secondary feature "A" may be created as (BET area * pore volume (V pore )), 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 for model training and analysis described below.

[0341] In some embodiments, the PCC modeling system 1440 can select the secondary features to be used during model training by using an automatic selection process. For example, the PCC modeling system 1440 can analyze the statistical significance of each primary feature, such as by a probability value. The probability value (p-value) is a measure of the significance of the variable to the model. A p-value less than 0.05 means that the factor in the model is statistically significant at a 95% confidence level, indicating that there is strong evidence against the result being random, and the probability that the result is random is less than 5%.

[0342] In some embodiments, the PCC modeling system 1440 may select a set number of secondary features. For example, for the number n of primary features analyzed by the PCC modeling system 1440, the set number of secondary features may be n C. In this example, the PCC modeling system 1440 may automatically select a value equal to (n+ n C) The total number of primary and secondary characteristics.

[0343] At operation 1640, in an exemplary embodiment, the PCC modeling system 1440 performs correlation and bivariate analysis of the model data. Fig. 16B, the analysis includes identifying a feature set for model training. At operation 1642, an expected feature set is identified for model training. The feature set includes a list of primary features 1602 (or first-order features) and secondary features 1604 (or second-order features) to be used in model training. As described above, the primary features 1602 include a list of physical characteristics or known variables (e.g., heat of adsorption, pore size, pore volume, Henry's constant, etc.) provided for the adsorbent in the model 1460, 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 ), isosteric heat of adsorption (Q st ) and average pore size And the secondary features 1604 include the three exemplary secondary features described above, namely, "A" = (BET area * pore volume (V pore )), "B" = (V pore * isosteric heat of adsorption (Qst)), and "C" = (BET area * Q st ). Thus, the training data can be considered to define an n-dimensional space, where n is the number of features 1606 used in model training.

[0344] At operation 1644, the PCC modeling system 1440 may generate a pair of plots or scatter plots for each unique combination of primary features 1602 and secondary features 1604 in the feature set 1606 using the training data adsorbent selected from the model data 1460. For example, the PCC modeling system 1440 may generate, for each unique combination of features 1606, a first pair of plots showing BET area and PCC capacity over the training data, a second pair of plots showing Langmuir surface area and PCC capacity over the training data, and a second pair of plots showing V surface area and PCC capacity over the training data. pore The PCC modeling system 1440 may display these graphs in a graphical user interface for the analyst 1402 to examine and consider. For some combinations, these graphs may help the analyst 1402 identify whether there is any correlation between the two variables within the training data, whether the correlation is linear or nonlinear, and whether it is a positive or negative correlation. Additionally, these graphs may help the analyst 1402 identify statistically significant variables within the training data.

[0345] At operation 1646, the PCC modeling system 1440 generates a correlation matrix 1608 of correlation coefficients for each pair of primary features 1602 and secondary features 1604 in the feature set 1606. More specifically, in this exemplary embodiment, the correlation matrix 1608 is an n-by-n matrix in which each unique feature 1602, 1604 in the feature set 1606 is assigned a row and a column (e.g., a square, reflection matrix). Each cell of the matrix 308 represents a certain combination of two features 1602, 1604 in the feature set 1606 (e.g., based on the specific row and column of the cell), and the value contained in the cell is a correlation coefficient representing the degree or magnitude of correlation between the two specific features. For each combination of two features 1602, 1604, the PCC modeling system 1440 calculates the correlation coefficient of the two features at operation 1648 (e.g., across training data). In this exemplary embodiment, the correlation coefficients are normalized from a range between +1.0-1.0, where more positive correlations between two features are closer to +1.0, more negative correlations are closer to -1.0, and neutral (e.g., weak or non-existent) correlations are closer to 0.0 (e.g., Pearson's correlation coefficient). At operation 1650, the PCC modeling system 1440 fills in the particular cells with the correlation coefficients associated with the two features 1602, 1604. Upon completion, the correlation matrix and associated values ​​can be displayed to the analyst 1402 for inspection and consideration, and in some embodiments can be presented as a heat map (e.g., with each individual cell colored based on its value), thereby allowing the analyst 1402 to more easily see the positive and negative correlations between particular features. Additional details about the exemplary correlation matrix 1608 are as follows: Fig.17 shown.

[0346] Back again Fig.16A , exemplary method 1600 continues at operation 1660, where PCC modeling system 1440 performs a regression analysis to generate a transfer function that can help roughly estimate the PCC performance of other (e.g., untested) adsorbents. More specifically, Fig. 16C An exemplary regression analysis process of operation 1660 is shown.

[0347] In this exemplary embodiment, a set of model training data is identified from the model data 1460 for use during the regression operation 1660. In some embodiments, and as described above, specific instances of training data may be manually identified (e.g., by the analyst 1402) or may be selected (e.g., automatically) by the PCC modeling system 1440. Thus, the training data indicates which known adsorbents are within the scope of this particular regression analysis, wherein the remaining model data may be used to validate the results of the training.

[0348] At operation 1664, a set of features is selected for an initial feature set 1680 (e.g., from the primary features 1602 and the secondary features 1604 of the complete feature set 1606). In some embodiments, all of the features of the complete feature set 1606 may be initially used as the initial feature set 1680. In other embodiments, the analyst 1402 may manually select the features in the initial feature set 1680 (e.g., based on reviewing a pair graph and / or a correlation matrix). In other embodiments, the PCC modeling system 1440 may automatically select the initial feature set 1680. For example, the PCC modeling system 1440 may selectively add all features 1602, 1604 that have a correlation coefficient with PCC capacity that is above a predetermined threshold (e.g., greater than 0.2) or below a predetermined threshold (e.g., less than -0.2) to the initial feature set 1680. A plurality of these features, i.e., f, are then used as the current feature set 1682 to begin regression.

[0349] At operation 1666, the PCC modeling system 1440 performs multiple linear regression on the model training data using the current feature set (e.g., ordinary least squares model fitting using the training data, where PCC productivity is the dependent variable of interest, such as based on PCC capacity and CO 2 Here, a linear regression method was applied to Equation 1 to investigate the parameters of interest (e.g., PCC capacity ) and the various physical properties selected for the initial feature set 1680 (e.g., BET area, pore volume, isosteric heat of adsorption, and second-order features "A," "B," and "C" described above):

[0350]

[0351] In this regression, each of the f current features 1682 is represented by X in Formula 1. i and the associated linear coefficient b i Initially, as the regression iterates, all initial features 1680 are included in the transfer function of Formula 1, and then the current features 1682 with the highest p-values ​​are eliminated until all current features 1682 have p-values ​​less than a predetermined value (e.g., less than 0.05, meaning they have a 95% probability of being statistically significant). The relevant variables in the model are those variables that have probability values ​​("p-values") less than a predetermined threshold.

[0352] More specifically, in this exemplary embodiment, at each step of the iteration, a p-value is generated for each feature remaining in the current feature set 1682. At 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 terminates. Otherwise, the iteration continues to operation 1670. At operation 1670, the PCC modeling system 1440 identifies the current feature with the highest p-value and removes the particular feature from the current feature 1682 for the next iteration. The regression process returns to operation 1666, continues on the reduced current feature set 1682, and generates new p-values ​​again until all remaining features are below a predetermined threshold. If the primary feature has a p-value above the threshold, but the secondary feature including the primary feature has a p-value below the threshold, the primary feature is kept as part of the model, even if its individual p-value is greater than the threshold. This is necessary to make the secondary features with p-values ​​below the threshold part of the model.

[0353] When the regression iteration is completed and exited, the PCC modeling system 1440 may have identified one or more remaining features to be included in the final feature set 1684, each of which has a p-value equal to or lower than a predetermined threshold and is therefore statistically significant. In this exemplary embodiment, the PCC modeling system 1440 checks the final results to determine possible indications of overfitting in the model. For the final feature set 1684, the PCC modeling system 1440 also generates an r-squared value and an adjusted r-squared value, and the difference between these two values ​​can be an indication of overfitting (e.g., if they are too far apart). If the difference between the r-squared value and the adjusted r-squared value (e.g., abs(r-squared-adjusted r-squared)) is greater than a predetermined threshold, there is a possibility of overfitting in the model. In this case, the PCC modeling system 1440 then analyzes each unique combination of the remaining features in the final feature set 1684, runs the model with that combination to generate an r-squared value and an adjusted r-squared value for each combination, and then selects the particular combination with the closest r-squared value and adjusted r-squared value (e.g., the smallest abs(r-squared - adjusted r-squared)).

[0354] The remaining features and their associated values ​​are used to generate the final transfer function from the model. More specifically, the regression produces the final coefficients for each remaining feature in the final feature set 1684, as well as a constant coefficient (e.g., a y-intercept value). Thus, X of Equation 1 f Each of the variables is identified with each of the remaining features and each associated coefficient b is f Add to Formula 1, and the constant coefficient b 0, to generate a final transfer function. This transfer function can then be used along with the expected adsorbent and its associated values ​​to determine the expected PCC capacity for that particular adsorbent.

[0355] In some embodiments, the PCC modeling system 1440 can use the model on the test data to evaluate its performance in predicting capacity. For example, the PCC modeling system 1440 can generate a residual plot of a linear regression model for both the training data and the test data, allowing the analyst 1402 to evaluate how well the model performs.

[0356] In one specific example, a regression operation 1660 is performed on an exemplary training set to obtain the isosteric heat of adsorption (Q st ), BET area, pore volume (V pore ) and an initial feature set of three exemplary secondary features "A", "B", and "C". In the first iteration, the p-value for BET Area was identified as the highest at 0.948 and was deleted. In the second iteration, the p-value for the "A" secondary feature was identified as the highest at 0.769 and was deleted. In the third iteration, the p-value for the "B" secondary feature was identified as the highest at 0.441 and was deleted. In the fourth iteration, the p-values ​​for all remaining current features (e.g., Q st 、V pore and "C" secondary features) are below 0.05, and therefore the regression iterations are terminated with these three features as the final feature set. However, in this example, the final r-squared value is 0.400, and the adjusted r-squared value is 0.363, a difference that triggers overfitting analysis. Since there are three remaining features in the final feature set 1684, each combination of those features is checked with 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, only [Q st ] produces an r-square of 0.567 and an adjusted r-square of 0.560, with a minimum difference of 0.007. Therefore, only Q st The features and their associated values ​​are used to generate the final transfer function with only one remaining feature (e.g. X 1 =Q st ),Right now where b 1 =0.0318 is Q st The final coefficients generated are 0=-0.4243 is a constant coefficient. In this particular example, applying the test data to the trained model yields a test r-squared value of 0.331, where the r-squared of the trained model is 0.567. Therefore, the formula only includes features with p-values ​​less than 0.05. In addition, the positive r-squared of the test data indicates that the model is able to use the heat of adsorption (Q st ) to explain about 60% of the capacity.

[0357] The PCC modeling system 1440 may use the generated transfer function to operate the post-combustion carbon capture system, such as, but not limited to, by determining one or more prospective sorbents to be used by the post-combustion carbon capture system. For example, the PCC modeling system 1440 may identify one or more prospective 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.

[0358] Fig.17 An exemplary correlation matrix 1608 is shown. In some embodiments, the correlation matrix 1608 is generated by the PCC modeling system 1440 and is FIG. 16B to FIG. 16C 1700 is used in the method 1600 described in . In this exemplary embodiment, the correlation matrix 1608 is a 9×9 square reflection matrix. It has nine rows 1702 and nine columns 1704, and nine features 1712 that are the subject of the exemplary model. Each of the nine features 1712 has an associated row 1702 and an associated column 1704. The features 1712 include six first-order ("primary") features 1712A and three second-order ("secondary") features 1712B, similar to FIG. 16B to FIG. 16C Each cell of the matrix includes a correlation coefficient calculated between two specific intersection features of that cell. For example, the correlation coefficient between BET area and PCC capacity is -0.12.

