Sorbent compositions, systems, and methods

Abstract

To provide sorbents functionalized with ligands having an aminosilicone functional group, and methods of making the same.SOLUTION: There is provided a functionalized sorbent comprising: a sorbent; and at least one functionalization ligand comprising an aminosilicone group, wherein the sorbent has an average particle length of 3 μm or less. It is preferable that the functionalized sorbent further comprises one or more functionalized ligands that do not contain amino silicone groups. A method of making a sorbent comprises: (I) forming a mixture comprising: a sorbent precursor; a crystal growth inhibitor; optionally a solvent; and optionally a non-solvent; and (II) reacting the mixture, wherein the sorbent has an average particle length of 3 μm or less.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure generally relates to sorbents functionalized with ligands having amino silicone functional groups, methods for producing the same, and methods for using the same. The present disclosure generally also relates to methods for producing aminoalkyl-substituted disiloxanes and aminoalkyl-substituted disiloxanes produced by the methods. The present disclosure generally also relates to collection systems, particularly collection systems that contribute to the optimization of carbon dioxide gas adsorption and desorption by water management and adsorbent beds using functionalized sorbents. The present disclosure generally also relates to systems and methods for modeling post-combustion or direct air carbon capture systems, particularly for modeling the predicted performance of novel sorbents (particularly organometallic structures) in post-combustion or direct air carbon capture systems, and systems and methods for operating post-combustion or direct air carbon capture systems using one or more promising sorbents based on carbon capture performance values determined by the modeling.

Background Art

[0002] Solid sorbents are useful for a wide variety of applications. For example, they are particularly useful for use in carbon capture sorbent systems, such as post-combustion carbon capture (PCC) and direct air capture (DAC) of carbon dioxide (CO 2 ). Solid sorbents used for carbon capture provide a promising and technically and economically superior alternative to conventional liquid amine-based CO 2 capture processes. For example, solid sorbents tend to have superior adsorption capacity, lower regeneration energy requirements, lower system complexity, and lower environmental and safety risks compared to active liquid amines.

[0003] There are two types of sorbent materials based on their adsorption mechanisms. The first type of physical sorbent is CO 2 and H 2To absorb gas species such as O, it relies on non-covalent interactions (such as van der Waals interactions, dipole-dipole interactions, etc.). Examples of physical sorbents include activated carbon, zeolites, and metal-organic frameworks (MOFs). The second type of chemisorbent adsorbs CO through reversible chemical reactions and the formation of ammonium carbamate, carbamic acid, ammonium carbonate, and / or ammonium bicarbonate. Specific examples of chemisorbents include amine-functionalized silica particles, amine-functionalized polymers and resins, amine-functionalized metal-organic frameworks (MOFs), and amine-functionalized covalent organic frameworks (COFs). 2 As a result of chemical bonding, chemisorbent materials generally have better selectivity for CO adsorption compared to physical sorbent materials towards interfering chemical species such as N, methane, and CO. However, the effectiveness of chemisorbent systems is limited by the compositional properties of the functionalized molecules performing chemisorption and the functionalization process. Therefore, there is a need for functionalized sorbents containing chemically and thermally stable molecular species that selectively absorb CO with high capacity and fast reaction rates.

[0004] Regarding this, in at least some known industrial and power generation processes, there may be a gas stream containing pollutants in the form of CO. Therefore, a collection system may be used to remove pollutants from the gas stream before discharging the exhaust stream into the atmosphere. For example, a carbon capture system may be used to capture CO and store it underground to reduce the amount of CO released into the atmosphere. 2 In at least some known carbon capture systems, an adsorbent bed may be used to capture and release CO. In some known systems, to improve the adsorption capacity and efficiency of the system, a solid sorbent material is used together with the adsorbent bed, in contrast to other known systems that use a liquid amine-based CO capture process. 2 To adsorb selectively, the chemisorbent materials generally have better selectivity for CO adsorption compared to physical sorbent materials towards interfering chemical species such as N, methane, and CO. However, the effectiveness of chemisorbent systems is limited by the compositional properties of the functionalized molecules performing chemisorption and the functionalization process. Therefore, there is a need for functionalized sorbents containing chemically and thermally stable molecular species that selectively absorb CO with high capacity and fast reaction rates. 2 To adsorb selectively, the chemisorbent materials generally have better selectivity for CO adsorption compared to physical sorbent materials towards interfering chemical species such as N, methane, and CO. However, the effectiveness of chemisorbent systems is limited by the compositional properties of the functionalized molecules performing chemisorption and the functionalization process. Therefore, there is a need for functionalized sorbents containing chemically and thermally stable molecular species that selectively absorb CO with high capacity and fast reaction rates.

[0005] Regarding this, in at least some known industrial and power generation processes, there may be a gas stream containing pollutants in the form of CO. Therefore, a collection system may be used to remove pollutants from the gas stream before discharging the exhaust stream into the atmosphere. For example, a carbon capture system may be used to capture CO and store it underground to reduce the amount of CO released into the atmosphere. 2 Regarding this, in at least some known industrial and power generation processes, there may be a gas stream containing pollutants in the form of CO. Therefore, a collection system may be used to remove pollutants from the gas stream before discharging the exhaust stream into the atmosphere. For example, a carbon capture system may be used to capture CO and store it underground to reduce the amount of CO released into the atmosphere. 2 To capture and store it underground and reduce the amount of CO released into the atmosphere, a carbon capture system may be used. 2 To capture and store it underground and reduce the amount of CO released into the atmosphere, a carbon capture system may be used.

[0006] In at least some known carbon capture systems, an adsorbent bed may be used to capture and release CO. 2 In at least some known carbon capture systems, an adsorbent bed may be used to capture and release CO. 2 In some known systems, to improve the adsorption capacity and efficiency of the system, a solid sorbent material is used together with the adsorbent bed, in contrast to other known systems that use a liquid amine-based CO capture process. 2Adsorption and desorption can be enhanced. However, the effectiveness of chemisorbent systems is often limited by functionalization and details of operating conditions.

[0007] CO 2 To increase the capture amount, in at least some known carbon capture systems, water is used to enhance the CO 2 capture efficiency. For example, a carbon capture system may use wet conditions to enhance the CO 2 adsorption performance. However, if the adsorption amount of H 2 O is too large, due to the interference of H 2 O molecules, the CO 2 adsorption capacity of the chemisorbent material used in the adsorbent bed may be reduced. Therefore, there is a need for a capture system that uses a functionalized chemisorbent in the presence of water to optimize the efficiency and productivity of carbon dioxide adsorption and desorption.

[0008] In this regard, aminoalkyl-substituted disiloxanes are useful for a variety of applications. For example, they are particularly useful for carbon capture systems or aminosilicone-based products.

[0009] Substituted disiloxanes are often produced via a plurality of known reactions. However, the known reactions may be limited in scope and may not be effective for the production of aminoalkyl-substituted disiloxanes. For example, the reaction pathway used in the process described in Chinese Patent Application Publication No. 102675596 is not suitable for aminoalkyl-substituted disiloxanes due to side reactions that preferentially produce cyclic products. Similarly, in the process described in Chinese Patent Application Publication No. 102351893, the starting materials can only be hydrolyzed into one compound. Furthermore, some processes such as those described in Li, et al., Thermochimica Acta, 2012, 545, 75 require multi-step reaction pathways and intermediate purification steps, may require a relatively large number of reaction steps, and / or may reduce the overall yield, increasing the cost and complexity of the process.

[0010] Thus, opportunities to produce aminoalkyl-substituted disiloxanes are limited. Therefore, there is a need for a simple method for producing aminoalkyl-substituted disiloxanes.

[0011] In this regard, some power plants may include a post-combustion carbon capture system configured to capture carbon dioxide (CO 2 ) from the flue gas generated. The PCC system is used to capture CO 2 from the flue gas generated in a power plant including, for example, a coal combustion system, a gas turbine, and / or a boiler. Certain PCC systems use organometallic structures to facilitate carbon capture. Organometallic structures typically include two main components: an inorganic metal component (referred to as a secondary building unit (SBU)) and an organic component (referred to as a linker). A wide variety of MOFs have been developed and tested for their capture capacity (e.g., an indicator of how effective a particular MOF is for CO 2 capture). However, there are potentially millions of combinations of metals, linkers, and other functional groups that can be used in MOFs, and it is economically difficult to create and study each possible combination in the real world.

[0012] This disclosure separately and collectively addresses these related needs.

PRIOR ART DOCUMENTS

PATENT DOCUMENTS

[0013]

PATENT DOCUMENT 1

PATENT DOCUMENT 2

NON-PATENT DOCUMENTS

[0014]

NON-PATENT DOCUMENT 1

SUMMARY OF THE INVENTION

[0015] In one aspect, a functionalized sorbent is provided. The functionalized sorbent includes a sorbent and one or more functionalized ligands including an aminosilicone group. The sorbent has an average particle length of 3 μm or less.

[0016] In another aspect, a method for manufacturing a sorbent is provided. The method includes (I) forming a mixture including a sorbent precursor, a crystal growth inhibitor, a solvent as an optional component, and a non-solvent as an optional component, and (II) reacting the mixture. The sorbent has an average particle length of 3 μm or less.

[0017] In another aspect, a method for collecting one or more gases is provided. The method includes (I) a step of exposing a gas source including one or more gases to a functionalized sorbent, the functionalized sorbent including a sorbent and one or more functionalized ligands including an aminosilicone group, and (II) a step of collecting an amount of the one or more gases with the functionalized sorbent. The sorbent has an average particle length of 3 μm or less.

[0018] In another aspect, a method for recovering one or more gases is provided. The method includes (I) a step of exposing a gas source including one or more gases to a functionalized sorbent, the functionalized sorbent including a sorbent and one or more functionalized ligands including an aminosilicone group, (II) a step of collecting an amount of the one or more gases with the functionalized sorbent, and (III) a step of releasing the one or more gases from the functionalized sorbent. The sorbent has an average particle length of 3 μm or less.

Brief Description of the Drawings

[0019] The above other features, aspects, and advantages of the present disclosure can be better understood by referring to the following detailed description in conjunction with the accompanying drawings. Throughout the drawings, like reference numerals represent like members.

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12A

Figure 12B

Figure 13

Figure 14

Figure 15

Figure 16A

Figure 16B

Figure 16C

Figure 17

Figure 18

Figure 19

Figure 20

Figure 21

Figure 22

Figure 23

Figure 24

Figure 25

Figure 26

Figure 27

Figure 28

Figure 29

Figure 30

Figure 31

Figure 32

Figure 33

Figure 34

Figure 35

Figure 36

Figure 37

[0020] Unless otherwise specified, the drawings attached to this application illustrate the features of the embodiments of the present disclosure. These features are expected to be applicable to a variety of systems including one or more embodiments of the present disclosure technology. Therefore, the drawings do not include all the conventional features known to those skilled in the art that are necessary for the implementation of the embodiments disclosed in this specification.

Embodiments for Carrying Out the Invention

[0021] Multiple embodiments of the present disclosure may be combined in any manner, including various combinations of composition embodiments, system embodiments, and method embodiments. For convenience, headings are provided, but they do not separate or limit the embodiments of the present disclosure. Therefore, the following embodiments are merely illustrative and do not limit the present disclosure.

[0022] Carbon Dioxide Capture System Using Functionalized Sorbents and Water Management In one aspect, a collection system for collecting carbon dioxide is provided. The collection system includes an adsorbent bed containing one or more adsorption modules and a functionalized sorbent, and the one or more adsorption modules are oriented to receive a gas stream, adsorb carbon dioxide from the gas stream by the functionalized sorbent, and discharge the gas stream. The repair system further includes a contactor for dynamically controlling the temperature and relative humidity of the one or more adsorption modules, and a controller configured to adjust the temperature and relative humidity based on the functionalized sorbent to increase the amount of carbon dioxide collected in the adsorbent bed.