[0359] Further aspects of the invention are provided by the subject matter of the following clauses:

[0360] 1. A power generation system, comprising: a capture system for capturing carbon dioxide; a controller configured to operate the capture system; and a modeling system, the modeling system comprising a processor configured to: identify a model training data set, each instance of the model training data set identifying an adsorbent used by the capture system, a carbon capture performance value of the adsorbent, and a plurality of primary feature values ​​associated with a plurality of primary features; generate one or more secondary features based on one or more primary features of the plurality of primary features, each of the one or more secondary features being a combination of at least two primary features of the plurality of primary features; determine a plurality of correlation amplitude values, the plurality of correlation amplitude values ​​including each primary feature of the plurality of primary features. The invention relates to a method for generating a carbon capture performance system comprising: determining a correlation magnitude value between the primary feature and each of the one or more secondary features; identifying a first subset of the model training data set based on the multiple correlation magnitude values; determining a statistical significance of each instance of the first subset of the model training data set; identifying a second subset of the model training data set based on the statistical significance, wherein the statistical significance of each instance of the second subset of the model training data set is below a predetermined threshold; generating a transfer function based on the second subset of the model training data set; and using the transfer function, determining one or more expected adsorbents to be used by the capture system based on the carbon capture performance value, wherein the controller uses the one or more expected adsorbents determined by the modeling system to operate the capture system.

[0361] 2. The power generation system according to the preceding clause, wherein generating the one or more secondary characteristics based on one or more primary characteristics of the plurality of primary characteristics comprises performing a univariate data analysis on the plurality of primary characteristics.

[0362] 3. A power generation system according to any of the preceding clauses, wherein determining the multiple correlation amplitude values ​​includes generating a correlation matrix including a plurality of cells, the plurality of cells being arranged into a plurality of rows and a plurality of columns for the plurality of primary features and the one or more secondary features, each of the plurality of cells including one of the multiple correlation amplitude values.

[0363] 4. A power generation system according to any of the preceding clauses, wherein the processor of the modelling system is configured to select an initial feature set from the plurality of primary features and the one or more secondary features.

[0364] 5. A power generation system according to any of the preceding clauses, wherein selecting the initial feature set comprises receiving user input from a user indicating a selection of one or more of the plurality of primary features and the one or more secondary features.

[0365] 6. A power generation system according to any of the preceding clauses, wherein selecting the initial feature set comprises selecting one or more features of the plurality of primary features and the one or more secondary features, each of the one or more features having a correlation coefficient greater than a predetermined threshold.

[0366] 7. A power generation system according to any of the preceding clauses, wherein each of the one or more characteristics has one or more PCC performance data values ​​greater than a predetermined threshold.

[0367] 8. A power generation system according to any of the preceding clauses, wherein the processor of the modeling system is configured to: determine an r-squared value and an associated adjusted r-squared value for each unique combination of each instance of the second subset of the model training data set; determine a difference between the r-squared value and the associated adjusted r-squared value for each instance of the second subset of the model training data set; and identify a third subset of the model training data set based on the difference, wherein the difference for each instance of the third subset of the model training data set is greater than a predetermined difference threshold.

[0368] 9. A power generation system according to any of the preceding clauses, wherein the difference for each instance of the third subset of the model training data set is less than the predetermined difference threshold.

[0369] 10. A power generation system according to any of the preceding clauses, wherein the plurality of primary characteristics comprises at least carbon capture capacity and isosteric heating value of adsorption.

[0370] 11. A power generation system according to any of the preceding clauses, wherein the one or more secondary characteristics are based on one or more of selectivity ratio, pore volume and isosteric heat of adsorption.

[0371] 12. A method for selecting one or more prospective adsorbents for use in operating a capture system to capture carbon dioxide, the method comprising: identifying a model training data set, each instance of the model training data set identifying an adsorbent used by the capture system, a carbon capture performance value of the adsorbent, and a plurality of primary feature values ​​associated with a plurality of primary features; generating one or more secondary features based on one or more of the plurality of primary features, each of the one or more secondary features being a combination of at least two of the plurality of primary features; determining a plurality of correlation magnitude values, the plurality of correlation magnitude values ​​comprising a correlation magnitude of each of the plurality of primary features with the one or more secondary features; The invention relates to a method for determining a first subset of the model training data set based on the plurality of correlation magnitude values ​​between each of the secondary features in the primary features; identifying a first subset of the model training data set based on the plurality of correlation magnitude values; determining a statistical significance of each instance of the first subset of the model training data set; identifying a second subset of the model training data set based on the statistical significance, wherein the statistical significance of each instance of the second subset of the model training data set is below a predetermined threshold; generating a transfer function based on the second subset of the model training data set; and using the transfer function, determining one or more expected adsorbents to be used by the capture system based on the carbon capture performance value, wherein a controller operates the capture system using the one or more expected adsorbents determined according to the transfer function.

[0372] 13. The method according to the preceding clause, wherein generating the one or more secondary features based on one or more primary features of the plurality of primary features comprises performing univariate data analysis on the plurality of primary features.

[0373] 14. A method according to any of the preceding clauses, wherein determining the multiple correlation amplitude values ​​includes generating a correlation matrix comprising a plurality of cells, the plurality of cells being arranged into a plurality of rows and a plurality of columns for the plurality of primary features and the one or more secondary features, each of the plurality of cells comprising one correlation amplitude value among the plurality of correlation amplitude values.

[0374] 15. The method of any of the preceding clauses, further comprising selecting an initial feature set from the plurality of primary features and the one or more secondary features.

[0375] 16. The method of any of the preceding clauses, wherein selecting the initial set of features comprises receiving user input from a user indicating a selection of one or more of the plurality of primary features and the one or more secondary features.

[0376] 17. A method according to any of the preceding clauses, wherein selecting the initial feature set comprises selecting one or more features from the plurality of primary features and the one or more secondary features, each of the one or more features having a correlation coefficient greater than a predetermined threshold.

[0377] 18. The method according to any of the preceding clauses further includes: determining an r-squared value and an associated adjusted r-squared value for each unique combination of each instance of the second subset of the model training dataset; determining a difference between the r-squared value and the associated adjusted r-squared value for each instance of the second subset of the model training dataset; and identifying a third subset of the model training dataset based on the difference.

[0378] 19. A method according to any of the preceding clauses, wherein identifying the third subset of the model training data comprises the difference for each instance of the third subset of the model training data set being greater than a predetermined difference threshold.

[0379] 20. A method according to any of the preceding clauses, wherein identifying the third subset of the model training data comprises the difference for each instance of the third subset of the model training data set being less than a predetermined difference threshold.

[0380] Solid adsorbent materials

[0381] In one aspect, a functionalized adsorbent is provided. The functionalized adsorbent comprises an adsorbent and at least one functionalized ligand comprising an aminosilicone group. The adsorbent has an average particle length of ≤3 μm. In another aspect, the adsorbent has an average particle length of ≤2 μm. In another aspect, the adsorbent has an average particle length of ≤1 μm.

[0382] It has been found that one or more of reduced adsorbent particle size, increased adsorbent aspect ratio, and aqueous adsorbent synthesis results in adsorbents with significantly improved CO 2 Absorption kinetics of adsorbents.

[0383] Generally, the adsorbent may include any suitable particle size known in the art to facilitate the functionalized adsorbent described herein. In some embodiments, the adsorbent has an average particle length of ≤3 μm, ≤2.9 μm, ≤2.8 μm, <2.7 μm, ≤2.6 μm, ≤2.5 μm, ≤2.4 μm, ≤2.3 μm, ≤2.2 μm, ≤2.1 μm, ≤2 μm, ≤1.9 μm, ≤1.8 μm, ≤1.7 μm, ≤1.6 μm, ≤1.5 μm, ≤1.4 μm, ≤1.3 μm, ≤1.2 μm, ≤1.1 μm, ≤1 μm, ≤0.9 μm, ≤0.8 μm, ≤0.7 μm, ≤0.6 μm, ≤0.5 μm, ≤0.4 μm, ≤0.3 μm, ≤0.2 μm, or ≤0.1 μm. In some embodiments, the adsorbent has an average particle length of ≥3 μm, ≥2.9 μm, ≥2.8 μm, ≥2.7 μm, ≥2.6 μm, ≥2.5 μm, ≥2.4 μm, ≥2.3 μm, ≥2.2 μm, ≥2.1 μm, ≥2 μm, ≥1.9 μm, ≥1.8 μm, ≥1.7 μm, ≥1.6 μm, ≥1.5 μm, ≥1.4 μm, ≥1.3 μm, ≥1.2 μm, ≥1.1 μm, ≥1 μm, ≥0.9 μm, ≥0.8 μm, ≥0.7 μm, ≥0.6 μm, ≥0.5 μm, ≥0.4 μm, ≥0.3 μm, ≥0.2 μm, or ≥0.1 μm.

[0384] Typically, the adsorbent may include any suitable aspect ratio known in the art to facilitate the functionalized adsorbents described herein. As used herein, the aspect ratio is the ratio between the average width of the adsorbent and the average length of the adsorbent. In some embodiments, the adsorbent has an aspect ratio ranging from about 0 to about 1. In some embodiments, the adsorbent has an aspect ratio of ≤1, ≤0.9, ≤0.8, ≤0.7, ≤0.6, ≤0.5, ≤0.4, ≤0.3, ≤0.2, or ≤0.1. In some embodiments, the adsorbent has an aspect ratio of ≥0.9, ≥0.8, ≥0.7, ≥0.6, ≥0.5, ≥0.4, ≥0.3, ≥0.2, ≥0.1, or ≥0.

[0385] For all particle size measurements we use average values, determined by measuring the length and width of the particles in the SEM images individually, or from the particle size distribution using a software package. Since it doesn't really matter how the measurements were made, I don't think we need to include the methods we used.

[0386] In some embodiments, the particle size is a single particle size.Single particle size measurements can be performed according to any suitable means known in the art, such as by measuring particle size in a SEM image.

[0387] In some embodiments, the particle size measurement is an average particle size measurement.Average particle size measurements can be made according to any suitable means known in the art, such as by analyzing particle size distribution information.

[0388] In general, the particle size of the adsorbent can be controlled, altered, or reduced according to any suitable technique known in the art to facilitate the functionalization of the adsorbents described herein. In some embodiments, suitable techniques for controlling, altering, or reducing particle size include mechanical grinding (e.g., mortar and pestle), use of a microfluidizer, dry milling, wet milling, chemical size reduction (e.g., incorporation of crystal growth inhibitors), acoustic cavitation, hydrodynamic cavitation, and combinations thereof.

[0389] Generally, the adsorbent can be in any suitable form known in the art to facilitate the functionalized adsorbent described herein. In some embodiments, the adsorbent is in a form selected from the group consisting of powders, pellets, composites, composites mixed with a binder, membranes, coatings, packed beds, columns, monoliths, and combinations thereof.

[0390] Exemplary embodiments described herein include an adsorbent system. Generally, the adsorbent system can be any suitable adsorbent system known in the art that promotes the functionalized adsorbent described herein. In some embodiments, the adsorbent system includes a functionalized adsorbent and an optional binder. In some embodiments, the adsorbent system is disposed on a polymer membrane.

[0391] In some embodiments, the adsorbent system comprises at least one contactor. In some embodiments, the adsorbent system comprises more than one contactor. In some embodiments, the adsorbent system comprises a contactor configured for an adsorption cycle and a contactor configured for a desorption cycle. The contactor can be any suitable contactor known in the art to promote the functionalized adsorbent described herein. In some embodiments, the adsorbent is integrated into at least one channel of the contactor. In some embodiments, the contactor is made of the adsorbent itself. In some embodiments, the contactor is coated with an adsorbent system. In some embodiments, the contactor comprises more than one adsorbent coating, wherein at least one adsorbent coating is an adsorbent system.

[0392] In some embodiments, the adsorbent system includes a skeleton. The skeleton can be any suitable skeleton known in the art that promotes the functionalized adsorbent described herein. The skeleton can be included in a contactor or between two contactors. The skeleton can be composed of one component or more than one component. In some embodiments, the skeleton is an air skeleton. In some embodiments, the configuration of the skeleton is selected from the group consisting of a polygonal configuration, a rectangular configuration, a square configuration, a circular configuration, an asymmetric configuration, and a combination thereof. In some embodiments, the adsorbent system is mounted on the skeleton.

[0393] In some embodiments, the adsorbent system includes at least one concentrator. The concentrator can be any suitable concentrator known in the art to facilitate the functionalized adsorbent described herein. The concentrator can be a passive concentrator or an active concentrator.

[0394] In some embodiments, the adsorbent system includes at least one component configured to drive fluid flow. The component configured to drive fluid flow can be any suitable component configured to drive fluid flow known in the art to promote the functionalized adsorbent described herein. In some embodiments, the component configured to drive fluid flow is selected from the group consisting of a pump, a fan, and a combination thereof.

[0395] In some embodiments, the adsorbent system includes at least one component configured to change temperature. The component configured to change temperature can be any suitable component configured to change temperature known in the art to facilitate the functionalized adsorbent described herein. In some embodiments, the component configured to change temperature is selected from the group consisting of a heater, a cooler, and a combination thereof.

[0396] In some embodiments, the adsorbent system includes at least one component configured to transport a fluid. The component configured to transport a fluid can be any suitable component configured to transport a fluid known in the art that facilitates the functionalized adsorbent described herein. In some embodiments, the component configured to transport a fluid is selected from the group consisting of a pipe, a perforated pipe, a plastic perforated pipe, a polymer perforated pipe, a metal perforated pipe, a composite perforated pipe, and combinations thereof.

[0397] In general, the functionalized adsorbents may be used for any suitable purpose known in the art that facilitates the use of the functionalized adsorbents described herein. In some embodiments, the functionalized adsorbents are used in adsorbent systems. In some embodiments, the functionalized adsorbents are used in carbon capture adsorbent systems. In some embodiments, the functionalized adsorbents are used in moisture adsorbent systems. In some embodiments, the functionalized adsorbents are used in carbon capture adsorbent systems in the presence of water. In some embodiments, the functionalized adsorbents are used to capture gases. In some embodiments, the functionalized adsorbents are used to capture CO after combustion. 2 and / or direct air capture CO 2 .

[0398] Exemplary embodiments described herein include methods of making adsorbent systems. Generally, the functionalized adsorbents can be prepared according to any suitable synthesis method known in the art that facilitates the functionalized adsorbents described herein.

[0399] In many embodiments, the method of preparing an adsorbent system comprises preparing an adsorbent, wherein the adsorbent has an average particle length of ≤3 μm, and optionally functionalizing the adsorbent with at least one functionalized ligand comprising an aminosilicone group. In some embodiments, the method of preparing an adsorbent system comprises preparing an adsorbent, wherein the adsorbent has an average particle length of <2 μm, and optionally functionalizing the adsorbent with at least one functionalized ligand comprising an aminosilicone group. In some embodiments, the method of preparing an adsorbent system comprises preparing an adsorbent, wherein the adsorbent has an average particle length of <1 μm, and optionally functionalizing the adsorbent with at least one functionalized ligand comprising an aminosilicone group.

[0400] In some embodiments, the method of preparing an adsorbent system comprises functionalizing the adsorbent with at least two functionalized ligands each comprising an aminoorganosilicon group, wherein the aminoorganosilicon groups are different from each other. In some embodiments, the method of preparing an adsorbent system further comprises functionalizing the adsorbent with at least one functionalized ligand that does not comprise an aminoorganosilicon group. In some embodiments, the method of preparing an adsorbent system comprises controlling the ratio between at least one functionalized ligand comprising an aminoorganosilicon group and at least one functionalized ligand that does not comprise an aminoorganosilicon group.

[0401] In some embodiments, the method of preparing the adsorbent system further comprises annealing the functionalized adsorbent. Annealing the adsorbent system may remove excess ligands. In some embodiments, annealing the functionalized adsorbent comprises annealing the functionalized adsorbent at an elevated temperature. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 50°C to about 400°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 100°C to about 300°C. In some embodiments, annealing the adsorbent comprises annealing the adsorbent at a temperature in the range of about 150°C to about 250°C.

[0402] Fig.34 is an exemplary method flow diagram 3410. In this exemplary embodiment, the method flow diagram 3410 depicts exemplary steps of a method embodiment described herein and is not intended to limit the method embodiment. In this exemplary embodiment, the method includes forming 3412 a mixture comprising: an adsorbent precursor; a crystal growth inhibitor; an optional solvent; and an optional non-solvent. The method also includes reacting 3414 the mixture. In some embodiments, the adsorbent has an average particle length of ≤3 μm. In some embodiments, the adsorbent has an average particle length of ≤2 μm. In some embodiments, the adsorbent has an average particle length of ≤1 μm.

[0403] Forming 3412 the mixture can be performed by any suitable means known in the art. In some embodiments, all components are added simultaneously. In some embodiments, at least one component is added at a different time than the other components.

[0404] In some embodiments, the adsorbent precursor comprises a MOF linker and a MOF metal or metal-containing cluster. The adsorbent precursor can be formed prior to the mixture forming 3412 and added to the mixture as a single component, or it can be formed in situ in the mixture during the mixture forming 3412. For example, the MOF linker can be deprotonated separately and then added or deprotonated in situ. Similarly, the MOF metal or metal-containing cluster can be preformed and then added or formed in situ.

[0405] In some embodiments, the solvent includes an aqueous solvent. In some embodiments, the solvent includes water. Using an aqueous solvent can provide several benefits. In particular, compared with at least some known methods for preparing MOF compounds, using an aqueous solvent has advantages in scalability, safety, cost and waste disposal. In addition, MOF compounds prepared with aqueous solvents are generally easier to purify than the same MOF compounds prepared according to known methods, such as by solvent washing. This improved purification is derived from the removal of the strongly bound solvent molecules (e.g., dimethylformamide (DMF)) used to prepare the same MOF compounds according to known methods, and it is relatively easy to remove solvent molecules (e.g., water) from the MOF compounds described herein. In addition, the purified MOF compounds do not include strongly bound solvent molecules that reduce gas absorption, surface area and / or total pore volume. Finally, purification is improved by requiring a purification method with less toxicity.

[0406] 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.

[0407] Typically, a non-solvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, a non-solvent is a liquid-based component contained in the reaction mixture. In some embodiments, a non-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, a non-solvent is selected from the group consisting of an organic solvent, an aqueous solvent, and a combination thereof.

[0408] In some embodiments, the crystal growth inhibitor is selected from the group consisting of salicylic acid, 4-fluorosalicylic acid, 4,4′-biphenylene glycol, 2,2′-bipyridine-5,5′-dicarboxylic acid (BPYDC), 2,2′-bipyridine-5,5′-dimethanol (BPYDM), benzoic acid, biphenylene glycol, bipyridine, and combinations thereof.

[0409] Fig.35 is an exemplary process flow diagram 3510. In this exemplary embodiment, process flow diagram 3510 depicts exemplary steps of a process embodiment described herein and is not intended to limit the process embodiments. In this exemplary embodiment, the process includes forming 3512 a mixture comprising: an adsorbent; at least one functionalized ligand comprising an amino organosilicon group; optionally at least one functionalized ligand not comprising an amino organosilicon group; optionally a solvent, and optionally a non-solvent. The process also includes functionalizing 3514 the adsorbent.

[0410] In some embodiments, functionalizing 3514 the adsorbent includes stirring the mixture.

[0411] In some embodiments, functionalizing 3514 the adsorbent includes functionalizing 114 the adsorbent in the presence of an inert gas.

[0412] In some embodiments, functionalizing 3514 the adsorbent includes functionalizing 3514 the adsorbent at a temperature in the range of about 0° C. to about 100° C. In some embodiments, functionalizing 3514 the adsorbent includes functionalizing 3514 the adsorbent at a temperature in the range of about 20° C. to about 80° C. In some embodiments, functionalizing 3514 the adsorbent includes functionalizing 3514 the adsorbent at a temperature in the range of about 20° C. to about 60° C.

[0413] In some embodiments, functionalizing 3514 the adsorbent includes functionalizing 3514 the adsorbent for a time in the range of about 1 minute to about 7 days. In some embodiments, functionalizing 3514 the adsorbent includes functionalizing 3514 the adsorbent for a time in the range of about 1 hour to about 3 days.

[0414] In some embodiments, the adsorbent is desolvated prior to functionalization 3514. In some embodiments, the adsorbent is dry prior to functionalization.

[0415] In some embodiments, the adsorbent is annealed after functionalization 3514. In some embodiments, annealing the adsorbent includes annealing the adsorbent at an elevated temperature. In some embodiments, annealing the adsorbent includes annealing the adsorbent at a temperature in the range of about 50°C to about 400°C. In some embodiments, annealing the adsorbent includes annealing the adsorbent at a temperature in the range of about 100°C to about 300°C. In some embodiments, annealing the adsorbent includes annealing the adsorbent at a temperature in the range of about 150°C to about 250°C.

[0416] 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.

[0417] Typically, a non-solvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, a non-solvent is a liquid-based component contained in the reaction mixture. In some embodiments, a non-solvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, a non-solvent is selected from the group consisting of an organic solvent, an aqueous solvent, and a combination thereof.

[0418] In some embodiments, the non-solvent facilitates functionalization. In some embodiments, the selectivity of functionalization is controlled by relative solubility. For example, one or more adsorbents or amines may have different solubility in a liquid-based reaction mixture compared to another adsorbent or amine or functionalized adsorbent. Thus, relative solubility introduces limiting reactions and / or reagents.

[0419] In many embodiments, the method may also include any other suitable processing steps known in the art that promote the success of the methods described herein. Such processing steps may include, but are not limited to, only washing, drying, filtering, purifying, separating, centrifuging, and any combination thereof. In some embodiments, the method also includes washing the functionalized adsorbent. In some embodiments, the method also includes purifying the functionalized adsorbent. In some embodiments, purification includes using distillation, vacuum distillation, and / or heating.

[0420] Exemplary embodiments described herein include methods of capturing at least one gas.

[0421] Fig.36 is an exemplary method flow chart 3610. In this exemplary embodiment, the method flow chart 3610 depicts exemplary method steps of the method embodiments described herein and is not intended to limit the method embodiments. The method includes receiving 3612 a gas source including at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent includes: an adsorbent; and at least one functionalized ligand comprising an aminoorganosilicon group. In some embodiments, the functionalized adsorbent includes at least two functionalized ligands each comprising an aminoorganosilicon group, wherein the aminoorganosilicon groups are different from each other. In some embodiments, the functionalized adsorbent also includes at least one functionalized ligand that does not include an aminoorganosilicon group. The method also includes capturing 3614 a certain amount of at least one gas with the functionalized adsorbent. The average particle length of the adsorbent is ≤1 μm.

[0422] In some embodiments, the method includes: (I) receiving 3612 a gas source comprising at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent includes an adsorbent and at least one functionalized ligand comprising an aminosilicone group; and (II) capturing 3614 a certain amount of the at least one gas with the functionalized adsorbent.

[0423] Generally, the gas source can be any suitable gas source known in the art to promote the methods described herein. In some embodiments, the gas source is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0424] Typically, the at least one gas can be any suitable gas known in the art to promote the methods described herein. In some embodiments, the at least one gas is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0425] In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 40% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 15% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v). In some embodiments, the at least one gas is present in the source gas in an amount greater than 10% (v / v).

[0426] In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 100 ppmv to about 1000 ppmv. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 300 ppmv to about 5000 ppmv.

[0427] In some embodiments, the at least one gas does not include water vapor.

[0428] In some embodiments, the at least one gas includes water vapor. In some embodiments, the at least one gas includes water vapor in an amount in the range of about 0.001% (v / v) to about 25% (v / v). In some embodiments, the at least one gas includes water vapor in an amount in the range of about 0.01% (v / v) to about 20% (v / v). In some embodiments, the at least one gas includes water vapor in an amount in the range of about 0.5% (v / v) to about 15% (v / v). In some embodiments, the at least one gas includes water vapor in an amount in the range of about 0.5% (v / v) to about 4% (v / v). In some embodiments, the at least one gas includes water vapor in an amount in the range of about 4% (v / v) to about 15% (v / v).

[0429] In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 10% (v / v) and water vapor is present. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 5% (v / v) and water vapor is present. In some embodiments, the at least one gas is present in the source gas in an amount ranging from about 0.001% (v / v) to about 1% (v / v) and water vapor is present. In some embodiments, the at least one gas is present in the source gas in an amount greater than about 10% (v / v) and water vapor is present. In some embodiments, water vapor is present in an amount ranging from about 0.001% (v / v) to about 25% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.01% (v / v) to about 20% (v / v). In some embodiments, water vapor is present in an amount ranging from about 0.5% (v / v) to about 10% (v / v).