[0023] Embodiments described herein relate to systems that use functionalized chemisorbents in the presence of water to contribute to the optimization of carbon dioxide adsorption and desorption by an adsorbent bed. Advantages of the systems described herein include at least (i) improving the efficiency and performance of carbon dioxide adsorption and desorption by utilizing temperature changes in the adsorbent bed, (ii) improving the efficiency and performance of carbon dioxide adsorption and desorption by utilizing functionalized sorbents in the adsorbent bed, (iii) improving the efficiency and performance of carbon dioxide adsorption and desorption by utilizing changes in the relative humidity of water in the adsorbent bed, and (iv) improving the performance of the capture system by adjusting the temperature and relative humidity of water in one or more adsorption modules within the adsorbent bed based on the functionalized sorbent in one or more adsorption modules.

[0024] Figure 1 is a schematic diagram of an exemplary capture system 100 that can be used for the recovery of CO 2 using an adsorbent bed 102. In an exemplary embodiment, the adsorbent bed 102 includes one or more adsorption modules 104. More specifically, in an exemplary embodiment, the adsorbent bed 102 includes four adsorption modules 104a-d. In some embodiments, the capture system 100 may include more than four or less than four adsorption modules 104. Further, in an exemplary embodiment, the adsorbent bed 102 includes an inlet 106 and an outlet 108. The inlet 106 and the outlet 108 are oriented such that during operation, the gas stream 110 entering from the inlet 106 is sent through each adsorption module 104 in series towards the outlet 108. As the gas stream 110 flows through each adsorption module 104, the adsorbent bed 102 captures CO 2 from the gas stream 110, and an exhaust stream 112 is discharged from the outlet 108.

[0025] The adsorption module 104 can include a solid sorbent for preferentially capturing specific components of the gas stream 110, such as CO 2 and H 2 O. In an exemplary embodiment, the adsorption module 104 includes a sorbent and, without limitation, the CO of the adsorbent bed 102 2It includes a functionalized sorbent 114 containing one or more functionalized ligands containing amine groups, such as amino silicone groups, which contribute to improving the capture capacity and productivity. Generally, the functionalized sorbent 114 can be in a form known in the art applicable to the systems described in this application. For example, the functionalized sorbent 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.

[0026] In an exemplary embodiment, after entering the inlet 106, the gas stream 110 is directed through the first module 104a of the adsorption module 104. Each adsorption module 104 contains a functionalized sorbent 114 for adsorbing CO 2 contained in the gas stream 110. In some embodiments, the functionalized sorbent 114 may be the same in each adsorption module 104. In another embodiment, the functionalized sorbent 114 may be changed in one or more adsorption modules 104.

[0027] Generally, the gas stream 110 can be an appropriate gas known in the art applicable to the systems described in this application. For example, the gas stream 110 can be air, flue gas, post-combustion gas, natural gas, and / or combinations thereof. In an exemplary embodiment, the gas stream 110 contains CO 2 and H 2 O. In some embodiments, CO 2 can be present in the gas stream 110 in the range of about 1% to about 10% by volume. In another embodiment, CO 2 can be present in the gas stream 110 in an amount less than 1% by volume, for example, in a volume of less than about 300 - 500 ppm. In yet another embodiment, CO 2 can be present in the gas stream 110 in an amount greater than 10% by volume. In some embodiments, H 2 O can be present in the gas stream in the range of about 0.01% to about 20% by volume. In another embodiment, H 2 O can be present in the gas stream 110 in an amount less than 7% by volume, for example, in the range of about 2% to 7% like in the air during hot and humid summer, or less than 2% like in the air during cold winter. In yet another embodiment, H 2O can be present in the gas stream 110 in an amount greater than 5 volume % as in the gas after combustion.

[0028] In an exemplary embodiment, the CO of the gas stream 110 2 concentration is generally highest when the gas stream 110 enters the inlet 106. CO 2 is adsorbed onto the functionalized sorbent 114 of each of the subsequent adsorption modules 104, so as the gas stream 110 flows through the adsorption modules 104a - d towards the outlet 108, the CO 2 concentration in the gas stream 110 decreases. In an exemplary embodiment, the CO 2 concentration in the gas stream 110 flowing through the adsorption modules 104a - d is lowest at the outlet 108 in a given adsorption cycle.

[0029] In an exemplary embodiment, the collection system 100 also includes a controller 116 that dynamically adjusts the operation of the collection system 100. For example, the controller 116 can maximize the capture of CO by changing the temperature of one or more of the adsorption modules 104 and / or changing the H 2 O content within one or more of the adsorption modules 104 as described below. 2

[0030] ​Controller 116 adjusts the operating conditions of the collection system 100 by dynamically regulating the temperature of each adsorption module 104a - d. In an exemplary embodiment, the adsorption module 104 includes a contactor 118. The contactor 118 includes a contactor inlet 120 and a contactor outlet 121. In an exemplary embodiment, a first flow 122 entering from the contactor inlet 120 adjusts the temperature of the adsorption module 104 by heat transfer. The contactor 118 may use indirect or direct heat transfer to adjust the temperature of the adsorption module 104. For example, the contactor 118 may include a fluid circuit (not shown) defined between and extending between the contactor inlet 120 and the contactor outlet 121, and indirect heat transfer may occur between the first flow 122 flowing within the fluid circuit (not shown) and the functionalized sorbent 114 within the adsorption module 104. Further, for example, the contactor 118 may be in direct fluid communication with the adsorption module 104, and direct heat transfer may occur between the first flow 122 and the functionalized sorbent 114 within 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.

[0031] Controller 116 may adjust the temperature of one or more adsorption modules 104 while monitoring the regulated temperature T of the first flow 122 reg . In some embodiments, the first flow 122 may be in liquid form. In another embodiment, the first flow 122 may be in gas form. The heat transfer between the first flow 122 and the functionalized sorbent 114 within one or more adsorption modules 104, whether direct or indirect, contributes to the control of the temperature of the functionalized sorbent 114. Controller 116 may monitor the regulated temperature T of the first flow 122 using a contactor sensor 130 (shown in FIG. 4) reg . Further, controller 116 may monitor the controlled temperature T of one or more adsorption modules 104 using a module sensor 134 (shown in FIG. 4) cntl . At operating conditions where the controlled temperature T of one or more adsorption modules 104 cntl is lower than desired, controller 124 may increase the regulated temperature T of the first flow 122 regcan be selectively increased to raise the temperature of one or more adsorption modules 104. Alternatively, at operating conditions where the controlled temperature T cntl of the adsorption module 104 is higher than desired, the controller 124 can selectively lower the regulated temperature T reg of the first stream 122 to lower the temperature of one or more adsorption modules 104.

[0032] Generally, the regulated temperature T reg of the first stream 122 and the temperature of the adsorption module 104 can be set to appropriate temperatures known in the art that contribute to the capture of CO 2 by the system described herein. In some embodiments, the regulated temperature T reg of the first stream 122 can be in the range of about 0 °C to about 150 °C. In another embodiment, the regulated temperature T reg of the first stream 122 can be in the range of about 60 °C to about 250 °C. In an exemplary embodiment, the regulated temperature T reg of the first stream 122 is monitored within each adsorption module 104a - d. In some embodiments, the regulated temperature T reg of the first stream 122 may be substantially uniform among the adsorption modules 104. In another embodiment, the regulated temperature T reg of the first stream 122 may vary among the adsorption modules 104a - d.

[0033] Furthermore, the controller 116 can vary the regulated temperature T reg w of the first stream 122 in any of the adsorption modules 104a - d. For example, one or more of the adsorption modules 104a - d may include two or more module sensors 134 (shown in FIG. 4). Then, the controller 116 can create a temperature profile that includes the varying values of the regulated temperature T reg of the first stream 122 in any or all of the adsorption modules 104a - d. In some embodiments, the varying values of the regulated temperature T reg of the first stream 122 can form a gradient temperature profile in any or all of the adsorption modules 104. In another embodiment, the regulated temperature T of the first stream 122reg The variable values can form a discrete temperature profile in any or all of the adsorption modules 104.

[0034] FIG. 2 is a schematic diagram of an exemplary collection system 200 that can be used for the collection of CO 2 using the adsorbent bed 102. The embodiment shown in FIG. 2 is the same as the embodiment shown in FIG. 1, although there are differences described in this application, and the same reference numerals as those used in FIG. 1 are used in FIG. 2. The controller 116 contributes to the adjustment of the operating conditions of the collection system 200 by dynamically adjusting the relative humidity of H 2 O through the adjustment of the H 2 O content within each adsorption module 104a - d. In an exemplary embodiment, the adsorption module 104 includes an injector 202 that includes an injector inlet 204. A second flow 206 entering from the injector inlet 204 contributes to the adjustment of the relative humidity of H 2 O through the adjustment of the H 2 O content within the adsorption module 104. In an exemplary embodiment, the second flow 206 contains H 2 O. The second flow 206 can contain H 2 O in liquid form (e.g., water) or gaseous form (e.g., water vapor). In some embodiments, H 2 O can be present in the second flow 206 in the range of about 0.1 volume % to about 20 volume %. In another embodiment, H 2 O can be present in the second flow 206 in the range of about 4 volume % to about 15 volume %. In yet another embodiment, H 2 O can be present in the second flow 206 in the range of about 0.5 volume % to about 4 volume %, as is generally found in the atmosphere.

[0035] The controller 116 can adjust the H 2 O content within one or more of the adsorption modules 104 by adjusting the flow rate of the second flow 206 to one or more of the adsorption modules 104. For example, the controller 116 can monitor the relative humidity level of the H 2 O concentration C of the adsorption module 104 using a module sensor 134 (shown in FIG. 4). The relative humidity of H 2H with respect to the O concentration C 2 Under operating conditions where the O relative humidity level is lower than desired, the controller 116 selectively increases the flow rate of the second stream 206 to add additional H to one or more adsorption modules 104 2 O can be injected. In one or more adsorption modules 104, H 2 Under operating conditions where the O relative humidity level is higher than desired, the controller 116 selectively decreases the flow rate of the second stream 206 to reduce the additional H 2 O amount injected into one or more adsorption modules 104. In another embodiment, at the beginning of the adsorption cycle, the controller 116 selectively increases the flow rate of the second stream 206 to add additional H 2 O is injected to increase the relative humidity beyond the desired relative humidity level, enabling rapid H 2 O adsorption may be possible. Then, in the latter stage of the adsorption cycle, the controller 116 may selectively decrease or stop the flow of the second stream 206 to lower the relative humidity level of one or more adsorption modules 104.

[0036] The controller 116 adjusts the temperature T of the first stream 122 of one or more adsorption modules 104 reg By monitoring, the H within one or more adsorption modules 104 2 O relative humidity may be adjusted. In one or more adsorption modules 104, H 2 Under operating conditions where the O relative humidity level is higher than desired, the controller 116 selectively raises the adjusted temperature T of the first stream 122 reg To raise the temperature of one or more adsorption modules 104, and by the increase in the saturation vapor pressure under the temperature rise, H 2 O relative humidity may be caused to decrease. In one or more adsorption modules 104, H 2 Under operating conditions where the O relative humidity level is lower than desired, the controller 116 selectively lowers the adjusted temperature T of the first stream 122 reg To lower the temperature of one or more adsorption modules 104, and H 2 O relative humidity may be caused to increase. The adjusted temperature T of the first stream 122reg can be increased or decreased using any of the systems described in this application.