[0430] In some embodiments, capturing 3614 an amount of at least one gas with a functionalized adsorbent includes adsorbing an amount of at least one gas with a functionalized adsorbent. In some embodiments, capturing 3614 an amount of at least one gas with a functionalized adsorbent includes adsorbing an amount of at least one gas with a functionalized adsorbent in the presence of water vapor.

[0431] In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 1% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 10% (v / v) to about 90% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 20% (v / v) to about 80% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 30% (v / v) to about 70% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 3614 with the functionalized sorbent is in a range from about 40% (v / v) to about 60% (v / v) of the at least one gas present in the source gas.

[0432] In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 1% (v / v) to about 25% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 1% (v / v) to about 20% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 1% (v / v) to about 15% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 1% (v / v) to about 10% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 1% (v / v) to about 5% (v / v) of the at least one gas present in the source gas.

[0433] In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 80% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 85% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 90% (v / v) to about 100% (v / v) of the at least one gas present in the source gas. In some embodiments, the amount of at least one gas captured 3614 with the functionalized adsorbent is in the range of about 95% (v / v) to about 100% (v / v) of the at least one gas present in the source gas.

[0434] In some embodiments, the source gas is modified to change the amount of water vapor. In some embodiments, changing the amount of water vapor includes increasing the amount of water vapor. In some embodiments, changing the amount of water vapor includes reducing the amount of water vapor. In some embodiments, increasing the amount of water vapor includes adding or injecting water vapor into the source gas. In some embodiments, reducing the amount of water vapor includes removing water vapor from the source gas by evaporation, condensation and / or pre-adsorption. In some embodiments, changing the amount of water vapor includes exhaust gas recirculation (EGR) and / or mixing.

[0435] In many embodiments, the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof is at a temperature. Each temperature may be varied to facilitate the methods described herein. Each temperature may have a uniform temperature profile, a gradient temperature profile, a discrete temperature profile, or a combination thereof.

[0436] In some embodiments, the method includes an adsorption cycle. In some embodiments, the method includes a desorption cycle. In some embodiments, during the gas adsorption cycle, at least one of the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof is at a temperature in the range of about 0°C to about 150°C. In some embodiments, during the gas desorption cycle, at least one of the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof is at a temperature in the range of about 60°C to about 250°C.

[0437] In some embodiments, the method includes controlling the temperature.The temperature of the functionalized adsorbent, the source gas, the at least one gas, or a combination thereof can be controlled.

[0438] Exemplary embodiments described herein include methods of collecting at least one gas from a gas source.

[0439] Fig.37is an exemplary method flow chart 3710. In this exemplary embodiment, method flow chart 3710 depicts exemplary method steps of the method embodiments described herein and is not intended to limit the method embodiments. The method includes receiving 3712 a gas source including at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent includes: an adsorbent; and at least one functionalized ligand comprising an aminoorganosilicon group. In some embodiments, the functionalized adsorbent includes at least two functionalized ligands each comprising an aminoorganosilicon group, wherein the aminoorganosilicon groups are different from each other. In some embodiments, the functionalized adsorbent also includes at least one functionalized ligand that does not include an aminoorganosilicon group. The method also includes capturing 3714 a certain amount of at least one gas with the functionalized adsorbent. The method also includes releasing 3716 at least one gas from the functionalized adsorbent. The average particle length of the adsorbent is ≤1 μm.

[0440] In some embodiments, the method includes: (I) receiving 3712 a gas source comprising at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent includes an adsorbent and at least one functionalized ligand comprising an aminosilicone group; (II) capturing 3714 a certain amount of the at least one gas with the functionalized adsorbent; and (III) releasing 3716 the at least one gas from the functionalized adsorbent.

[0441] In some embodiments, releasing 3716 at least one gas from the functionalized adsorbent includes purging the at least one gas from the functionalized adsorbent with a purge gas. In some embodiments, releasing 3716 at least one gas from the functionalized adsorbent includes receiving a change in temperature or pressure at the functionalized adsorbent.

[0442] In some embodiments, at least one gas is released 3716 from the functionalized adsorbent into a receiving gas. In some embodiments, the receiving gas is selected from the group consisting of air, N 2 , steam, and combinations thereof. In some embodiments, after receiving the at least one gas, the receiving gas is removed from the presence of the functionalized adsorbent. In some embodiments, the receiving gas has a higher concentration of at least one gas than the source gas.

[0443] Other aspects of the disclosure are provided by the subject matter of the following clauses:

[0444] 1. A functionalized adsorbent comprising:

[0445] Adsorbents; and

[0446] at least one functionalized ligand comprising an aminoorganosilicon group;

[0447] The adsorbent has an average particle length of ≤3 μm.

[0448] 2. The functionalized adsorbent according to the preceding embodiment, further comprising at least one functionalized ligand that does not contain an amino organosilicon group.

[0449] 3. The functionalized adsorbent according to any one 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.

[0450] 4. The functionalized adsorbent according to any one of the preceding embodiments, wherein the functionalized adsorbent is a functionalized MOF compound of formula (AI):

[0451]

[0452] in:

[0453] M is the MOF metal or metal-containing cluster;

[0454] L is a MOF linker;

[0455] F A is the at least one functionalized ligand comprising an amino organosilicon group;

[0456] F B is at least one functionalized ligand that does not contain an amino organosilicon group;

[0457] x is a value in the range of 1 to 6;

[0458] y is a value in the range of 1 to 6;

[0459] a is a value greater than 0 and less than or equal to 2; and

[0460] b is a value in the range of 0 to 2.

[0461] 5. The functionalized adsorbent according to any one of the preceding embodiments, wherein the MOF metal or metal-containing cluster comprises a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, their ions, their hydrates, their salts, their halides, their fluorides, their chlorides, their bromides, their iodides, their nitrates, their acetates, their sulfates, their phosphates, their carbonates, their oxides, their formates, their carboxylates, and combinations thereof.

[0462] 6. The functionalized adsorbent according to any one of the preceding embodiments, wherein the MOF linker comprises a linker selected from the group consisting of: a polyhedral linker, 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H 4 dobpdc), 4,4′-dioxybiphenyl-3,3′-dicarboxylate (dobpdc 4 -), 4,4"-dioxo-[1,1':4',1"-terphenyl]-3,3"-dicarboxylate (dotpdc 4 -), 2,5-dioxybenzene-1,4-dicarboxylate (dobdc 4 -), 4,6-dihydroxyisophthalic acid (m-dobdc 4 -), 3,3′-dioxo-biphenyl-4,4′-dicarboxylate (p-carboxylate-dobpdc 4 -), 4,4′-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H 4 ODA), 4,4′-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H 4 TDA), 4,4′-dihydroxyazobenzene-3,3′-dicarboxylic acid (H 4OSA), dicarboxylates, terephthalic acid, tricarboxylates, 1,3,5-benzenetricarboxylic acid, nitrogen azoles, tetrazoles, 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, terephthalic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline -3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, floret-3,9-dicarboxylic acid, floret dicarboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquine 1,4-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2′-biquinoline-4,4′-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenonedicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E 400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diaminodiphenyl ether imide dicarboxylic acid, 4,4'-diaminodiphenylmethane imide dicarboxylic acid,4'-Diaminodiphenylsulfone diimide dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 8-methoxy-2,3-naphthalene dicarboxylic acid, 8-nitro-2,3-naphthalene dicarboxylic acid, 8-sulfo-2,3-naphthalene dicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2'-3'-diphenyl-p-terphenyl-4,4"-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinoline dicarboxylic acid, 4,5-imidazole dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, trihexadecanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptane dicarboxylic acid acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosene dicarboxylic acid, 4,4′-dihydroxydiphenylmethane-3,3′-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorescein-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 acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic acid , 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurinetricarboxylic acid, 1,1-dioxide-pyrene [1,12-BCD] thiophene-3,4,9,10-tetracarboxylic acid, pyrene tetracarboxylic acid, pyrene-3,4,9,10-tetracarboxylic acid, pyrene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, meso-1,2,3,4-butane tetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, polyhedral linkers, dihedral linkers, trihedral linkers, tetrahedral linkers, pentahedral linkers, hexahedral linkers, heptahedral linkers, octahedral linkers, mixed linkers, asymmetric linkers, metal linkers, N-heterocyclic linkers, their protonated, partially or completely deprotonated forms, and combinations thereof.

[0463] 7. The functionalized adsorbent according to any one of the preceding embodiments, wherein the adsorbent has an aspect ratio > 0.2.

[0464] 8. The functionalized adsorbent according to any one of the preceding embodiments, wherein the adsorbent has an average particle length of <1 μm.

[0465] 9. The functionalized adsorbent according to any one of the preceding embodiments, wherein 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).

[0466]

[0467]

[0468] in:

[0469] R 1 , R 2 , R 3 , R 4 , R 9 , R 10 , R 13 , R 14 and R 18 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0470] R 5 , R6 , R 11 , R 15 and R 17 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 alkyl,

[0471] R 7 , R 8 , R 12 and R 16 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl group, and a substituent of formula (A-VIII)

[0472]

[0473] in:

[0474] The wavy bond indicates the bonding position to formula (A-II) or formula (A-III) or formula (A-IV) or formula (AV) or formula (A-VI) or formula (A-VII);

[0475] R 19 , R 20 , R 21 , R 22 , R 23 and R 24 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C 1 -C 6Straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl;

[0476] R 25 and R 26 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl and substituted or unsubstituted C 4 -C 6 Cycloalkyl, or when taken together, R 25 and R 26 forming a monocyclic ring selected from the group consisting of heterocycloalkyl and heteroaryl;

[0477] R 27 , R 28 and R 29 are each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, ether, -OCH 2 CH 2 -、-OCH 2 CH 2 CH 2 -、-OCH 2 CH 2 CH 2 CH 2 -、-NHCH 2 CH 2 -、-NHCH 2 CH 2 CH 2 - and -NHCH 2 CH2 CH 2 CH 2 -;

[0478] R 30 Selected from the group consisting of hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Straight chain alkyl, substituted or unsubstituted C 1 -C 3 Straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 4 -C 6 Cycloalkyl, heterocycloalkyl, and heteroaryl;

[0479] i is an integer ranging from 0 to 20;

[0480] k is an integer ranging from 0 to 20;

[0481] m is an integer in the range of 0 to 20; and

[0482] n is an integer ranging from 0 to 20.

[0483] 10. The functionalized adsorbent according to any one of the preceding embodiments, wherein the at least one functionalized ligand comprising an aminosilicone group is selected from the group consisting of:

[0484]

[0485]

[0486]

[0487]

[0488]

[0489] as well as

[0490]

[0491] 11. An adsorbent system comprising the functionalized adsorbent according to any one of the preceding embodiments.

[0492] 12. A method for preparing an adsorbent, the method comprising:

[0493] (I) forming a mixture, the mixture comprising:

[0494] Adsorbent precursors;

[0495] Crystal growth inhibitors;

[0496] optional solvent; and

[0497] optionally a non-solvent; and

[0498] (II) reacting the mixture;

[0499] The adsorbent has an average particle length of ≤3 μm.

[0500] 13. The method according to the preceding embodiment, wherein the sorbent precursor comprises a MOF linker and a MOF metal or a metal-containing cluster.

[0501] 14. The method according to any one of the preceding embodiments, wherein the solvent comprises an aqueous solvent.

[0502] 15. The method according to any one of the preceding embodiments, wherein the crystal growth inhibitor is selected from the group consisting of salicylic acid, 4-fluorosalicylic acid, 4,4′-biphenylene glycol, 2,2′-bipyridine-5,5′-dicarboxylic acid (BPYDC), 2,2′-bipyridine-5,5′-dimethanol (BPYDM), benzoic acid, biphenylene glycol, bipyridine, and combinations thereof.

[0503] 16. A method for preparing a functionalized adsorbent, the method comprising:

[0504] (I) forming a mixture, the mixture comprising:

[0505] An adsorbent prepared according to any one of the preceding embodiments;

[0506] at least one functionalized ligand comprising an aminoorganosilicon group;

[0507] optionally at least one functionalized ligand not comprising an aminosilicone group;

[0508] optional solvent; and

[0509] optionally a non-solvent; and

[0510] (II) Functionalizing the adsorbent.

[0511] 17. A method of capturing at least one gas, the method comprising:

[0512] (I) receiving a gas source comprising the at least one gas at a functionalized adsorbent, wherein the functionalized adsorbent comprises:

[0513] An adsorbent, wherein the adsorbent has an average particle length of ≤3 μm;

[0514] at least one functionalized ligand comprising an aminosilicone group; and

[0515] (II) capturing a quantity of the at least one gas with the functionalized adsorbent.

[0516] 18. A method according to the preceding embodiments, 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 gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0517] 19. The method according to any of the preceding embodiments, wherein the at least one gas is selected from the group consisting of air, flue gas, combustion gas, natural gas, synthesis gas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide and combinations thereof.

[0518] 20. A method of collecting at least one gas from a gas source, the method comprising:

[0519] capturing the at least one gas according to the method of any of the preceding embodiments, and

[0520] (III) releasing the at least one gas from the functionalized adsorbent.

[0521] Example

[0522] Without further detailed description, it is believed that those skilled in the art can make the most of the present invention using the foregoing description. Therefore, the following examples are to be construed as illustrative only and not to limit the present disclosure in any way. The starting materials for the following examples may not necessarily be prepared by a specific preparation run, the procedures of which are described in other embodiments. It should also be understood that any numerical range described herein includes all values ​​from the lower limit to the upper limit. For example, if the range is stated as 10 to 50, it is intended to explicitly list values ​​such as 12 to 30, 20 to 40, or 30 to 50 in this specification. These are only examples of specific intent, and all possible combinations of numerical values ​​between and including the lowest and highest values ​​listed are considered to be explicitly stated in the present application.

[0523] Carbon dioxide capture system using functionalized adsorbents and water management

[0524] Example A1. Comparison of moisture isotherms .

[0525] Figure 5 The H values ​​of adsorbents functionalized with AEAM, spermidine, a hybrid with spermine:AEAM=0.65:0.35 (“Hybrid Compound 1”), and a hybrid with spermine:AEAM=0.32:0.46 (“Hybrid Compound 2”) measured using DVS gravimetric analysis at 25°C are shown. 2 O adsorption capacity as a function of relative humidity. This figure illustrates the water adsorption isotherm and therefore the H 2 The relative humidity at which the inflection point of monolayer adsorption of O occurs varies with the chemical structure of the functionalized adsorbent. Figure 5 As shown, the shapes of the water adsorption isotherms for all adsorbents except AEAM are closest to type IV, including a flat region leading to an inflection point corresponding to the monolayer coverage of the two hybrid compounds at about 30% relative humidity and spermidine at about 35% relative humidity and H 2 O adsorption.

[0526] Example A2. Water adsorption isotherm of hybrid compound 1 .

[0527] Figure 6 The H of hybrid compound 1 (spermine:AEAM=0.65:0.35) at different temperatures is shown. 2 O adsorption capacity as a function of relative humidity. Figure 7 The H of hybrid compound 1 (spermine:AEAM=0.65:0.35) measured using DVS gravimetric analysis at different temperatures is shown. 2 O adsorption capacity and H 2 These plots illustrate that, despite differences in absolute HO partial pressure, the shape of the water isotherms, and therefore the H 2 The relative humidity at which the inflection point of O monolayer adsorption occurs remains approximately the same.

[0528] Example A3. Adsorption properties of hybrid compound 1 .

[0529] Figure 8 shows that at 40°C and 4.5v% CO 2 The CO of hybrid compound 1 (spermine: AEAM = 0.65: 0.35) was measured using DVS gravimetric analysis under the following conditions: 2 and H 2 O adsorption performance as a function of relative humidity. 2 Adsorption is sensitive to relative humidity. Figure 5 As shown in the hybrid compound 1, H 2 The inflection point of O monolayer adsorption appears to be a critical threshold. Since DVS gravimetric analysis is based on measuring the change in cumulative mass, it is not possible to predict the adsorption of O in binary systems (e.g., CO in this case). 2and H 2 O), due to the lack of differentiation among the components, it is impossible to accurately calculate the individual CO 2 Adsorption amount and H 2 O adsorption. However, the 2 and H 2 O single sensor breakthrough test rig and analyzer to quantitatively assess discrete CO 2 and H 2 O adsorption.

[0530] Example A4. Adsorption performance of hybrid compound 1 as a function of temperature, water content and relative humidity .

[0531] Fig. 9 The results show the molecular weight of hybrid compound 1 (spermine:AEAM=0.65:0.35) at 4.5 v% CO measured using DVS gravimetric analysis at different temperatures. 2 CO 2 Adsorption performance as a function of water pressure (kPa). Fig.10 The H of hybrid compound 1 (spermine:AEAM=0.65:0.35) measured using DVS gravimetric analysis at different temperatures is shown. 2 O adsorption capacity as a function of water pressure (kPa). Fig.11 The CO of hybrid compound 1 (spermine:AEAM=0.65:0.35) measured using DVS gravimetric analysis at different temperatures is shown. 2 The adsorption performance as a function of relative humidity. These figures show that although the adsorption performance of hybrid compound 1 varies with temperature and water pressure, high performance can be maintained by adjusting the relative humidity by adjusting the temperature and water content. These figures further indicate that CO 2 Adsorption is sensitive to relative humidity. Figure 5 As shown in the hybrid compound 1, H 2 The inflection point for O monolayer adsorption appears to be a critical threshold. Similarly, the values ​​specified for CO should be used. 2 and H 2 A breakthrough test bench for individual sensors and analyzers for quantitative assessment of discrete CO 2 and H 2 O adsorption.

[0532] Example A5. Comparison of adsorption capacity .

[0533] Fig. 12A The results of DVS gravimetric analysis of hybrid compound 1 (spermine:AEAM=0.65:0.35) on dry CO at 40°C are shown. 2 and 30% relative humidity wet CO 2 CO 2Adsorption isotherm. The figure illustrates that the adsorption capacity of hybrid compound 1 increased under wet conditions at 30% relative humidity compared to dry conditions.

[0534] Fig. 12B shows that at 25°C and 400ppmv CO 2 concentrations under DAC-related conditions, using a separate CO 2 and H 2 Hybrid compound 3 (spermine:AEAM=0.69:0.23) measured by penetration test equipment of O sensor on dry CO 2 and wet CO with different relative humidity 2 CO 2 Adsorption. Fig. 12B The pure H of hybrid compound 3 is also shown. 2 O adsorption isotherms. This figure quantitatively illustrates that, at least for the test conditions relevant to DAC applications, (1) relative to dry CO 2 (i.e. has a relative humidity of 0%), wet CO 2 Causes CO 2 Adsorption increased, (2)CO 2 The amount of adsorption is sensitive to the actual relative humidity, and (3) once a minimum relative humidity is reached, CO 2 The adsorption seems to be flat, with H 2 The inflection point of O monolayer adsorption is consistent, such as Fig. 12B The hybrid compound 3 is shown.

[0535] Described herein are exemplary systems for using functionalized chemical adsorbents in the presence of water to facilitate optimized adsorption and desorption of carbon dioxide by an adsorbent bed. The exemplary systems as described herein can provide several advantages over conventional designs and methods, including at least: improved efficiency and performance of carbon dioxide adsorption and desorption due to using variations in temperature and / or relative humidity of water within an adsorbent bed, variations in functionalized adsorbents within an adsorbent bed, and / or improved performance of the capture system due to adjusting temperature and relative humidity of water within one or more adsorbent modules within an adsorbent bed based on functionalized adsorbents within one or more adsorbent modules.

[0536] Synthesis of Aminoalkyl Substituted Disiloxanes .

[0537] Example B1. Synthesis of aminomethyl-substituted disiloxane 1,3-bis(2-aminoethylamino) with 4 equivalents of ethylenediamine (methyl)tetramethyldisiloxane .

[0538] Ethylenediamine (396 mL, 5.93 mol) was added to a 2 L three-necked round bottom flask equipped with an addition funnel and a reflux condenser. The flask was placed in an ice-water bath and heated with N 2The headspace was purged. Chloromethyldimethylethoxysilane (240 mL, 1.48 mol) was added to the addition funnel and added dropwise to the ethylenediamine over 1 hour, during which time the reaction exothermed to 90°C to 100°C. After an additional hour, the mixture was stirred by 1 The reaction was judged to be 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 allowed to cool to room temperature while stirring, at which point 300 mL of chloroform was added dropwise. The resulting mixture was stirred vigorously for 1 hour, after which the organic layer was separated and the aqueous layer was extracted with a minimum volume of chloroform. The combined organic layers were dried under reduced pressure at room temperature. The resulting material was then purified by vacuum distillation. A first fraction containing primarily cyclic byproducts and some product was collected at 40°C to 80°C and 380 mTorr. 1 The remaining material (167 g, 81% yield) was >75% pure by H NMR spectroscopy. 1 H NMR (CDCl 3 )δ:2.80(t,4H,H 2 NCH 2 CH 2 ), 2.65(t, 4H, H 2 NCH 2 ), 2.05(s, 4H, SiCH 2 ), 1.30(br s, 6H, NH&NH 2 ), 0.12(s, 12H, SiCH 3 ).

[0539] Example B2. Aminomethyl substituted disiloxane 1,3-bis(3-aminopropylaminomethyl)tetramethyldisiloxane Synthesis of alkane .

[0540] The same procedure as in Example B1 was performed, but in a 250 mL three-necked flask, 1,3-propylenediamine (52 mL, 0.62 mol), chloromethyldimethylethoxysilane (25 mL, 0.15 mol), 40 mL of water, and 40 mL of chloroform were used. The resulting material was then purified by vacuum distillation. The first fraction containing mainly cyclic byproducts and some product was collected at 40°C to 65°C. 1 The remaining material (17.6 g, 74% yield) was >95% pure by H NMR spectroscopy. 1 H NMR (CDCl 3 )δ:2.75(t,4H,H 2 NCH 2 CH 2 CH 2 ), 2.65(t, 4H, H 2 NCH 2 ), 2.05(s, 4H, SiCH 2), 1.60 (multiplet, 4H, H 2 NCH 2 CH2), 1.30 (br s, 6H, NH&NH 2 ), 0.12(s, 12H, SiCH 3 ).

[0541] Example B3. Aminomethyl substituted disiloxane 1,3-bis(2-methyl-3-aminopropylaminomethyl)tetramethyl Synthesis of 1,2-disiloxane .

[0542] The same procedure as in Example B1 was performed, 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. 1 The remaining material (0.60 g, 51% yield) was >95% pure by H NMR spectroscopy. 1 H NMR (CDCl 3 )δ: 2.8-2.5 (overlapping multiple peaks, 8H, H 2 NCH 2 CH(CH 3 )CH 2 ), 2.05 (multiplet, 4H, SiCH 2 ), 1.75 (multiplet, 2H, H 2 NCH 2 CH), 1.95 (br s, 6H, NH&NH 2 ), 0.90(d, 6H, H 2 NCH 2 CHCH 3 )0.12(s,12H,SiCH 3 ).

[0543] Example B4. Aminomethyl substituted disiloxane 1,3-bis(2,2-dimethyl-3-aminopropylaminomethyl) Synthesis of Tetramethyldisiloxane .

[0544] The same procedure as Example B1 was performed, but using 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 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 80°C to 90°C. 1 The remaining material (0.95 g, 74% yield) was >95% pure by H NMR spectroscopy. 1 H NMR (CDCl 3)δ: 3.10 (br s, 6H, NH&NH 2 ), 2.67(s, 4H, H 2 NCH2), 2.60 (s, 4H, H 2 NCH 2 C(CH 3 ) 2 CH2), 2.15(s, 4H, SiCH 2 ), 0.95(s, 12H, H 2 NCH 2 C(CH3) 2 ), 0.19(s, 12H, SiCH 3 ).

[0545] Example B5. Synthesis of aminomethyl-substituted disiloxane 1,3-bis(2-aminoethylamino) with 8 equivalents of ethylenediamine (methyl)tetramethyldisiloxane .