[0037] The controller 116 promotes the optimization of the adsorption and desorption of CO by adjusting the operating conditions of the collection system 200 to maintain the relative humidity of each adsorption module 104a - d. The relative humidity of each adsorption module 104a - d can be based on the regulated temperature T of the first stream 122 2 and the H reg O concentration C of the adsorption module 104. In an exemplary embodiment, the controller 116 adjusts the regulated temperature T of the first stream 122 2 and the H 2 O concentration C of the adsorption module 104 based on the H 2 O adsorption isotherm of the functionalized sorbent 114 within the adsorption module 104 to promote the optimization of the adsorption and desorption of CO 2 by monolayer adsorption of H reg O. 2 In general, the collection system 200 may have an appropriate adsorption isotherm that contributes to the collection of CO by the systems described in this application. There are six types of moisture adsorption isotherms as defined by the IUPAC, and their shape depends on the relative humidity and temperature (shown in Figure 3). Among these six types, types II, IV, and VI each show a flat region (e.g., an "inflection point") up to a knee point that generally corresponds to the monolayer coating and adsorption of H

[0038] O (shown in Figure 3). In an exemplary embodiment, the controller 116 adjusts the operating conditions of the collection system 200 for the monolayer coating and adsorption of H 2 O by the functionalized sorbent 114 to promote the optimization of the adsorption and desorption of CO 2 O. For example, the collection system 200 can have an adsorption isotherm of type II, type IV, or type VI (shown in Figure 3), which are particularly beneficial for ensuring monolayer coating and adsorption of H 2 O and increasing the CO 2 adsorption capacity of the functionalized sorbent 114. 2 O. 2

[0039] The adsorption isotherm depends not only on relative humidity and temperature, but also on the sorbent material. In many embodiments, the functionalized sorbent 114 can be any functionalized sorbent material that contributes to the capture of CO 2 by the systems described herein. In an exemplary embodiment, the functionalized sorbent 114 includes a sorbent and one or more functionalized ligands including an amino silicone group for optimizing the capacity and productivity of CO 2 capture against the adsorption of H 2 O.

[0040] Generally, the functionalized sorbents according to the present disclosure can be used with the compositions, systems, and methods according to the present disclosure. The functionalized sorbents are not limited to the specific embodiments disclosed herein.

[0041] In some embodiments, the functionalized sorbent includes a first type of functionalized ligand, and the first type of functionalized ligand includes one or more functionalized ligands including an amino silicone group. Generally, one or more functionalized ligands including an amino silicone group include suitable ligands contributing to the functionalized sorbents described herein. One or more functionalized ligands including an amino silicone group include only one functionalized ligand including an amino silicone group, or two or more functionalized ligands each including an amino silicone group.

[0042] Generally, the sorbent can be a known suitable sorbent contributing to the functionalized sorbents described herein. In some embodiments, the sorbent is selected from the group consisting of coordination structure compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCPs), covalent organic framework (COF) compounds, zeolite imidazolate framework (ZIF) compounds, crystalline porous materials, crystalline open framework structures, reticular chemistry, silica particles, zeolites, silicoaluminophosphates (SAPOs), aluminophosphates (AlPOs), polyaromatic frameworks (PAFs), activated carbons, molecular organic solids, and combinations thereof.

[0043] The MOF compound used in the present application is a type of compound in which an organic ligand coordinates with a metal ion or cluster to form a one-dimensional, two-dimensional, or three-dimensional structure. The metal ion or cluster acts as a joint and binds with organic ligands in multiple directions, while the organic ligand acts as a linker in the network structure. The MOF compound has modularity that can be adjusted during synthesis, bringing about precise chemical and structural control. Characteristics such as porosity, stability, particle morphology, and conductivity can be adjusted according to specific applications.

[0044] In many embodiments, the sorbent is an MOF compound comprising an MOF metal or metal-containing cluster and an MOF linker.

[0045] In some embodiments, the MOF metal can be a suitable MOF metal known in the art that contributes to the functionalized sorbent described in the present application. In another embodiment, 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 contains Mg.

[0046] In some embodiments, the MOF metal-containing cluster can be a suitable MOF metal-containing cluster known in the art that contributes to the functionalized sorbent described in the present application. In some embodiments, the MOF metal-containing cluster includes an MOF metal node and a linker strut, and the MOF metal and the linker are as defined in the present application respectively. In another embodiment, the MOF metal-containing cluster includes an MOF metal-oxy cluster.

[0047] In some embodiments, the MOF linker can be a suitable MOF linker known in the art that contributes to the functionalized sorbent described herein. Generally, the shape and connectivity of the linker contribute to the structure of the resulting MOF compound. By adjusting the linker shape, length, and functional groups, the size, shape, and internal surface properties of the MOF compound can be tailored to the target application.

[0048] In at least some embodiments, the MOF linker is a linker selected from the group consisting of polytopic linkers, ditopic linkers, tritopic linkers, tetratopic linkers, pentatopic linkers, hexatopic linkers, heptatopic linkers, octatopic linkers, mixed linkers, asymmetric linkers, metallolinkers, N - heterocyclic linkers, and combinations thereof.

[0049] In at least some embodiments, the MOF linker is a polytopic linker, 4,4’ - dihydroxy - [1,1’ - biphenyl] - 3,3’ - dicarboxylic acid (H 4 dobpdc), 4,4’ - dioxided biphenyl - 3,3’ - dicarboxylate (dobpdc 4- ), 4,4” - dioxido - [1,1’:4’,1” - terphenyl] - 3,3” - dicarboxylate (dotpdc 4- ), 2,5 - dioxido benzene - 1,4 - dicarboxylate (dobdc 4- ), 4,6 - dihydroxyisophthalic acid (m - dobdc 4- ), 3,3’ - dioxido - biphenyl - 4,4’ - dicarboxylate (para - carboxylate - dobpdc 4- ), 4,4’ - [oxalylbis(imino)]bis(2 - hydroxybenzoic acid) (H 4 ODA), 4,4’ - [1,4 - phenylene bis - (carbonylimino)]bis(2 - hydroxybenzoic acid) (H 4 TDA), 4,4’ - dihydroxyazobenzene - 3,3’ - dicarboxylic acid (H 4a linker selected from the group consisting of OSA), these protonated forms, partial or fully deprotonated forms, and combinations thereof. As another example, in at least some embodiments, the MOF linker is a linker selected from the group consisting of dicarboxylates (e.g., terephthalic acid), tricarboxylates (e.g., 1,3,5-benzenetricarboxylic acid), azolates, tetraazolates, and combinations thereof.

[0050] As another example, in at least some embodiments, the MOF linker is 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, 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, diimidodicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis-(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7,-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-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'-bipyridine-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenonedicarboxylic acid, Pluriol E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diaminodiphenyl ether diimidodicarboxylic acid, 4,4'-diaminodiphenylmethane diimidodicarboxylic acid, 4,4'-diaminodiphenyl sulfone diimidodicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2'-3'-diphenyl-p-terphenyl-4,4”-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosanedicarboxylic 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,It is a dicarboxylic acid linker selected from the group consisting of 3-dicarboxylic acid, 2,9-dichlorofluorbine-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, and combinations thereof.,

[0051] 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.

[0052] 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-peryl[1,12-bcd]thiophene-3,4,9,10-tetracarboxylic acid, perylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, meso-1,2,3,4-butane tetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenone tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, tetrahydrofuran tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, and combinations thereof.

[0053] In an exemplary embodiment, the MOF linker is 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H 4 dobpdc) and / or 4,4'-dioxide biphenyl-3,3'-dicarboxylate (dobpdc 4- ). In some embodiments, dobpdc includes 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid, its monocarboxylate form, its dicarboxylate form, its monophenoxide form, its diphenoxide form, and combinations thereof.

[0054] In some embodiments, the MOF linker is one or more of the linkers shown below.

[0055]

Chemical formula

[0056] [Chem.]

[0057] [Chem.]

[0058] In some embodiments, the MOF compound is a MOF compound of the MOF-74 family. In some embodiments, the MOF compound is a MOF compound of the MOF-274 family. In some embodiments, the MOF compound is a MOF compound of the MOF-303 family. In some embodiments, the MOF compound is Mg 2 (dobpdc).

[0059] In some embodiments, the functionalized sorbent is a functionalized MOF compound of the following formula (A-I). M x L y F A a F B b (Formula A-I) Wherein, M is a MOF metal or a metal-containing cluster, L is a MOF linker, F A is one or more functionalized ligands containing an aminosilicon group, F B is one or more functionalized ligands not containing an aminosilicon group, x is a numerical value in the range of 1 to 6, y is a numerical value in the range of 1 to 6, a is a numerical value greater than 0 and less than or equal to 2, b is a numerical value in the range of 0 to 2.

[0060] In some embodiments, the functionalized sorbent includes a second type of functionalized ligand, and the second type of functionalized ligand includes one or more functionalized ligands that do not contain an aminosilicon group. In some embodiments, the functionalized sorbent also includes one or more functionalized ligands that do not contain an aminosilicon group. Generally, one or more functionalized ligands that do not contain an aminosilicon group can include suitable ligands that contribute to the functionalized sorbents described herein. One or more functionalized ligands that do not contain an aminosilicon group may include only one functionalized ligand that does not contain an aminosilicon group, or may include two or more functionalized ligands that do not contain an aminosilicon group.

[0061] In some embodiments, one or more functionalized ligands that do not contain an aminosilicon group are selected from the group consisting of amine ligands, monoamine ligands, diamine ligands, triamine ligands, tetraamine ligands, pentaamine ligands, hexaamine ligands, polyamine ligands, alkylamine ligands, and 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-propanediamine, bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane (spermidine), triethylenetetramine, N,N'-bis(2-aminoethyl)-1,3-propanediamine, 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, N,N'-bis(3-aminopropyl)-1,4-diaminobutane (spermine), tetraethylenepentamine, and / or combinations thereof.

[0062] Generally, one or more functionalized ligands containing an aminosilicone group and one or more functionalized ligands not containing an aminosilicone group may be present in an appropriate ratio known in the art that contributes to the functionalized sorbent described in the present application. In some embodiments, the ratio is selected from the group consisting of molar ratio, weight ratio, and volume ratio. In some embodiments, one or more functionalized ligands containing an aminosilicone group and one or more functionalized ligands not containing an aminosilicone group are present in a ratio within the range of about 10:1 to about 1:10. In some embodiments, one or more functionalized ligands containing an aminosilicone group and one or more functionalized ligands not containing an aminosilicone group are present in a ratio within the range of about 9:1 to about 1:9. In some embodiments, one or more functionalized ligands containing an aminosilicone group and one or more functionalized ligands not containing an aminosilicone group are present in a ratio within the range of about 8:1 to about 1:8. In some embodiments, one or more functionalized ligands containing an aminosilicone group and one or more functionalized ligands not containing an aminosilicone group are present in a ratio within the range of about 7:1 to about 1:7. In some embodiments, one or more functionalized ligands containing an aminosilicone group and one or more functionalized ligands not containing an aminosilicone group are present in a ratio within the range of about 6:1 to about 1:6. In some embodiments, one or more functionalized ligands containing an aminosilicone group and one or more functionalized ligands not containing an aminosilicone group are present in a ratio within the range of about 5:1 to about 1:5. In some embodiments, one or more functionalized ligands containing an aminosilicone group and one or more functionalized ligands not containing an aminosilicone group are present in a ratio within the range of about 4:1 to about 1:4. In some embodiments, one or more functionalized ligands containing an aminosilicone group and one or more functionalized ligands not containing an aminosilicone group are present in a ratio within the range of about 3:1 to about 1:3. In some embodiments, one or more functionalized ligands containing an aminosilicone group and one or more functionalized ligands not containing an aminosilicone group are present in a ratio within the range of about 2:1 to about 1:2. In some embodiments, one or more functionalized ligands containing an aminosilicone group and one or more functionalized ligands not containing an aminosilicone group are present in a ratio of 1:1.

[0063] In some embodiments, one or more functionalized ligands comprising an aminosilicone group are present in an amount less than one or more functionalized ligands that do not comprise an aminosilicone group.

[0064] In some embodiments, one or more functionalized ligands comprising an aminosilicone group and one or more functionalized ligands that do not comprise an aminosilicone group are present in a ratio of about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, or about 1:10.

[0065] In many embodiments, one or more functionalized ligands comprising an aminosilicone group can be one or more functionalized ligands comprising a suitable aminosilicone group known in the art that contribute to the functionalized sorbent described herein.