[0546] Ethylenediamine (793 mL, 11.9 mol) was added to a 2 L three-necked round bottom flask equipped with an addition funnel and a reflux condenser. The flask was placed in an ice-water bath and heated with N 2 The headspace was purged. Chloromethyldimethylethoxysilane (240 mL, 1.48 mol) was added to the addition funnel and added dropwise to the ethylenediamine over 1 hour, during which time the reaction exothermed to 90°C to 100°C. After an additional hour, the mixture was stirred by 1 The reaction was judged to be 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 allowed to cool to room temperature while stirring, at which point 300 mL of chloroform was added dropwise. The resulting mixture was stirred vigorously for 1 hour, after which the organic layer was separated and the aqueous layer was extracted with a minimum volume of chloroform. The combined organic layers were dried under reduced pressure at room temperature. The resulting material was then purified by vacuum distillation. A first fraction containing primarily cyclic byproducts and some product was collected at 40°C to 80°C and 380 mTorr. 1 The remaining material (326 g, 79% yield) was >90% pure by H NMR spectroscopy. 1 H NMR (CDCl 3 )δ:2.80(t,4H,H 2 NCH 2 CH 2 ), 2.65(t, 4H, H 2 NCH 2 ), 2.05(s, 4H, SiCH 2 ), 1.30(br s, 6H, NH&NH 2 ), 0.12(s, 12H, SiCH 3 ).

[0547] Example B6. Synthesis of aminomethyl-substituted disiloxane 1,3-bis(2-aminoethyl) using 10 equivalents of ethylenediamine aminomethyl)tetramethyldisiloxane .

[0548] Ethylenediamine (400 mL, 5.99 mol) was added to a 2 L three-necked round bottom flask equipped with an addition funnel and a reflux condenser. The flask was placed in an ice-water bath and heated with N 2 The headspace was purged. Chloromethyldimethylethoxysilane (97 mL, 0.59 mol) was added to the addition funnel and added dropwise to the ethylenediamine over 1 hour, during which time the reaction exothermed to 90°C to 100°C. After an additional hour, the mixture was stirred by 1 The reaction was judged to be 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 allowed to cool to room temperature while stirring, at which point 300 mL of chloroform was added dropwise. The resulting mixture was stirred vigorously for 1 hour, after which the organic layer was separated and the aqueous layer was extracted with a minimum volume of chloroform. The combined organic layers were dried under reduced pressure at room temperature. The resulting material was then purified by vacuum distillation. A first fraction containing primarily cyclic byproducts and some product was collected at 40°C to 80°C and 380 mTorr. 1 The remaining material (117 g, 70% yield) was >95% pure by H NMR spectroscopy. 1 H NMR (CDCl 3 )δ:2.80(t,4H,H 2 NCH 2 CH 2 ), 2.65(t, 4H, H 2 NCH 2 ), 2.05(s, 4H, SiCH 2 ), 1.30(br s, 6H, NH&NH 2 ), 0.12(s, 12H, SiCH 3 ).

[0549] Comparative Example B1. Attempt to synthesize aminomethyl-substituted disiloxane 1 from 1,3-bis(chloromethyl)tetramethyldisiloxane. 3-Bis(2-aminoethylaminomethyl)tetramethyldisiloxane .

[0550] Ethylenediamine (13 g, 0.216 mol, 10 equiv) was added to a 50 ml three-necked round bottom flask equipped with a nitrogen blanket, a magnetic stirring bar, a condenser and an addition funnel. It was then heated to 110°C in an oil bath. Once the temperature in the oil bath was stable, 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 this temperature overnight. The reaction was cooled and stirred for 2 hours. 1H NMR analysis was performed to check whether the reaction was complete. The reaction mixture was then poured into a 250 ml separatory funnel, partitioned between chloroform and 10% NaOH, washed three times with deionized water, once with saturated sodium chloride, and then dried over anhydrous potassium chloride. After filtration, the chloroform was stripped on a rotary evaporator to obtain a clear, colorless, viscous liquid. 1 H NMR analysis showed a product mixture containing the cyclic byproduct 2,2,6,6-tetramethyl-1-oxa-4-aza-2,6-disilacyclohexane-4-ethylamine. The desired 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane was not formed.

[0551] Comparative Example B2. Attempt to synthesize aminomethyl-substituted disiloxane 1,3-bis(iodomethyl)tetramethyldisiloxane 3-Bis(2-aminoethylaminomethyl)tetramethyldisiloxane .

[0552] Ethylenediamine (13 g, 0.216 mol, 10 equiv) was added to a 50 ml three-necked round bottom flask equipped with a nitrogen blanket, a magnetic stirring 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 was performed to check whether the reaction was complete. The reaction mixture was then poured into a 250 ml separatory funnel, partitioned between chloroform and 10% NaOH, washed three times with deionized water, once with saturated sodium chloride, and then dried over anhydrous potassium chloride. After filtration, the chloroform was stripped on a rotary evaporator to obtain a clear, colorless, viscous liquid. 1 H NMR analysis showed clean formation of the cyclic byproduct 2,2,6,6-tetramethyl-1-oxa-4-aza-2,6-disilacyclohexane-4-ethylamine. The desired 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane was not formed. 1 H NMR (CDCl 3 )δ:2.70(t,2H,CH 2 ), 2.40(t, 2H, CH 2 ), 1.75 (overlapping s, 4H+2H, SiCH 2 NCH 2 Si+H 2 N), 0.10(s, 12H, SiCH 3 ).

[0553] Solid adsorbent materials

[0554] In these examples, MOF-274[Mg 2(dobpdc)] is used as an illustrative example. However, the present embodiments are not limited to MOF-274 and are broadly applicable to any other materials or methods according to the present disclosure.

[0555] Characterization techniques .

[0556] granularity

[0557] The average particle shape and size were characterized by scanning electron microscopy (SEM). The aspect ratio was defined as the ratio of the average width to the average length.

[0558] Determination of CO by dynamic vapor sorption analyzer (DVS) gravimetric analysis 2 and H 2 O absorption .

[0559] Study of CO using Dynamic Vapor Sorption Analyzer (DVS) Gravimetric Analysis 2 and H 2 O adsorption performance. In the experiments of this work, the gases used were CO 2 The DVS Vacuum Analyzer is designed to accurately measure the change in mass 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 often suspended on the other side of the microbalance as a "reference"). The DVS Vacuum simultaneously controls and measures the inlet and outlet flow rates of the sorbate while recording the change in sample mass. The main instrument is a microbalance (UltraBalance T M) is housed in a precisely temperature-controlled enclosure called an incubator. This ensures a highly stable instrument baseline and accurate control of vapor generation at the experimental temperature.

[0560] As shown below, two cyclic, sequential adsorption test protocols were developed. At the beginning of each test, the adsorbent material of interest was heated to 120 °C and less than 10 -5 mbar vacuum under 30-90 minutes of activation (or regeneration) step. At a given temperature, the set water partial pressure is introduced under vacuum without carrier gas interference. The weight of the sample is measured directly and continuously using an ultra-precision microbalance from Surface Measurement Systems with a resolution of 0.1 μg. All adsorption measurements in this work were performed using mass balance mode, where the mass balance standard was set to mass change per minute (dm / dt<0.0035).

[0561] CO absorption through penetration testing equipment 2 and H 2 O .

[0562] CO 2 and H 2The O adsorption performance can also be studied using a homemade breakthrough test rig. The test rig has a sample chamber containing the test sample in the form of adsorbent powder or coated form (i.e., adsorbent-binder film on a substrate), and separate and calibrated CO ions located at both the gas inlet before the sample chamber and the gas outlet after the sample chamber. 2 and relative humidity (RH) sensors. Dry or wet CO with preset RH levels 2 Under these conditions, the test equipment can measure CO 2 and H 2 Individual breakthrough curves for O. The absorption can be calculated by integrating the breakthrough curve over time.

[0563] CO2 and H 2 O uptake and kinetics .

[0564] CO 2 Absorption or capacity is expressed in terms of CO adsorbed per gram of adsorbent 2 The number of grams (gCO 2 / g adsorbent). CO 2 Absorption can usually be considered to grow exponentially with time, which can be expressed as Where Q max and Q (t) are the equilibrium absorption and the absorption at a given adsorption time t (min), respectively, and k is a characteristic of the exponential growth with the unit of 1 / min. The term k is used to compare CO 2 The kinetics or rate of absorption, i.e., the larger the k, the higher the CO 2 The absorption kinetics are faster.

[0565] Example C1. General Procedure for MOF and Adsorbent Synthesis .

[0566] First, the MOF is synthesized by an aqueous preparation, washed three times with water, and washed three times with isopropanol. The reaction can be carried out using a non-aqueous solvent such as a dimethylformamide (DMF) / methanol (MeOH) mixture, an aqueous solvent, or both, as disclosed in PCT / US2022 / 082243. The material is then dried by vacuum filtration to obtain approximately 70% to 75% solvated material. To prepare the material for loading, it is desolvated in a 120°C vacuum oven overnight to reduce the alcohol content to 0.5-1 equivalents of isopropyl alcohol (IPA) / metal site, thereby protecting the open metal sites from oxidation while also removing excess solvent from the pores of the MOF. As Fig.18 As shown, through 1 H NMR determines how much residual solvent (e.g., Mg) remains in the MOF. 2 (dobpdc) 1(alcohol) x), the exact molar amount of MOF can be determined. Thus, by adding 1-4 equivalents of amine in a nonpolar solvent, a Mg 2 (dobpdc) 1 (amine) x Composition of materials. Fig.19 Shown in is a SEM image of an exemplary MOF-274 (sample ID #A2111) prepared according to the standard aqueous procedure.

[0567] Example C2. General method for analyzing amine content by NMR .

[0568] To digest the MOF with added amine, 10 mg of the material was mixed with 20 μL of 35% DCl in D 2 O solution, 200 μL of D 2 O and 600 μL DMSO-d 6 The vial was sonicated to dissolve the matrix and 1 H NMR. By comparing the backbone ligand peaks (H 4 dobpdc) and amine peak 1 H NMR integration was used to determine the loading amount.

[0569] Example C3. Particle Size Reduction .

[0570] The particle size or length of the rod-like crystals can be reduced by a number of options including, but not limited to, mechanical grinding such as mortar and pestle, use of a microfluidizer, dry or wet milling, or by chemical means such as incorporation of crystal growth inhibitors. Table 1 summarizes the particle size and aspect ratio of MOF-274 prepared according to some embodiments.

[0571] Table 1. Average particle size and aspect ratio of MOF-274 prepared with and without crystal growth inhibitor .

[0572]

[0573] Example C4. General procedure for the synthesis of small-sized MOF-274 using a crystal growth inhibitor .

[0574] By first adding x moles of H 4 Mg dobpdc, y moles of a synthetic crystal growth inhibitor and (x)*4+(y)*2 moles of NaOH were dissolved in water by heating to 60°C to synthesize 2 (dobpdc). Exemplary synthetic crystal growth inhibitors include, but are not limited to, salicylic acid (SA), 4-fluorosalicylic acid (FSA), 4,4′-bisphenol (BP), 2,2′-bipyridine-5,5′-dicarboxylic acid (BPYDC), and 2,2′-bipyridine-5,5′-dimethanol (BPYDM). With respect to 99.9 mol% to 50 mol% of H 4dobpdc, the molar amount of the crystal growth inhibitor can range from 0.1 mol% to 50 mol%. Mg is added to the deprotonated solution of the linker and the crystal growth inhibitor. 2+ Aqueous solution of salt in which the counter anion is NO 3 - , Cl - Br - 、SO 4 -2 ,OAc - , O -2 、Otf - Mg 2+ The addition of salt can be done quickly (e.g. < 1 min) or dropwise over an extended period of time (e.g. > 1 h). Heat to 97 °C and under N 2 The mixture was refluxed for 12 to 16 hours. The white precipitate was washed three times with water and three times with isopropanol and stored in a solvated form for further use.

[0575] Example C5. Exemplary procedure for synthesizing small-sized MOF-274 using salicylic acid as a crystal growth inhibitor .