[0066] In some embodiments, one or more functionalized ligands comprising an aminosilicone group comprise one or more amines selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof. In some embodiments, one or more functionalized ligands comprising an aminosilicone group comprise one or more primary amines or one or more secondary amines.

[0067] In some embodiments, one or more functionalized ligands comprising an aminosilicone group comprise one or more amines selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentamines, hexamines, polyamines, and combinations thereof.

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

[0069] In some embodiments, the one or more functionalized ligands comprising an aminosilicone group comprise a symmetric structure. In some embodiments, the one or more functionalized ligands comprising an aminosilicone group comprise an asymmetric structure.

[0070] In some embodiments, when the one or more functionalized ligands comprising an aminosilicone group comprise a disiloxane group, the one or more functionalized ligands comprising an aminosilicone group comprise the same amine on both sides of the disiloxane group. In some embodiments, when the one or more functionalized ligands comprising an aminosilicone group comprise a disiloxane group, the one or more functionalized ligands comprising an aminosilicone group comprise different amines on both sides of the disiloxane group.

[0071] In some embodiments, the one or more functionalized ligands comprising an aminosilicone group are amino-substituted siloxanes of the following formula (A-II), formula (A-III), formula (A-IV), formula (A-V), formula (A-VI), or formula (A-VII).

[0072] [Chemical formula]

[0073] [Chemical formula] Wherein, R 1 、R2 , R 3 , R 4 , R 9 , R 10 , R 13 , R 14 and R 18 are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl, and are selected from the group consisting of 3 -C 6 branched alkyl, R 5 , R 6 , R 11 , R 15 and R 17 are each independently a direct bond, substituted or unsubstituted C 1 -C 6 linear 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, and are selected from the group consisting of R 7 , R 8 , R 12 and R 16 are each independently a direct bond, substituted or unsubstituted C 1 -C 6 linear 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 and a substituent of the following formula (A-VIII), and are selected from the group consisting of

[0074]

Chemical

[0075] In some embodiments, one or more functionalized ligands comprising an amino silicone group are selected from the following group.

[0076]

Chemical formula

[0077]

Chemical formula

[0078]

Chemical formula

[0079]

Chemical formula

[0080]

Chemical formula

[0081]

Chemical formula

[0082] Figure 4 is a schematic diagram of an exemplary control system 400 that can be used for CO 2 capture in a capture system such as capture system 100 (shown in FIG. 1) and / or capture system 200 (shown in FIG. 2). In an exemplary embodiment, the controller 116 includes a memory 402 and a processor 404. The controller 116 can adjust the temperature of one or more adsorption modules 104a-d based on data received by the control system 400 from a contactor sensor 130, such as the regulated temperature T reg of the first stream 122. The controller 116 can use data stored in the memory 402 (e.g., the regulated temperature Treg Based on a comparison with a desired range), instructions stored in the memory 402, and / or data analyzed by the processor 404, the temperature of one or more adsorption modules 104a - d can be adjusted.

[0083] Furthermore, the controller 116 can, but is not limited to, control the temperature T within one or more adsorption modules 104a - d cntl and / or H 2 Based on data received by the control system 400 from the O - phase relative humidity module sensor 134, the temperature of one or more adsorption modules 104a - d can be adjusted. The controller 116 can compare data stored in the memory 402 (e.g., the desired range of control temperature T cntl and / or H 2 O relative humidity), instructions stored in the memory 402, and / or data analyzed by the processor 404, and based on this comparison, adjust the temperature of one or more adsorption modules 104a - d.

[0084] In this application, an exemplary system for using a functionalized chemisorbent in the presence of water to contribute to the optimization of carbon dioxide adsorption and desorption by an adsorbent bed will be described. The exemplary system described in this application provides several advantages, including, at least, an improvement in the efficiency and performance of carbon dioxide adsorption and desorption by utilizing temperature changes in the adsorbent bed, an improvement in the efficiency and performance of carbon dioxide adsorption and desorption by using a functionalized sorbent in the adsorbent bed, an improvement in the efficiency and performance of carbon dioxide adsorption and desorption by utilizing changes in moisture relative humidity in the adsorbent bed, and an improvement in the performance of the capture system by adjusting the temperature and moisture relative humidity within one or more adsorption modules in the adsorbent bed based on the functionalized sorbent within one or more adsorption modules.

[0085] Additional aspects of the present invention are set forth in the following embodiments section.

[0086] [Embodiment 1] A capture system for use in capturing carbon dioxide, the capture system comprising an adsorbent bed including one or more adsorption modules and a functionalized sorbent, the one or more adsorption modules being oriented to receive a gas stream, adsorb carbon dioxide from the gas stream by the functionalized sorbent, and discharge the gas stream; a contactor for use in dynamically controlling the temperature and relative humidity of the one or more adsorption modules; and a controller configured to adjust the temperature and relative humidity based on the functionalized sorbent to increase the amount of carbon dioxide captured in the adsorbent bed.

[0087] [Embodiment Item 2] The capture system according to Embodiment Item 1, wherein the contactor is oriented to receive a regulating fluid for use in dynamically controlling the temperature of the one or more adsorption modules.

[0088] [Embodiment Item 3] The capture system according to Embodiment Item 1 or Embodiment Item 2, further comprising one or more injectors oriented to discharge a moisture stream for controlling the moisture relative humidity of the one or more adsorption modules.

[0089] [Embodiment Item 4] The capture system according to any one of Embodiment Items 1 to 3, wherein the controller is further configured to lower the fluid temperature of the regulating fluid received by the contactor to promote an increase in the moisture relative humidity.

[0090] [Embodiment Item 5] The capture system according to any one of Embodiment Items 1 to 4, wherein the controller is further configured to adjust the moisture relative humidity of the one or more adsorption modules to promote an increase in the amount of carbon dioxide captured in the adsorbent bed.

[0091] [Embodiment Item 6] The collection system according to any one of Embodiment Items 1 to 5, wherein the controller is further configured to increase the relative humidity of the moisture in one or more adsorption modules to promote an increase in the amount of carbon dioxide collected by the functionalized sorbent.

[0092] [Embodiment Item 7] The collection system according to any one of Embodiment Items 1 to 6, wherein the controller is further configured to increase the pressure of the moisture flow discharged from the injector to promote an increase in the relative humidity of the moisture in one or more adsorption modules.

[0093] [Embodiment Item 8] The collection system according to any one of Embodiment Items 1 to 7, wherein the controller is further configured to adjust the temperature and relative humidity of the moisture in one or more adsorption modules to achieve a desired relative humidity based on the moisture adsorption isotherm of the functionalized sorbent.

[0094] [Embodiment Item 9] The collection system according to any one of Embodiment Items 1 to 8, wherein the temperature and relative humidity of the moisture in one or more adsorption modules are based on the relative humidity at the knee point of the moisture adsorption isotherm of the functionalized sorbent.

[0095] [Embodiment Item 10] The collection system according to any one of Embodiment Items 1 to 9, wherein one or more adsorption modules include a plurality of adsorption modules connected in a series flow arrangement.

[0096] [Embodiment Item 11] The collection system according to any one of Embodiment Items 1 to 10, wherein one or more injectors include injectors coupled to each of the plurality of adsorption modules.

[0097] [Embodiment Item 12] The collection system according to any one of Embodiment Items 1 to 11, wherein the controller is further configured to adjust the temperature and moisture relative humidity of each of the plurality of adsorption modules.

[0098] [Embodiment Item 13] The collection system according to any one of Embodiment Items 1 to 12, wherein the functionalized sorbent includes a sorbent and one or more functionalized ligands containing an amine group.

[0099] [Embodiment Item 14] The collection system according to any one of Embodiment Items 1 to 13, wherein the one or more functionalized ligands containing an amine group include one or more amines selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof.

[0100] [Embodiment Item 15] The collection system according to any one of Embodiment Items 1 to 14, wherein the one or more functionalized ligands containing an amine group include one or more amines selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentamines, hexamines, polyamines, and combinations thereof.

[0101] [Embodiment Item 16] The collection system according to any one of Embodiment Items 1 to 15, wherein the functionalized sorbent includes a sorbent and one or more functionalized ligands containing an aminosilicon group.

[0102] [Embodiment Item 17] The collection system according to any one of Embodiment Items 1 to 16, wherein the functionalized sorbent is a functionalized MOF compound of the following formula (A-I). M x L y F A a F B b (Formula A-I) In the formula, M is a MOF metal or a metal-containing cluster, L is a MOF linker, F A is one or more functionalized ligands containing an amino silicone group, F B is one or more functionalized ligands not containing an amino silicone group, x is a numerical value within the range of 1 to 6, y is a numerical value within the range of 1 to 6, a is a numerical value greater than 0 and less than or equal to 2, b is a numerical value within the range of 0 to 2.

[0103] [Embodiment Item 18] The collection system according to any one of Embodiment Items 1 to 17, wherein the MOF metal or metal-containing cluster contains a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof.

[0104] [Embodiment Item 19] The MOF linker is a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H 4 dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4''-dioxide-[1,1':4',1''-terphenyl]-3,3''-dicarboxylate (dotpdc 4- ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-dobdc 4- ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc 4- ), 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (H4 ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H 4 TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H 4(OSA), dicarboxylates, terephthalic acid, tricarboxylates, 1,3,5-benzenetricarboxylic acid, azolates, tetraazolates, 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, 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, diimidodicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis-(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7,-Hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-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'-bipyridine-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenonedicarboxylic acid, Pluriol E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diaminodiphenyl ether diimide dicarboxylic acid, 4,4'-diaminodiphenylmethane diimide dicarboxylic acid, 4,4'-diaminodiphenyl sulfone diimide dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2'-3'-diphenyl-p-terphenyl-4,4”-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosanedicarboxylic 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-dichlorofluorbine-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-f]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurintricarboxylic acid, 1,1-dioxide-perylro[1,12-bcd]thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-Naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3’,4,4’-benzophenonetetracarboxylic acid, tetrahydrofuran tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, polytopic linker, ditopic linker, tritopic linker, tetratopic linker, pentatopic linker, hexatopic linker, heptatopic linker, octatopic linker, mixed linker, asymmetric linker, metallolinker, N-heterocyclic linker, one or more linkers selected from the group consisting of protonated forms, partially or fully deprotonated forms thereof, and combinations thereof, a collection system according to any one of Embodiment Items 1 to 18.,

[0105] [Embodiment Item 20] One or more functionalized ligands containing an amino silicone group, a collection system according to any one of Embodiment Items 1 to 19, comprising one or more aminosilicones selected from the group consisting of linear aminosilicone, cyclic aminosilicone, branched aminosilicone, amino-substituted siloxane, linear amino-substituted disiloxane, cyclic amino-substituted disiloxane, linear amino-substituted trisiloxane, cyclic amino-substituted trisiloxane, linear amino-substituted tetrasiloxane, cyclic amino-substituted tetrasiloxane, linear amino-substituted polysiloxane, cyclic amino-substituted polysiloxane, silsesquioxane, octahedral silsesquioxane, and combinations thereof.

[0106] Synthesis of Aminoalkyl-Substituted Disiloxanes In one aspect, a method for producing an aminoalkyl-substituted disiloxane is provided. The method includes: I) forming a mixture including a di- or polyamine containing one or more primary amine groups 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.

[0107] In another aspect, an aminoalkyl-substituted disiloxane of formula (B-I) is provided. The formula is as follows.

[0108] [Chemical Formula] In the formula, 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 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl, R 16 and R 17 are each independently selected from the group consisting of a direct bond, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl and C 6 alkyl, R 18 and R 19 are each independently selected from the group consisting of substituents of formula (B-IV),

[0109] [Chemical Formula] In the formula, the wavy bond indicates the bonding position with formula (B-I), R 25 , R 26 , R 27 , R 28 , R 29and R 30 is each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted C 1 -C 6 linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl, and is selected from the group consisting of R 31 and R 32 is each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted C 1 -C 3 linear alkyl, substituted or unsubstituted branched 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 R 31 and R 32 forms a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl R 33 , R 34 and R 35 is each independently a direct bond, substituted or unsubstituted C 1 -C 6 linear 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, 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 selected from the group consisting of - R 36 is hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted C 1 -C 3 linear alkyl, substituted or unsubstituted branched 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, selected from the group consisting of heterocycloalkyl and heteroaryl, m is an integer from 0 to 20, provided that the aminoalkyl-substituted disiloxane is not of the following formula.

[0110]

Chemical formula

[0111] The embodiments described in the present application address at least some of the drawbacks of known methods for producing aminoalkyl-substituted disiloxanes. Exemplary embodiments described in the present application are methods for producing aminoalkyl-substituted disiloxanes, the methods comprising: I) forming a mixture comprising a di- or polyamine containing one or more primary amine groups 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. Exemplary embodiments described in the present application result in the desired product with no side reactions and / or fewer steps, better yields, and higher purity than known methods for producing aminoalkyl-substituted disiloxanes.

[0112] In many embodiments, the method is a one-pot synthesis. As used herein, a one-pot synthesis is a synthesis that occurs within a single reaction vessel. There is no need to remove intermediates from the reaction vessel for separation and / or purification. A one-pot synthesis may include one reaction or two or more reactions. One-pot syntheses are particularly beneficial for reducing the complexity of reactions and eliminating time-consuming and costly separation and purification.

[0113] In many embodiments, the aminoalkyl-substituted disiloxane is an amino-C 1 -C 6 alkyl-substituted disiloxane. Embodiments that include C 1 -C 6 alkyl groups form more thermodynamically favorably than other compounds that include large aminoalkyl substituents or other substituents. In some embodiments, the aminoalkyl-substituted disiloxane is an aminomethyl-substituted disiloxane.

[0114] 13 is an exemplary method flowchart 1310. In this exemplary embodiment, the method flowchart 1310 illustrates basic method steps of exemplary embodiments described herein and is not intended to limit the embodiments of the method. First, a mixture is formed that includes a di- or polyamine containing one or more primary amine groups and a silane (1312). The mixture is reacted in a first reaction (1314) and a hydrolysis agent is added to the mixture (1316). The mixture is then reacted in a second reaction to form an aminoalkyl-substituted disiloxane (1318).

[0115] 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):

[0116] [ka] During the ceremony, R 12 , R 13 , R 14 , R 15 , each independently represents hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C 3 -C 6 selected from the group consisting of branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R 16 and R 17 are each independently a direct bond, a substituted or unsubstituted C 1 -C 6 Linear 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 6A group consisting of alkyl, preferably C 1 -C 6 linear alkyl, more preferably C 1 alkyl selected from, R 18 and R 19 are each independently selected from the group consisting of substituents of formula (B-IV),

[0117]

Chemical formula

[0118] [Chemical formula]

[0119] In some embodiments, the aminoalkyl-substituted disiloxane is selected from the following group.

[0120] [Chemical formula]

[0121] [Chemical formula]

[0122] In some embodiments, the di- or polyamine containing one or more primary amine groups can be a suitable di- or polyamine containing one or more primary amine groups known in the art that is suitable for the method described in the present application. In another embodiment, the di- or polyamine containing one or more primary amine groups is a compound of formula (B-II).

[0123] [Chemical formula] Wherein, R 1 、R 2 、R 3 、R 4 、R 5 and R 6 are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C 3 -C 6Branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C 3 -C 6 Selected from the group consisting of branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl, R 7 and R 8 are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted C 1 -C 3 linear alkyl, substituted or unsubstituted branched 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 R 7 and R 8 form a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl, R 9 , R 10 and R 11 are each independently a direct bond, substituted or unsubstituted C 1 -C 6 linear 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 -, -NHCH2 CH 2 -, -NHCH 2 CH 2 CH 2 - and -NHCH 2 CH 2 CH 2 CH 2 selected from the group consisting of n is an integer within the range of 0 to 20, preferably within the range of 0 to 10, and more preferably within the range of 0 to 3.

[0124] In some embodiments, the silane can be a suitable silane known in the art that contributes to the methods described herein. In some embodiments, the silane is an alkoxysilane. In at least some embodiments, the silane is a compound of the following formula (B-III).

[0125]

Chemical formula

[0126] In some embodiments, R 23 and R 24 are each independently a substituted or unsubstituted C 1 -C 6 linear alkyl, a 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 selected from the group consisting of linear alkyl.

[0127] In some embodiments, R 23 is C 1 alkyl.

[0128] In some embodiments, R 24 is C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, aryl, or phenyl.

[0129]

Chemical formula

[0130] In many embodiments, reacting the mixture in the first reaction (1314) can be carried out under suitable reaction conditions known in the art that contribute to the methods described herein. In some embodiments, reacting the mixture in the first reaction (1314) includes stirring the mixture.

[0131] In many embodiments, reacting the mixture in the first reaction (1314) can be carried out for a suitable time known in the art that is conducive to the methods described herein. In some embodiments, the mixture is reacted in the first reaction (1314) for a period within the range of about 1 second to about 12 hours. In some embodiments, the mixture is reacted in the first reaction (1314) for a period within the range of about 1 second to about 6 hours. In some embodiments, the mixture is reacted in the first reaction (1314) for a period within the range of about 1 second to about 3 hours. In some embodiments, the mixture is reacted in the first reaction (1314) for a period within the range of about 1 hour to about 3 hours. In some embodiments, the mixture is reacted in the first reaction (1314) for a period within the range of about 2 hours to about 3 hours.

[0132] In some embodiments, reacting the mixture in the first reaction (1314) involves dropwise adding a silane (e.g., chloromethyldimethylethoxysilane) to a neat di- or polyamine containing one or more primary amine groups over about 1 hour. The reaction temperature rises to about 90 °C due to the exothermic reaction and is maintained at this temperature during the continuation of the reaction (for a total of about 2 - 3 hours). At this time, the HCl salt of the amine is formed and may precipitate to varying degrees depending on the amine.

[0133] In some embodiments, the hydrolyzing agent is added dropwise to the mixture (1316). In some embodiments, the hydrolyzing agent is added to the mixture over a predetermined time. In some embodiments, the hydrolyzing agent is added to the mixture over a period within the range of about 1 second to about 12 hours (1316). In some embodiments, the hydrolyzing agent is added under exothermic conditions over 30 minutes (1316) and the mixture is cooled to room temperature before reacting in the second reaction (1318).

[0134] In some embodiments, the hydrolyzing agent is added under exothermic conditions over 30 minutes (1316) before reacting the mixture in the second reaction (1318). In these embodiments, after completing the reaction (1318), the reaction mixture is cooled to room temperature.

[0135] In many embodiments, the hydrolyzing agent can be a suitable hydrolyzing agent known in the art that contributes to the methods described herein. In some embodiments, the hydrolyzing agent is an aqueous solution. In some embodiments, the hydrolyzing agent is water.

[0136] In many embodiments, reacting the mixture in a second reaction (1318) can be carried out under suitable reaction conditions known in the art that contribute to 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.

[0137] In some embodiments, further, the aminoalkyl-substituted disiloxane is extracted from the reaction mixture. In some embodiments, further, the aminoalkyl-substituted disiloxane is extracted from the reaction mixture with an organic solvent.

[0138] In some embodiments, extraction of the aminoalkyl-substituted disiloxane from the reaction mixture includes dropwise adding an organic solvent (e.g., chloroform and / or toluene) to the reaction mixture over 30 minutes and vigorously stirring the reaction mixture until it is cooled to about 1 hour or room temperature. Once cooled, the organic layer is isolated, the aqueous layer is back-extracted with a minimal amount of organic solvent, the combined organic layers are concentrated under vacuum, triturated once with an organic solvent, and dried under vacuum.

[0139] In some embodiments, the aminoalkyl-substituted disiloxane is further purified. In some embodiments, additional purification includes distillation, vacuum distillation, and / or use of heat. In some embodiments, additional purification includes use of vacuum distillation to remove impurities and by-products. In these embodiments, the residual material in the distillation pot is a product with a higher purity than the product before purification.

[0140] In many embodiments, reacting the mixture in the second reaction (1318) can be carried out at an appropriate time known in the art that contributes to the methods described herein. In some embodiments, the mixture is reacted in the second reaction (1318) for a period within the range of about 1 second to about 12 hours. In some embodiments, the mixture is reacted in the second reaction (1318) for a period within the range of about 1 second to about 6 hours. In some embodiments, the mixture is reacted in the second reaction (1318) for a period within the range of about 1 second to about 3 hours. In some embodiments, the mixture is reacted in the second reaction (1318) for a period within the range of about 1 hour to about 3 hours. In some embodiments, the mixture is reacted in the second reaction (1318) for a period within the range of about 2 hours to about 3 hours.

[0141] In many embodiments, the method may include appropriate process steps known in the art that contribute to the success of the methods described herein. Such process steps include, but are not limited to, washing, drying, filtering, purifying, separating, centrifuging, and combinations thereof. In some embodiments, the method further includes washing the aminoalkyl-substituted disiloxane compound. In some embodiments, the method further includes purifying the aminoalkyl-substituted disiloxane compound. In some embodiments, purification includes distillation, vacuum distillation, and / or use of heat. In some embodiments, the method further includes removing volatile reaction by-products.

[0142] In some embodiments, the method includes: I) forming a mixture comprising a di- or polyamine containing one or more primary amine groups and chloromethyldimethylalkoxysilane; II) reacting the mixture in a first reaction by controlled exotherm; 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.

[0143] In many embodiments, the aminoalkyl-substituted disiloxane can be used according to suitable purposes known in the art. In some embodiments, the aminoalkyl-substituted disiloxane is used in a carbon capture system. In some embodiments, the aminoalkyl-substituted disiloxane is used in an aminosilicone-based product.

[0144] Additional aspects of the disclosed technology are set forth in the following embodiments section.

[0145] [Embodiment Item 1] A method for producing an aminoalkyl-substituted disiloxane, the method comprising: I) forming a mixture comprising a di- or polyamine containing one or more primary amine groups 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.

[0146] [Embodiment Item 2] The method according to Embodiment Item 1, wherein the aminoalkyl-substituted disiloxane is a compound of the following formula (B-I).

[0147] [Chemical Formula] Wherein 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 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl, R 16 and R 17 are each independently a direct bond, substituted or unsubstituted C1 -C 6 Linear 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 Selected from the group consisting of R 18 And R 19 Are each independently selected from the group consisting of substituents of formula (B-IV),

[0148]

Chemical formula

[0149] [Embodiment Item 3] The method according to Embodiment Item 1 or Embodiment Item 2, wherein the aminoalkyl-substituted disiloxane is a compound selected from the group consisting of those shown below.

[0150] [Chemical formula]

[0151] [Chemical formula]

[0152] [Embodiment Item 4] The method according to any one of Embodiment Items 1 to 3, wherein the di- or polyamine containing one or more primary amine groups is a compound of the following formula (B-II).

[0153] [Chemical formula] In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, substituted or unsubstituted linear 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, R 7 and R 8 are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted C 1 -C 3 linear alkyl, substituted or unsubstituted branched 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 R 7 and R 8 form a single ring selected from the group consisting of heterocycloalkyl or heteroaryl, R 9 , R 10 and R 11 are each independently a direct bond, substituted or unsubstituted C 1 -C 6 linear 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 CH2 - and -NHCH 2 CH 2 CH 2 CH 2 selected from the group consisting of n is an integer from 0 to 20.

[0154] [Embodiment Item 5] The method according to any one of Embodiment Items 1 to 4, wherein the silane is a compound of the following formula (B-III).

[0155] [Chemical formula] In the formula, R 20 is selected from the group consisting of halides, fluorides, chlorides, bromides and iodides, R 21 and R 22 are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl, 3 -C 6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl, R 23 and R 24 are each independently substituted or unsubstituted C 1 -C 6 linear 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.