[0576] Preparation of Mg on a 300 mL scale 2 First, the linker, crystal growth inhibitor, and base were added to a 500 mL round-bottom flask and heated to dissolve in water. In this example, the linker, crystal growth inhibitor, and base were added to a 500 mL round-bottom flask and heated to dissolve in water. 2 The mixture was heated to 60°C and sodium hydroxide (76 mmol, 3.04 g) and H 4 dobpdc (18 mmol, 4.94 g) and salicylic acid (2 mmol, 0.276 g) were dissolved in water (220 mL) in a flask until the solution became clear. 3 ) 2 The hexahydrate (45 mmol, 11.54 g) was dissolved in 80 mL of water in a separate container and quickly added to the deprotonated linker solution to precipitate the MOF. The mixture was reacted in an open flask at ambient pressure and gently refluxed at about 97 ° C for 12-16 hours. The reaction produced the MOF compound Mg 2 (dobpdc)(salicylate) x , which was subsequently washed three times with water, three times with isopropanol, and stored in alcohol. To measure the surface area, the material was activated at 250°C to obtain the highest absorption. For each individual batch, the reaction produced 4.2 g to 4.7 g (72% to 81% yield) of Mg 2 (dobpdc)(salicylate)x. The material can be desolvated at 85°C and loaded normally as conventional MOF-274. Fig. 20Shown are SEM images of exemplary MOF-274 prepared using salicylic acid (left) and fluorosalicylic acid (right) as crystal growth inhibitors.

[0577] Example C6. Exemplary process for synthesizing small-sized MOF-274 using 4,4′-biphenol as a crystal growth inhibitor. sequence .

[0578] Preparation of Mg on a 20 mL scale 2 First, the linker, crystal growth inhibitor, and base were added to a 20 mL scintillation vial and heated to dissolve in water. In this example, sodium hydroxide (4 mmol, 0.160 g), H 4 dobpdc (0.9 mmol, 0.247 g) and 4,4′-bisphenol (0.1 mmol, 0.019 g) were dissolved in water (10 mL) in a vial until the solution became clear. 3 ) 2 The hexahydrate (2 mmol, 0.512 g) was dissolved in 5 mL of water in a separate container and quickly added to the deprotonated linker solution to precipitate the MOF. The mixture was reacted in a vial at ambient pressure and gently refluxed at about 97 °C for 12-16 hours. The reaction produced the MOF compound Mg 2 (dobpdc)(BP) x , which was subsequently washed three times with water, three times with isopropanol, and stored in alcohol. To measure the surface area, the material was activated at 250 °C to obtain the highest absorption. The reaction produced Mg in yields between 37% and 72%, depending on the amount of inhibitor used. 2 (dobpdc)(BP) x The material can be desolvated at 85 °C and loaded normally as conventional MOF-274. Fig.21 Shown is the powder X-ray diffraction spectrum of MOF-274 synthesized using 4,4′-biphenol as a crystal growth inhibitor, where the MOF-274 phase is retained at 50 mol% BP input. Fig. 22 As shown, the incorporation of 4,4'-biphenol significantly reduced the particle size.

[0579]

[0580] Example C7. Exemplary procedure for the synthesis of small-sized MOF-274 using BPYDC as a crystal growth inhibitor .

[0581] Preparation of Mg on a 20 mL scale 2 First, the linker, crystal growth inhibitor, and base were added to a 20 mL scintillation vial and heated to dissolve in water. In this example, sodium hydroxide (4 mmol, 0.160 g), H4 dobpdc (0.9 mmol, 0.247 g) and 2,2′-bipyridine-5,5′-dicarboxylic acid (0.1 mmol, 0.024 g) were dissolved in water (10 mL) in a vial until the solution became clear. 3 ) 2 The hexahydrate (2 mmol, 0.512 g) was dissolved in 5 mL of water in a separate container and quickly added to the deprotonated linker solution to precipitate the MOF. The mixture was reacted in a vial at ambient pressure and gently refluxed at about 97 °C for 12-16 hours. The reaction produced the MOF compound Mg 2 (dobpdc)(BPYDC) x , which was subsequently washed three times with water, three times with isopropanol, and stored in alcohol. To measure the surface area, the material was activated at 250 °C to obtain the highest absorption. The reaction produced Mg in yields between 68% and 74%, depending on the amount of inhibitor used. 2 (dobpdc)(BPYDC)x. The material can be desolvated at 85°C and loaded normally as conventional MOF-274. Fig.23 Shown is the powder X-ray diffraction spectrum of MOF-274 synthesized using 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC) as a crystal growth inhibitor. When BPYDC input is up to 50 mol%, the MOF-274 phase is retained. Fig.24 As shown, the incorporation of BPYDC significantly reduced the particle size.

[0582]

[0583] Example C8. Exemplary procedure for the synthesis of small-sized MOF-274 using BPYDM as a crystal growth inhibitor .

[0584] Preparation of Mg on a 20 mL scale 2 First, the linker, crystal growth inhibitor, and base were added to a 20 mL scintillation vial and heated to dissolve in water. In this example, sodium hydroxide (4 mmol, 0.160 g), H 4 dobpdc (0.9 mmol, 0.247 g) and 2,2′-bipyridine-5,5′-dimethanol (0.1 mmol, 0.022 g) were dissolved in water (10 mL) in a vial until the solution became clear. 3 ) 2The hexahydrate (2 mmol, 0.512 g) was dissolved in 5 mL of water in a separate container and quickly added to the deprotonated linker solution to precipitate the MOF. The mixture was reacted in a vial at ambient pressure and gently refluxed at about 97 °C for 12-16 hours. The reaction produced the MOF compound Mg 2 (dobpdc)(BPYDM) x , which was subsequently washed three times with water, three times with isopropanol, and stored in alcohol. To measure the surface area, the material was activated at 250 °C to obtain the highest absorption. The reaction produced Mg in yields ranging from 53% to 81%, depending on the amount of inhibitor used. 2 (dobpdc)(BPYDM) x . Fig.25 Shown is the powder X-ray diffraction spectrum of MOF-274 synthesized using 2,2′-bipyridine-5,5′-dimethanol (BPYDM) as a crystal growth inhibitor. The particle length of MOF-274 initially decreases with increasing BPYDM incorporation. However, as Fig.26 As shown, further increasing the BPYDM loading leads to an increase in particle length and a decrease in aspect ratio.

[0585]

[0586]

[0587] Example C9. Bare MOF Example: Improving CO 2 Kinetics of absorption .

[0588] Comparative Example-1 (Comparative-1): Following the general procedure described in Example C1, an aqueous solvent (H 2 O) Preparation of a bare MOF sample with ID A2173.

[0589] Comparative Example-2 (Comparative-2): A bare MOF sample with ID A315B was prepared following the general procedure described in Example C5, but using non-aqueous solvent DMF.

[0590] Inventive Example-1 (Inventive Example-1): According to the general procedure described in Example C1, an aqueous solvent (H 2 O) Preparation of a bare MOF sample with ID A2177.

[0591] Inventive Example-2 (Inventive Example-2): A bare MOF sample with ID A316 was prepared according to the general procedure described in Example C5, but using salicylic acid (SA) as a crystal growth inhibitor and an aqueous solvent (H 2 O).

[0592] Inventive Example-3 (Inventive Example-3): A bare MOF sample with ID A39C was prepared according to the general procedure described in Example C5, but using salicylic acid (SA) as a crystal growth inhibitor and an aqueous solvent (H 2 O).

[0593] Table 2 summarizes the synthesis details, particle size, aspect ratio, and the dry CO 2 CO measured using DVS gravimetric analysis 2 The combination of reduced particle size, increased aspect ratio, and aqueous MOF synthesis apparently leads to MOFs with significantly improved CO absorption performance. 2 Absorption kinetics of MOFs.

[0594] Table 2. MOF synthesis details, particle size, aspect ratio and CO 2 performance .

[0595]

[0596] Example C10. Adsorbent Example: Improving CO 2 Kinetics of absorption .

[0597] Aqueous synthesis of MOF-274[Mg 2 (dobpdc)] is used as an illustrative example. An exemplary adsorbent material is MOF-274 synthesized using an aqueous solvent and further functionalized with a hybrid amine consisting of spermine and AEAM according to the present disclosure and as disclosed in PCT / US2023 / 060396 and PCT / US2023 / 021542. Fig. 27 Shown are the chemical structures of spermine and some exemplary aminosiloxanes. The chemical structures of other aminosiloxanes can be found in the present disclosure and PCT / US2023 / 060396 and PCT / US2023 / 021542. MOF-274 (typically including hexagonal channels) synthesized according to the general procedure as described in Example C1 has a narrow and long rod shape with a length of 1 to several microns (Fu et al., Science Advances, 2023, 9, 6 and US 2022 / 0266219).

[0598] MOF-274 prepared according to Example C1, an adsorbent functionalized with spermine and AEAM was used as a comparative example (hereinafter referred to as Comparative-3) (GE115-A259). MOF-274 (ID#A21) has a particle size of about 2.2 μm ( Fig.28 ).

[0599] Fig.29Shown is an exemplary SEM image of an embodiment of the present invention (hereinafter referred to as Invention-4) (GE115-A272). GE115-A259 and GE115-A272 used the same batch of MOF. The only difference was that the MOF used for GE115-A272 was ground with a mortar and pestle before amine loading to reduce the particle length from 2.2 μm to 0.8 μm. Fig.30 Shown is an exemplary SEM image of another inventive example (hereinafter referred to as Invention-5) (GE115-A279). The MOF used for GE115-A279 was mechanically ground prior to amine loading to reduce particle length.

[0600] Using DVS gravimetric analysis, the 2 Measuring CO 2 and H 2 O absorption. Detailed amine loading, CO 2 Absorption and CO 2 The kinetics are summarized in Table 3. It can be seen that the inventive examples with reduced particle length exhibit similar CO 2 absorption, but the kinetics are greatly increased.

[0601] Table 3. Detailed amine loading and CO of exemplary adsorbents including spermine and AEAM. 2 Adsorption performance .

[0602]

[0603] Example C11. Improving working capacity by adjusting the ratio of hybrid amines .

[0604] Including spermine, APAP ( Fig. 27 ; N 1 , N 1′ -((1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(propane-1,3-diamine)) and their mixtures in different ratios functionalized in aqueous MOF-274[Mg 2 (dobpdc)] was used as an illustrative example (Table 4). MOF-274 with an average particle size of 0.4 μm was synthesized according to the procedure described in Example C4. Fig.31 The penetration test equipment shown measures CO 2 and H 2 O absorption was performed under DAC-related conditions (25 °C, 50% RH and 400 ppmvv CO 2 ) was measured using the above penetration test equipment. Fig.32 Shown are 100 mbar CO measured using DVS gravimetric analysis at 120°C. 2 Concentration of dry CO2 absorption, which is used as CO at 100 mbar 2 An indication of the desorption residual under partial pressure. Subtracting the desorption residual from the adsorption capacity provides the CO 2 Estimation of absorbed working capacity ( Fig.33 The adsorbent with pure spermine (GE5-A2175) had the highest adsorption uptake under DAC-related conditions as well as the highest desorption residual amount, resulting in 0.07 g CO 2 The adsorbent with pure APAP (GE281-111B1) has greatly reduced desorption residual amount and adsorption capacity, resulting in 0.01gCO 2 / g working capacity of adsorbent. Compared with the adsorbent with pure spermine or pure APAP, the adsorbent with hybrid amines (GE283-151A and GE284-151B) can have a significantly increased working capacity.

[0605] Table 4. Adsorbents including pure spermine, pure APAP and mixtures in different ratios .

[0606] Adsorbent ID Example amine Spermine APAP GE5-A2175 Compare-4 Pure spermine 1.04 0 GE284-151B The present invention-6 Hybrid Amine 0.84 0.13 GE283-151A The present invention-7 Hybrid Amine 0.68 0.23 GE281-111B1 The present invention-8 Pure APAP 0 0.98

[0607] It has been found that one or more of reduced adsorbent particle size, increased adsorbent aspect ratio, and aqueous adsorbent synthesis results in adsorbents with significantly improved CO 2 Absorption kinetics of the adsorbent. Generally, higher CO 2 The absorption rate translates into higher CO captured per unit time. 2 , which then reduces the cost and potential energy use of capture.

[0608] definition .

[0609] As used herein, references to “an exemplary embodiment” or “one embodiment” or “some embodiments” of the present disclosure are not intended to be interpreted as excluding the existence of additional embodiments that also incorporate the recited features.

[0610] Although specific features of various embodiments of the present invention may be shown in some drawings and not in other drawings, this is for convenience only. According to the principles of the present invention, any feature of a drawing may be referenced and / or claimed in combination with any feature of any other drawing.