[0156] [Embodiment Item 6] The method according to any one of Embodiment Items 1 to 5, wherein the silane is any of the following.

[0157]

Chemical formula

[0158] [Embodiment Item 7] The method according to any one of Embodiment Items 1 to 6, wherein reacting the mixture in the first reaction includes stirring the mixture.

[0159] [Embodiment Item 8] The method according to any one of Embodiment Items 1 to 7, wherein reacting the mixture in the first reaction includes reacting the mixture for a first time.

[0160] [Embodiment Item 9] The method according to any one of Embodiment Items 1 to 8, wherein the first time is a time within the range of about 1 second to about 12 hours.

[0161] [Embodiment Item 10] The method according to any one of Embodiment Items 1 to 9, wherein the hydrolyzing agent is an aqueous solution.

[0162] [Embodiment Item 11] The method according to any one of Embodiment Items 1 to 10, wherein the hydrolyzing agent is water.

[0163] [Embodiment Item 12] The method according to any one of Embodiment Items 1 to 11, wherein the hydrolyzing agent is added to the mixture over a second time.

[0164] [Embodiment Item 13] The method according to any one of Embodiment Items 1 to 12, wherein the second time is a time within the range of about 1 second to about 12 hours.

[0165] [Embodiment Item 14] The method according to any one of Embodiment Items 1 to 13, wherein the hydrolyzing agent is dropped into the mixture.

[0166] [Embodiment Item 15] The method according to any one of Embodiment Items 1 to 14, further comprising purifying the aminoalkyl-substituted disiloxane.

[0167] [Embodiment Item 16] The method according to any one of Embodiment Items 1 to 15, wherein one or more method steps include adjusting the temperature of the mixture.

[0168] [Embodiment Item 17] The method according to any one of Embodiment Items 1 to 16, wherein reacting the mixture in a second reaction includes adjusting the temperature of the mixture.

[0169] [Embodiment Item 18] The method according to any one of Embodiment Items 1 to 17, wherein reacting the mixture in a second reaction includes cooling the mixture.

[0170] [Embodiment Item 19] The method according to any one of Embodiment Items 1 to 18, wherein the method is a one-pot synthesis.

[0171] [Embodiment Item 20] An aminoalkyl-substituted disiloxane produced by the method according to any one of Embodiment Items 1 to 19.

[0172] [Embodiment Item 21] An aminoalkyl-substituted disiloxane of the following formula (B-I).

[0173] [Chemical Formula] In the formula, R 12 , R 13 , R 14 , R15 , each independently represents hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C 3 -C 6 selected from the group consisting of branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R 16 and R 17 are each independently a direct bond, a substituted or unsubstituted C 1 -C 6 Linear 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 is selected from the group consisting of alkyl, R 18 and R 19 are each independently selected from the group consisting of substituents of formula (B-IV),

[0174] [ka] During the ceremony, The wavy bonds indicate the bond positions with formula (BI), R 25 , R 26 , R 27 , R 28 , R 29 and R 30 are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 Linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C 3 -C 6 Branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted C 1 -C 6Linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C 3 -C 6 Selected from the group consisting of branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl, R 31 and R 32 are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted C 1 -C 3 linear alkyl, substituted or unsubstituted branched 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 R 31 and R 32 form a single ring selected from the group consisting of heterocycloalkyl or heteroaryl, R 33 , R 34 and R 35 are each independently a direct bond, substituted or unsubstituted C 1 -C 6 linear 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 CH2 -, -NHCH 2 CH 2 CH 2 - and -NHCH 2 CH 2 CH 2 CH 2 selected from the group consisting of R 36 is hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted C 1 -C 3 linear alkyl, substituted or unsubstituted branched 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, selected from the group consisting of heterocycloalkyl and heteroaryl, m is an integer from 0 to 20, provided that the aminoalkyl-substituted disiloxane is not of the following formula.

[0175]

Chemical formula

[0176] [Embodiment Item 22] The aminoalkyl-substituted disiloxane according to Embodiment Item 21, which is a compound selected from the group consisting of the following.

[0177]

Chemical formula

[0178]

Chemical formula

[0179] Machine Learning Model Incorporating Physical Characteristics of Sorbents for Post-Combustion Carbon Capture In one aspect, a power generation system is provided. The power generation system includes a capture system for use in capturing carbon dioxide, a controller configured to operate the capture system, and a modeling system including a processor. The processor is configured to identify a model training dataset, and each instance of the model training dataset identifies an adsorbent used in 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, based on one or more of the plurality of primary features, one or more secondary features, each of the one or more secondary features being a combination of two or more of the plurality of primary features, and to determine a plurality of correlation values including a correlation value between each of the plurality of primary features and each of the one or more secondary features. The processor is also configured to identify a first subset of the model training dataset based on the plurality of correlation values, to determine a statistical significance for each instance of the first subset of the model training dataset, and to identify a second subset of the model training dataset based on the statistical significance, wherein the statistical significance for each instance of the second subset of the model training dataset is less than a predetermined threshold. The processor is further configured to generate a transfer function based on the second subset of the model training dataset and to use the transfer function to determine one or more promising adsorbents to be used in the capture system based on the carbon capture performance value. The controller operates the capture system using one or more promising adsorbents determined by the modeling system.

[0180] In another aspect, a method for selecting one or more promising sorbents used in the operation of a carbon dioxide capture system is provided. The method includes the step of identifying a model training data set, where each instance of the model training data set identifies a sorbent used in the capture system, a carbon capture performance value of the sorbent, and a plurality of primary feature values associated with a plurality of primary features. The method includes generating one or more secondary features based on one or more of the plurality of primary features, where each of the one or more secondary features is a combination of two or more of the plurality of primary features, determining a plurality of correlation values including a correlation value between each of the plurality of primary features and each of the one or more secondary features, and identifying a first subset of the model training data set based on the plurality of correlation values. The method also includes determining statistical significance for each instance of the first subset of the model training data set, and identifying a second subset of the model training data set based on the statistical significance, where the statistical significance for each instance of the second subset of the model training data set is less than a predetermined threshold, and generating a transfer function based on the second subset of the model training data set. The method further includes determining, using the transfer function, one or more promising sorbents to be used in the capture system based on the carbon capture performance value, and a controller operates the capture system using the one or more promising sorbents determined by the modeling system.

[0181] In one embodiment, a computer program is provided, which is implemented on a computer-readable medium. In an exemplary embodiment, the system is executed on a single computer system and does not require a connection to a server computer. In additional embodiments, the system is executed in a Windows® environment (Windows is a registered trademark of Microsoft Corporation, Redmond, WA, USA). In yet another embodiment, the system is executed in a mainframe environment and a UNIX® server environment (UNIX is a registered trademark of X / Open Company Limited, Reading, Berkshire, UK). In additional embodiments, the system is executed in an iOS® environment (iOS is a registered trademark of Cisco Systems, Inc., San Jose, CA, USA). In yet another embodiment, the system is executed in a MacOS® environment (MacOS is a registered trademark of Apple Inc., Cupertino, CA, USA). In yet another embodiment, the system is executed in an Android® OS (Android is a registered trademark of Google Inc., Mountain View, CA, USA). In another embodiment, the system is executed in a Linux® OS (Linux is a registered trademark of Linus Torvalds, Boston, MA, USA). The application is adaptable and is designed to operate in various environments without sacrificing its main functions. In some embodiments, the system includes multiple components distributed among multiple computing devices. One or more components may be in the form of computer-executable instructions implemented on a computer-readable medium.

[0182] Embodiments of the present invention relate to systems and methods for analyzing the physical characteristics of sorbents for post-combustion carbon capture (PCC), particularly components of metal-organic frameworks (MOF) and carbon dioxide (CO 2A system and method for modeling aspects of metal-organic frameworks (MOFs) based on their performance at a 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 attendant components. This model is then used to evaluate the predicted performance of other MOFs based on specific components of those MOFs. Such modeling helps scientists and engineers evaluate various MOFs without physically testing each candidate, leading to the acceleration of the development of MOFs with improved CO 2 capture capacity performance.

[0183] FIG. 14 shows an exemplary PCC modeling system 1440 that can be used to predict how well a particular MOF performs when capturing carbon dioxide (CO 2 ) from the exhaust gas 1416 of a coal-fired power plant 1410. In this example embodiment, the power plant 1440 generates electrical power 1412 that is distributed via a power transmission and distribution network 1414. The power plant 1440 also includes a post-combustion carbon capture (PCC) system 1420 configured to remove CO 2 from the exhaust gas 1416 and then release the treated exhaust to the environment. The PCC system 1420 of this example includes a metal-organic framework (MOF) 1422 that performs the capture function of the PCC system 1420. The MOF 1422 consists of three main components: a metal 1424, an organic linker 1426, and one or more functional groups 1428. During operation, the PCC system 1420 yields several performance results, which are represented herein as "capture performance" 1430 (e.g., PCC capacity) for illustrative purposes. The PCC modeling system 1440 is configured to estimate how a particular MOF (e.g., a specific combination of components and various attendant physical characteristics) will function when implemented in the PCC system 1420 (e.g., performance prediction in a "real-world" setting).

[0184] In an embodiment of this example, the PCC modeling system 1440 includes a data collection and preparation module 1442 configured to identify and store data used for training a machine learning model (e.g., a supervised prediction model). This preparation module 1442 stores historical records of various sorbents (e.g., MOF 1422), as well as the characteristics and known performance associated with them. Each historical record includes, for example, sorbent data such as the components of a particular sorbent (e.g., information regarding the metal 1424 used in the secondary building unit (SBU), information regarding the organic linker 1426, and / or information regarding the functional group 1428 or amine associated with a particular MOF 1422), various physical characteristics of the sorbent (e.g., pore diameter, pore volume, pore size distribution, surface area, etc.), and known performance data regarding the sorbent (e.g., isosteric heat of adsorption (Q ST ), Henry's law constant (Henry constant), selectivity ratio, mmol CO 2 sorbent capacity per gram of sorbent, mmol CO 2 sorbent productivity per gram of sorbent per unit time, etc., at a specific pressure and / or temperature). Each of these historical records may be stored as model data 1460 (e.g., in a database) and may include other data described in this application. Some of these data may be collected from publications, and other records may include data measured in a laboratory or data collected from the operating performance of the PCC system 1420 (e.g., data collected during operation).

[0185] The PCC modeling system 1440 also includes an exploratory data analysis module 1444 configured to assist analyst 1402 in performing univariate data analysis regarding the patterns of historical data. In an exemplary embodiment, the exploratory data analysis module 1444 is configured to generate a graph that displays one component of a known MOF for one feature so that analyst 1402 can view the trends of features among various MOFs. For example, the analysis module 1444 can generate plots of chemical sorbents and physical sorbents, two types of MOFs, and how they behave with respect to Henry's constant, selectivity ratio, heat of adsorption, PCC capacity, and PCC productivity (e.g., as composites between those two types of MOFs). In another example, the analysis module 1444 can generate plots of various metal types in a physical sorbent or chemical sorbent MOF and their respective heats of adsorption (e.g., numerical ranges, average values, etc. for each metal type). These plots are compiled and generated from the historical records identified in the model data 1460 and can be displayed to analyst 1402 via the display of the computing device 1404. From this data, analyst 1402 can further identify one or more secondary features, which, as further described below, can be combinations of two or more primary features. Such secondary features can be used in subsequent model training and analysis.

[0186] In this example embodiment, the PCC modeling system 1440 also includes a correlation and bivariate analysis module 1446 configured to analyze model data 1460 for positive or negative correlations between pairs of various features of the history record. For example, this analysis module 1446 can identify a set of primary features and optionally one or more secondary features and perform a correlation analysis between the associated features. For each specific pair of two features, the analysis module 1446 calculates a correlation coefficient (e.g., for all records of the model data 1460), and the correlation coefficient indicates how correlated these two features are with each other (e.g., a positive coefficient indicates a positive correlation between the two features, and a negative coefficient indicates a negative correlation between those two features). These correlation coefficients can be, for example, Pearson's correlation coefficients. These correlation coefficients can be displayed to the analyst 1402 in matrix form, and the analyst 1402 can then view the strength of the correlations between various feature pairs. In some examples, the matrix can be a heat map that color-codes each correlation coefficient based on the magnitude of the correlation coefficient, with a color (e.g., dark blue) having a strong positive correlation at one end of the spectrum and another color (e.g., dark red) having a strong negative correlation at the opposite end of the spectrum. In some examples, the analysis module 1446 may generate a pair plot for each pair of features, enabling the analyst 1402 to evaluate what type of relationship (e.g., linear, non-linear, etc.) the two features have.

[0187] The PCC modeling system 1440 also includes a regression analysis module 1448 configured to perform regression analysis using model data 1460. In an embodiment of this example, the regression analysis module 1448 identifies one or more features of interest for regression analysis. In some embodiments, the analyst 1402 can examine the correlation matrix and / or pair plot described above to select a subset of features of interest. In some embodiments, the regression analysis module 1448 can automatically identify one or more features of interest for regression analysis (e.g., based on the correlation coefficients of the matrix). For example, the regression analysis module 1448 can select all features that have a positive correlation coefficient (e.g., a strong positive correlation) where the PCC capacity exceeds a specific threshold. In some embodiments, the regression analysis module 1448 can select all features that have a negative correlation coefficient (e.g., a strong negative correlation) where the PCC capacity is less than a specific threshold. In some embodiments, the features used to initiate the regression analysis are manually selected by a user or the like.

[0188] Once a subset of features has been identified, the regression analysis module 1448 executes a regression analysis process starting from that subset of features. In some embodiments, a portion of the model data 1460 may be identified, either automatically or manually, as training data (e.g., for use in this regression analysis process), and the remaining portion of the model data 1460 may be left for evaluating the resulting model (e.g., 60% training data, 40% test data). In an embodiment of this example, the regression analysis process is executed in one or more stages, each stage including performing multiple linear regression analyses on the current set of features. Based on the results of each stage, one or more features are excluded from subsequent analysis stages, and a downselected (narrowed selection) subset of features for the next analysis stage remains until a certain stopping criterion is achieved. At this final stage, the regression analysis module 148 generates a transfer function using the ultimately remaining downselected features (e.g., PCC capacity as a function of certain downselected features). Applying this transfer function to the novel MOF and its associated feature values makes it possible to predict how the novel MOF will perform with respect to PCC capacity, productivity, etc.

[0189] Additional details and related functions executed in the PCC modeling system 1440 will be described in more detail with respect to FIGS. 16 and 17.

[0190] FIG. 15 is a graph 1500 showing a decrease in adsorption productivity for an exemplary sorbent (e.g., MOF) when transitioning from a synthetic powder measured under equilibrium conditions to a final film coating on a substrate measured under dynamic conditions. In an embodiment of this example, the Y-axis 1502 of the graph 1500 is kilograms of CO 2 (kgCO 2 (kgCO 2) It is the adsorbent productivity of MOF indicated in units of per kilogram of adsorbent (kgs) per hour (hr). The X-axis shows several stages 1504 of PCC productivity from the equilibrium powder productivity at the initial stage 1504A, through the dynamic time effect stage 1504B, the film mass transfer effect stage 1504C, the thermodynamic effect (working capacity between adsorption and desorption) stage 1504D, to the final film working productivity stage 1504E. In this example, at the initial stage 1504A, the adsorbent shows a productivity of about 0.58 kgCO 2 / kgs / hr. At each of the stages 1504A - 1504E, the adsorbent undergoes various productivity decreases based on the various effects described above. For example, in the dynamic time effect stage 1504B, the adsorbent drops by about 0.2 and undergoes a productivity decrease 1512 to approximately 0.35 kgCO 2 / kgs / hr. Further, for example, in the film mass transfer effect stage 1504C, the adsorbent drops by about 0.05 and undergoes a second productivity decrease 1514 just below about 0.3 kgCO 2 / kgs / h. Further, for example, in the thermodynamic effect working capacity stage 1504D, the adsorbent drops by about 0.1 and undergoes a third productivity decrease 1516 to the final coating working productivity 1520 of about 0.2 kgCO 2 / kgs / hr. Thus, in this example, the adsorbent undergoes a total productivity decrease 1522 of about 0.38 kgCO 2 / kgs / hr, i.e., a decrease of about 65% (e.g., about 35% utilization). This knockdown effect is specific to each adsorbent, film coating, and cycle time operation.

[0191] The decrease in PCC productivity of the adsorbent shown in the example of Figure 15 generally depends on the coating type and measurement type characteristics and may be due to a combination of multiple factors (e.g., not reaching equilibrium due to the kinetics of the adsorption cycle time, coating mass transfer resistance, heating of the adsorbent due to the isosteric heat of adsorption, and decrease in performance capacity, etc.). Without the PCC modeling system 1440 of Figure 14, all of these factors have to be determined experimentally to understand the final productivity of a given adsorbent.

[0192] For initial sorption at low concentrations, the equilibrium capacity of the sorbent is determined by the Henry's constant. The sorbent capacity N of sorbent i i is a function of the Henry's constant H i and is the product of the Henry's constant and the gas-phase concentration C of the sorbate i , such that N i = H i C i . The larger the value of the Henry's constant, the steeper the initial slope of the isotherm. This means that sorbents with a large H i have a large capacity for the sorbate in the low-concentration linear region of such isotherms. Maximizing H i also increases the productivity of the sorbent at low gas-phase sorbate concentrations. Thus, the PCC modeling system 1440 analyzes how various MOF components independently vary according to the Henry's constant to search for sorbents with a high Henry's constant for CO 2 adsorption. Since the Henry's constant is a thermodynamic term (not a kinetic term, for example), the kinetics of the sorbent may be evaluated to determine sorbent productivity. These measurements are not typically reported in the literature for known MOFs, and thus, this PCC modeling system 1440 may first search for the Henry's constant to identify MOF components that may have the maximum capacity for CO 2 at the lowest CO 2 gas-phase concentration. If kinetic absorption data are available, they are used as inputs to the PCC modeling system.

[0193] Figures 16A-16C are flowcharts illustrating an exemplary method 1600 for analyzing the predicted performance of promising sorbents in a post-combustion carbon capture system. In some embodiments, method 1600 may be performed by the PCC modeling system 1440, and the identified sorbent is the PCC system 1420 of FIG. 14. In an embodiment of this example, method 1600 includes collecting, or alternatively identifying, model training data for known sorbents (e.g., MOFs for which known performance data exist) in operation step 1610.

[0194] The model training data to be identified includes, in an exemplary embodiment, instances of individual sorbents stored in a database such as a model data database, as well as their specific compositions and known performance data (e.g., various variables for a specific known sorbent). Each sorbent may include information regarding the components of that specific sorbent instance (e.g., specific metals, organic linkers, and / or functional groups or functionalities), various physical characteristics of the sorbent instance (e.g., pore diameter, pore volume, heat of adsorption at equilibrium, Henry's constant, selectivity ratio, Langmuir / BET surface area, absorption rate, etc.), known performance data regarding the sorbent instance (e.g., PCC capacity and productivity), and optionally other information regarding the sorbent instance, such as a unique identifier or other sorbent data (e.g., classification as a physical sorbent or chemical sorbent). Examples of metals include, for example, nickel, chromium, magnesium, copper, manganese, zirconium, zinc, cobalt, indium, iron, aluminum, dysprosium, titanium, potassium, etc., or some combinations or alloys.Examples of organic linkers include, for example, 1,4-dioxide-2,5-benzenedicarboxylate (DOBDC), 1,4-benzenedicarboxylate (BDC), 4,4'-oxide-1,1'-biphenyl-3,3'-dicarboxylate (DOBPDC), 1,3,5-tri(1H-1,2,3-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'-dicarboxylate (BPDC), 1,1'-biphenyl-3,3',5,5'-tetracarboxylate (BPTC), 1,5-dioxide-2,6-naphthalenedicarboxylate (DONDC), 1,2,4,5-benzenetetracarboxylate (BTEC), 1,4-bis(1H-pyrazol-4-ylethynyl)benzene (BPEP), 2,5-di(1H-1,2,4-triazol-1-yl)terephthalate (BTTA), 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine (TDPAT), 2,3,5,6-tetrachloroterephthalate (TCDC), 4,4'-dibenzoic acid-2,2'sulfone (SBPDC), and the like. Examples of functionalities include, for example, open metal site [OMS], microporosity [MP], Lewis base site [LBS], polar functional site [PFS], post-synthesis modification [PSM], and the like. Examples of metals, linkers, functional groups, and physical characteristics have been given, but others are possible and are within the scope of the present disclosure. Depending on the situation, such sorbent model training data may be collected manually (e.g., by analyst 1402) and recorded in the model data database. In some embodiments, the PCC modeling system 1440 may be configured to collect such data (e.g., from performance or test data obtained via the PCC system 1420 via other online databases).

[0195] This sorbent data is used in the PCC modeling system 1440 and, in the embodiments of this example, is used as model training data for training a machine learning model to analyze the predictive performance of promising sorbents (e.g., novel combinations of metals, linkers, and functional groups that have not yet been studied and tested in the real world). This model training data can be used as labeled training data in model construction (e.g., instances of model training data with known results or "labels" for specific "inputs"). In some embodiments, one subset of the model training data may be identified for training the model and another subset may be identified for testing the model (e.g., identifying 60% of the sorbents for training and 40% for testing, 70% for training and 30% for testing, etc.). In some embodiments, the analyst 1402 manually identifies sorbents for training and testing (e.g., by specific rows in a database). In some embodiments, the PCC modeling system 1440 automatically identifies the training subset and the testing subset (e.g., using a pre-set percentage, random selection, etc.).

[0196] In some embodiments, the method 1600 also includes, in the operation step 1620, performing aspects of univariate data analysis on the model training data. This data analysis includes evaluating specific individual sorbent variables (such as specific components or features) against other variables (such as other components, features, performance values, etc.) across the entire training data. This analysis can be used to identify high-level trends associated with specific components or features.

[0197] In an embodiment of this example, the PCC modeling system 1440 provides the analyst 1402 with a graphical user interface that displays a plot of a particular feature against other target features of interest, enabling the analyst 1402 to investigate trends and relationships between those particular features. The interface enables the analyst 1402 to select a primary variable (e.g., as a domain) and a secondary variable of interest (e.g., as a range), and then the PCC modeling system 1440 may calculate numerical ranges (e.g., a domain that varies with discrete values along with a continuous secondary variable) for mean / average / median and / or bar graphs, forest plots, etc. across all the training data having those variables, or may generate a scatter plot, etc. (e.g., in the case of continuous primary and secondary variables). For example, the PCC modeling system 1440 may generate a plot of the heat of adsorption per equivalent or the Henry's constant or the average pore diameter against the organic linker, or may separately identify physical adsorbents or chemical adsorbents (e.g., by color-coding or shading). In another example, the PCC modeling system 1440 may generate a plot of the heat of adsorption per equivalent or the selectivity ratio of a metal identified in the training data.

[0198] In operation step 1630, in an embodiment of this example, the PCC modeling system 1440 generates secondary features for use in model training. Secondary features are combinations of two or more primary features. The term "primary feature" refers to one of the known variables such as the heat of adsorption per equivalent, Henry's constant, pore diameter, pore volume, surface area, etc. (e.g., existing main effect parameters of adsorption that have existed in the past). The term "secondary feature" refers to a combination of two or more primary features (e.g., interaction parameters) involved in the interaction between two primary features. In some embodiments, the analyst 1402 may manually create secondary features within the PCC modeling system 1440 by specifying two or more primary features to be combined as new secondary features of the model. In one example, the secondary feature "A" is (BET surface area × pore volume (V pore ), and the secondary feature "B" is (V pore × heat of adsorption per equivalent (Q ST)) as the secondary feature "C" (BET surface area × Q ST ) can be created. These secondary features can be used for model training and analysis described below.