[0611] While the invention has been described in terms of various specific embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the claims.

[0612] When introducing elements of the various embodiments disclosed herein, the articles "a," "an," "the," and "said" are intended to mean that there are one or more of the elements. The terms "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0613] Unless otherwise indicated, approximate language as used herein, such as "substantially", "substantially" and "about" indicate that as those of ordinary skill in the art will recognize, the terms so modified may apply only to approximate degrees, rather than absolute or perfect degrees. Therefore, the values ​​modified by one or more terms (such as "about", "approximately" and "substantially") are not limited to the specified exact values. In at least some cases, approximate language may correspond to the precision of the instrument used to measure the value. In addition, unless otherwise indicated, the terms "first", "second" etc. are only used as marks in this article, and are not intended to impose order, position or hierarchical requirements on the items to which these terms are related. In addition, for example, the reference to the "second" item does not require or exclude the existence of, for example, the "first" or lower numbered items or the "third" or higher numbered items.

[0614] Unless otherwise indicated, approximate language as used herein, such as "substantially", "substantially" and "about" indicate that as those of ordinary skill in the art will recognize, the terms so modified may apply only to approximate degrees, rather than absolute or perfect degrees. Therefore, the values ​​modified by one or more terms (such as "about", "approximately" and "substantially") are not limited to the specified exact values. In at least some cases, approximate language may correspond to the precision of the instrument used to measure the value. In addition, unless otherwise indicated, the terms "first", "second" etc. are only used as marks in this article, and are not intended to impose order, position or hierarchical requirements on the items to which these terms are related. In addition, for example, the reference to the "second" item does not require or exclude the existence of, for example, the "first" or lower numbered items or the "third" or higher numbered items.

[0615] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any device or system and performing any combined method. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements that are not substantially different from the literal language of the claims.

[0616] It will be readily appreciated by those skilled in the art that some of the substituents disclosed herein depend on the presence of other substituents and are therefore optional. 9 When it is a direct key, R 1 and R 2 is an optional substituent not present in the compound. Similarly, in Formula A-II, when n is 0, in R 9 With R 10 There is a direct bond between them, and R 3 , R 4 and R 11 is an optional substituent that is not present in the compound. The optional nature of a substituent in one embodiment does not limit the presence of a substituent in another embodiment.

[0617] As used herein, the term "alkyl", whether used alone or in compound words such as "haloalkyl", includes straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl and isopropyl, or the different butyl, pentyl or hexyl isomers. Alkyl groups defined by multiple carbon atoms, such as C 6 Alkyl groups are understood to have that many carbon atoms, but are not otherwise limited.

[0618] As used herein, the term "heteroalkyl" refers to an alkyl chain in which at least one of the atoms forming the backbone of the chain is other than carbon.

[0619] As used herein, "aminoalkyl" includes N groups substituted with straight or branched chain alkyl groups.

[0620] As used herein, the term "halogen" or "halide", whether used alone or in a compound word such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. In addition, when used in a compound word such as "haloalkyl", the alkyl group may be partially or fully substituted with the same or different halogen atoms. Examples of "haloalkyl" include F 3 C、ClCH 2 CF 3 CH 2 and CF 3 CCl 2 The term "haloalkoxy" and the like are defined similarly to the term "haloalkyl". Examples of "haloalkoxy" include CF 3 O、CCl 3 CH 2 O.F 2 CHCH 2 CH 2 O and CF 3 CH 2 O.

[0621] As used herein, the term "heterocycle" means a ring in which at least one of the atoms forming the ring backbone is not carbon. Unless otherwise indicated, a heterocycle may be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocycle satisfies Hückel's rule, the ring is also referred to as a "heteroaryl" or aromatic heterocycle. A "saturated heterocycle" refers to a heterocycle containing only single bonds between ring members.

[0622] As used herein, the term "aminosilicone group" includes functional groups containing both an amine group and a siloxane group (also known as a disiloxane group), wherein the siloxane group includes a Si-O-Si linkage.

[0623] 1 H NMR spectra are reported in ppm downfield from tetramethylsilane; “s” indicates a singlet, “d” indicates a doublet, “dd” indicates a doublet of a doublet, “ddd” indicates a doublet of a doublet of a doublet, “t” indicates a triplet, “m” indicates a multiplet, and “brs” indicates a broad singlet.

[0624] As used herein, the terms "software" and "firmware" are interchangeable and include any computer program stored in a memory for execution by a processor, including RAM memory, ROM memory, EPROM memory, EEPROM memory, and non-volatile RAM (NVRAM) memory. The above memory types are examples only and are not limited to the types of memory that can be used to store computer programs.

[0625] As used herein, a processor may include any programmable system, including systems using microcontrollers, reduced instruction set circuits (RISC), application specific integrated circuits (ASICs), logic circuits, and any other circuits or processors capable of performing the functions described herein. The above examples are exemplary only and are therefore not intended to limit the definition and / or meaning of the term "processor" in any way.

[0626] The systems and processes are not limited to the specific embodiments described herein. In addition, the components of each system and each process can be practiced independently and separated from other components and processes described herein. Each component and process can also be used in combination with other component packages and processes.

[0627] As used herein, the term "non-transitory computer-readable medium" is intended to mean any tangible computer-based device implemented in any method or technology for short-term and long-term storage of information, such as computer-readable instructions, data structures, program modules and submodules, or other data in any device. Therefore, the methods described herein may be encoded as executable instructions embodied in a tangible non-transitory computer-readable medium, including but not limited to storage devices and / or memory devices. Such instructions, when executed by a processor, cause the processor to perform at least a portion of the methods described herein. In addition, as used herein, the term "non-transitory computer-readable medium" includes all tangible computer-readable media, including but not limited to non-transitory computer storage devices, including but not limited to volatile and non-volatile media, and removable and non-removable media such as firmware, physical and virtual storage devices, CD-ROMs, DVDs, and any other digital sources such as networks or the Internet, as well as digital means to be developed, with the only exception of transient propagation signals.

Claims

1. A functionalized adsorbent comprising: Adsorbents; and at least one functionalized ligand comprising an aminosilicone group; The adsorbent has an average particle length of ≤3 μm.

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

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

10.

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

5. The functionalized adsorbent according to claim 4, wherein the MOF metal or metal-containing cluster comprises a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, their ions, their hydrates, their salts, their halides, their fluorides, their chlorides, their bromides, their iodides, their nitrates, their acetates, their sulfates, their phosphates, their carbonates, their oxides, their formates, their carboxylates, and combinations thereof.

6. The functionalized adsorbent according to claim 4, wherein the MOF linker comprises a linker selected from the group consisting of: a polyhedral linker, 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid (H4dobpdc), 4,4′-dioxybiphenyl-3,3′-dicarboxylate (dobpdc 4 -), 4,4"-dioxo-[1,1':4',1"-terphenyl]-3,3"-dicarboxylate (dotpdc 4 -), 2,5-dioxybenzene-1,4-dicarboxylate (dobdc 4 -), 4,6-dihydroxyisophthalic acid (m-dobdc 4 -), 3,3′-dioxo-biphenyl-4,4′-dicarboxylate (p-carboxylate-DOBPDC 4 -), 4,4′-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4′-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4′-dihydroxyazobenzene-3,3′-dicarboxylic acid (H4OSA), dicarboxylates, terephthalic acid, tricarboxylates, 1,3,5-benzenetricarboxylic acid, nitrogen azoles, tetrazoles, 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-Benzenedicarboxylic acid, terephthalic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4′-diaminophenylmethane-3,3′-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, floret-3,9-dicarboxylic acid, floret dicarboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-2 50-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-cis-dicarboxylic acid, 2,2′-Biquinoline-4,4′-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenonedicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E 400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazine dicarboxylic acid, 5,6-dimethyl-2,3-pyrazine dicarboxylic acid, 4,4'-diaminodiphenyl ether diimide dicarboxylic acid, 4,4'-diaminodiphenyl methane diimide dicarboxylic acid, 4,4'-diaminodiphenyl sulfone diimide dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 8-methoxy-2,3-naphthalene dicarboxylic acid, 8-nitro-2,3-naphthalene dicarboxylic acid, 8-sulfo-2,3-naphthalene dicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2'-3'-diphenyl-p-terphenyl-4,4"-dicarboxylic acid, di phenyl ether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, trihexadecanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dicarboxylic acid Hydrogenated anthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorescein ring-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2′,5′-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-deoxy-1,5-dicarboxylic acid, Hydrobornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurinetricarboxylic acid, 1,1-dioxide-pyro[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, pyro[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, pyro[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, pyro[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-dodecane tetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, polyhedral linkers, dihedral linkers, trihedral linkers, tetrahedral linkers, pentahedral linkers, hexahedral linkers, heptahedral linkers, octahedral linkers, mixed linkers, asymmetric linkers, metal linkers, N-heterocyclic linkers, their protonated, partially or completely deprotonated forms, and combinations thereof.

7. The functionalized adsorbent of claim 1, wherein the adsorbent has an aspect ratio > 0.

2.

8. The functionalized adsorbent of claim 1, wherein the adsorbent has an average particle length of <1 μm.

9. The functionalized adsorbent according to claim 1, wherein the at least one functionalized ligand comprising an aminosilicone group is an amino-substituted siloxane of formula (A-II), formula (A-III), formula (A-IV), formula (AV), formula (A-VI), or formula (A-VII). in: R1, R2, R3, R4, R9, R 10 , R 13 , R 14 and R 18 Each is independently selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C3-C6 branched chain alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; R5, R6, R 11 , R 15 and R 17 each independently selected from the group consisting of a direct bond, a substituted or unsubstituted C1-C6 straight chain alkyl, a substituted or unsubstituted C3-C6 branched chain alkyl, a C1 alkyl, a C2 alkyl, a C3 alkyl, a C4 alkyl, a C5 alkyl and a C6 alkyl, R7, R8, R 12 and R 16 Each is 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) in: The wavy bond indicates the bonding position 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 each independently selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C3-C6 branched chain alkyl, substituted or unsubstituted straight chain heteroalkyl, substituted or unsubstituted C1-C6 straight chain heteroalkyl, substituted or unsubstituted branched chain heteroalkyl, substituted or unsubstituted C3-C6 branched chain heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; R 25 and R 26 R is each independently selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C1-C3 straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C3-C6 branched chain alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl and substituted or unsubstituted C4-C6 cycloalkyl, or when taken together, R 25 and R 26 forming a monocyclic ring selected from the group consisting of heterocycloalkyl and heteroaryl; R 27 , R 28 and R 29 Each is 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, an ether, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2-, and -NHCH2CH2CH2CH2-; R 30 Selected from the group consisting of hydrogen, substituted or unsubstituted straight chain alkyl, substituted or unsubstituted C1-C6 straight chain alkyl, substituted or unsubstituted C1-C3 straight chain alkyl, substituted or unsubstituted branched chain alkyl, substituted or unsubstituted C3-C6 branched chain alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocycloalkyl and heteroaryl; j is an integer ranging from 0 to 20; k is an integer ranging from 0 to 20; m is an integer in the range of 0 to 20; and n is an integer ranging from 0 to 20.

10. The functionalized adsorbent according to claim 1, wherein the at least one functionalized ligand comprising an aminosilicone group is selected from the group consisting of: as well as 11. An adsorbent system comprising the functionalized adsorbent according to claim 1.

12. A method for preparing an adsorbent, the method comprising: (I) forming a mixture, the mixture comprising: Adsorbent precursors; Crystal growth inhibitors; optional solvent; and optionally a non-solvent; and (II) reacting the mixture; The adsorbent has an average particle length of ≤3 μm.

13. The method of claim 12, wherein the sorbent precursor comprises a MOF linker and a MOF metal or a metal-containing cluster.

14. The method of claim 12, wherein the solvent comprises an aqueous solvent.

15. The method of claim 12, wherein the crystal growth inhibitor is selected from the group consisting of salicylic acid, 4-fluorosalicylic acid, 4,4'-biphenylene glycol, 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC), 2,2'-bipyridine-5,5'-dimethanol (BPYDM), benzoic acid, biphenylene glycol, bipyridine, and combinations thereof.

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