[0199] In some embodiments, the PCC modeling system 1440 can select 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 of the primary features, such as through probability values. The probability value (p-value) is a measure of the significance of a variable with respect to a model. A p-value less than 0.05 indicates that the factor in the model is statistically significant with 95% confidence, showing strong evidence against the result being random, and the probability that the result is random is less than 5%.

[0200] In some embodiments, the PCC modeling system 1440 selects a predetermined number of secondary features. For example, if the number of primary features analyzed by the PCC modeling system 1440 is n, the set number of secondary features can be n C. In this example, the total number of primary and secondary features (n + n C) can be automatically selected by the PCC modeling system 1440.

[0201] In operation step 1640, in the embodiment of this example, the PCC modeling system 1440 performs correlation and bivariate analysis of the model data. Referring now to FIG. 16B, this analysis includes identifying a feature set for model training. In operation step 1642, a promising feature set for model training is identified. This feature set includes a list of primary features 1602 (or primary characteristics) and secondary features 1604 (or secondary characteristics) to be used in model training. As described above, the primary features 1602 include a list of physical features or known variables (such as heat of adsorption, pore diameter, pore volume, Henry's constant, etc.) assigned to the sorbent in the model data 1460, and the secondary features 1604 include combinations of those features defined in operation step 1630. The primary features 1602 and the 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 surface area, Langmuir surface area, pore volume (V pore ), heat of adsorption at equilibrium (Q ST ), and average pore diameter (Å), and the secondary features 1604 include the three exemplary secondary features described above, namely, "A" = (BET surface area × pore volume (V pore ), "B" = (V pore × heat of adsorption at equilibrium (Q ST )) and "C" = (BET surface 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.

[0202] In operation step 1644, the PCC modeling system 1440 may create a pair plot or scatter plot for each combination of the primary features 1602 and the secondary features 1604 in the feature set 1606. For example, the PCC modeling system 1440 creates a first pair plot showing the BET area and PCC capacity on the training data, a second pair plot showing the Langmuir surface area and PCC capacity on the training data, and a V poreand generate a third pair plot showing the PCC capacity, etc. The PCC modeling system 1440 may display these plots in a graphical user interface for inspection and consideration by the analyst 1402. For several combinations, these plots help the analyst 1402 identify whether there is a correlation between these two variables in the training data, whether the correlation is linear or non-linear, and whether they are positively or negatively correlated. Further, these plots help the analyst 1402 identify statistically significant variables in the training data.

[0203] In operation step 1646, the PCC modeling system 1440 generates a correlation matrix 1608 of correlation coefficients for various pairs of primary features 1602 and secondary features 1604 in the feature set 1606. More specifically, in the embodiment of this example, the correlation matrix 1608 is an n×n matrix, and both rows and columns are assigned to the individual features 1602, 1604 in the feature set 1606 (e.g., a square reflection matrix). Each cell of the matrix 308 represents a combination of two features 1602, 1604 within the feature set 1606 (e.g., based on the specific row and column of that cell), and the value contained in that cell is a correlation coefficient representing the degree or magnitude of the correlation between those two features. For each combination of two features 1602, 1604, the PCC modeling system 1440 calculates the correlation function of these two features (e.g., over the entire training data) in operation step 1648. The correlation coefficient is normalized from the range of +1.0 to -1.0 in the embodiment of this example, and the stronger the positive correlation between two features, the closer it is to +1.0, the stronger the negative correlation, the closer it is to -1.0, and a neutral (e.g., weak or non-existent) correlation is close to 0.0 (e.g., Pearson's correlation coefficient). In operation step 1650, the PCC modeling system 1440 places the correlation coefficients associated with these two features in specific cell(s). Once completed, this correlation matrix and the numerical values associated with them are displayed to the analyst 1402 for inspection and consideration, and in some embodiments, it may be presented as a heat map (e.g., individual cells are color-coded based on their values) to make it easier for the analyst 1402 to distinguish the positive and negative correlations between specific features. Details regarding the exemplary correlation matrix 1608 will be described later with respect to FIG. 17.

[0204] Referring again to FIG. 16A, the method 1600 of this example continues to operation step 1660, where the PCC modeling system 1440 performs a regression analysis to generate a transfer function that can be used to estimate the PCC performance of other (e.g., unexamined) sizing agents. More specifically, FIG. 16C shows an example of the regression analysis process of operation step 1660.

[0205] In an embodiment of this example, a set of model training data for use during the regression operation step 1660 is identified from the model data 1460. In some embodiments, as described above, specific instances of the training data may be manually identified (e.g., by the analyst 1402) or alternatively selected (e.g., automatically) by the PCC modeling system 1440. The training data thus represents which known sorbents are within the scope of this particular regression analysis, and the remaining model data can be used to verify the results of this training.

[0206] In operation step 1664, a set of features is selected with respect to the initial feature set 1680 (e.g., from the primary features 1602 and secondary features 1604 of the all-feature set 1606). In some embodiments, initially all features of the all-feature set 1606 may be used as the initial feature set 1680. In another embodiment, the analyst 1402 manually selects the features of the initial feature set 1680 (e.g., based on an examination of the pair plot and / or correlation matrix). In yet another embodiment, the PCC modeling system 1440 may automatically select the initial feature set 1680. For example, the PCC modeling system 1440 can add all features 1602, 1604 to the initial feature set 1680 having a correlation coefficient greater than a predetermined threshold (e.g., greater than 0.2) or less than a predetermined threshold (e.g., less than -0.2) for the PCC capacity. These features f are used as the current feature set 1682 for starting the regression.

[0207] In operation step 1666, the PCC modeling system 1440 uses the current feature set (e.g., for PCC capacity and CO 2When PCC productivity, as determined based on absorption rate (e.g., adsorption kinetics), is the dependent variable of interest, a multiple linear regression is performed on the model training data (using an ordinary least squares model fit of the training data), where a linear regression method is applied to the following Equation 1 to examine the dependence between the parameter of interest (e.g., PCC capacity, Å) and the various physical attributes selected for the initial feature set 1680 (e.g., BET surface area, pore volume, equivalent heat, and secondary features "A", "B", and "C" as described above):

[0208]

number

[0209] In this regression, each of the f current features 1682 has an associated linear coefficient b i Along with X i The regression is repeated by first including all initial features 1680 in the transfer function of Equation 1 and then removing the current features 1682 with the highest p-values ​​until all current features 1682 have p-values ​​below a predefined threshold (e.g., less than 0.05, meaning they are statistically significant with a 95% probability). The relevant variables in the model are those with probability values ​​(p-values) below a predefined threshold.

[0210] More specifically, in this example embodiment, at each step of the iteration, a p-value is generated for each feature remaining in the current set of features 1682. In test 1668, the PCC modeling system 1440 checks whether the regression is complete by evaluating the p-values of the current features 1682. If all of the remaining p-values of the current features 1682 are below a predetermined threshold, the iteration ends. Otherwise, the iteration proceeds to operation step 1670. In operation step 1670, the PCC modeling system 1440 identifies the current feature having the highest p-value and excludes that particular feature from the current features 1682 for the next iteration. The regression process returns to operation step 1666, continues with the reduced current feature set 1682, and generates new p-values again until all of the remaining features are below the predetermined threshold. If a primary feature has a p-value exceeding the threshold, but a secondary feature including that primary feature has a p-value below the threshold, the primary feature is retained as part of the model even if the individual p-value of that primary feature is greater than the threshold. This is necessary to retain the secondary feature having a p-value below the threshold as part of the model.

[0211] When the regression iteration is completed and the iteration ends, the PCC modeling system 1440 may have finished identifying one or more remaining features to include in the final feature set 1684, each of which has a p-value below a predetermined threshold and is statistically significant. In an embodiment of this example, the PCC modeling system 1440 examines whether there are signs of overfitting in the model or the final result. For the final feature set 1684, the PCC modeling system 1440 also generates r-squared and adjusted r-squared values, and the difference between these two numerical values can be an indicator of overfitting (for example, when they are far apart). If the difference between the r-squared value and the adjusted r-squared value (for example, abs(r-squared value - adjusted r-squared value)) is greater than a predetermined threshold, there may be a possibility of overfitting in the model. In such a situation, the PCC modeling system 1440 analyzes each combination of the remaining features in the final feature set 1684, runs the model with that combination, generates r-squared and adjusted r-squared values for each combination, and selects the combination with the closest r-squared value and adjusted r-squared value (for example, the minimum abs(r-squared value - adjusted r-squared value)).

[0212] Using the remaining features and their associated numerical values, a final transfer function is generated from this model. More specifically, by regression, a final coefficient for each of the remaining features in the final feature set 1684, as well as a constant (for example, the y-intercept), are obtained. Thus, each of the X f variables is identified by each of the remaining features, and the coefficient b f associated with each is added to Equation 1 along with the constant b 0 to generate the final transfer function. Thus, when this transfer function is used together with promising sorbents and their associated numerical values, the predicted PCC capacity of that specific sorbent can be determined.

[0213] In some embodiments, the PCC modeling system 1440 may use the model with test data to evaluate how it performs in terms of predictive ability. For example, the PCC modeling system 1440 may generate residual plots for a linear regression model with both training data and test data, so that the analyst 1402 can evaluate the performance of the model.

[0214] In a particular example, the regression operation step 1660 is performed with an exemplary training set that starts with an initial set of features of the heat of adsorption at equal amounts (Q ST ), BET surface area, pore volume (V pore ) and three exemplary secondary features "A", "B" and "C". In the first iteration, the p-value of the BET surface area is identified as the highest at 0.948 and is excluded. In the second iteration, the p-value of the secondary feature "A" is identified as the highest at 0.769 and is excluded. In the third iteration, the p-value of the secondary feature "B" is identified as the highest at 0.441 and is excluded. In the fourth iteration, the p-values of all remaining current features (e.g., Q ST , V pore and the secondary feature "C") are less than 0.05, and the regression iteration is 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, and the difference triggers an analysis of overfitting. Since there are three features remaining in the final feature set 1684, each combination of these features was examined with the model (e.g., a total of 3!=6 combinations, namely [Q ST , [Q ST , V pore , [Q ST , V pore , "C"], [V pore , [V pore , "C"] and ["C"]). In this example, only the combination of [Q ST gives an r-squared value of 0.567 and an adjusted r-squared value of 0.560, with the lowest difference of 0.007. Therefore, using the single feature Q ST and its associated numerical values, the remaining feature is only one (i.e., X 1 = Q ST)'s final transfer function, i.e., Å = b 1 X 1 +b 0 = 0.0318 × Q ST - 0.4243 is generated. Here, b 0 = - 0.4243 is a constant. In this particular example, when the test data is applied to the final model, a test r - squared value of 0.331 is obtained, and the r - squared value of the training model was 0.567. Thus, the equation contains only one feature with a p - value less than 0.05. Further, the positive r - squared value of the test data indicates that this model can explain 60% of the capacity using the heat of adsorption (Q ST ).

[0215] The PCC modeling system 1440 can be used to operate a post - combustion carbon capture system by determining one or more promising sorbents to be used in a post - combustion carbon - based system, for example, but not limited to, the generated transfer function. For example, the PCC modeling system 1440 can identify one or more promising sorbents based on the carbon capture performance values obtained from the transfer function in order to improve the overall carbon capture performance of the post - combustion carbon capture system.

[0216] FIG. 17 shows an example of a correlation matrix 1608. In some embodiments, the correlation matrix 1608 is generated by the PCC modeling system 1440 and used in the method 1600 described in FIGS. 16B - 16C. In the embodiments of this example, the correlation matrix 1608 is a 9×9 square reflection matrix. There are 9 rows 1702 and 9 columns 1704, and there are 9 features 1712 that are the subject of the model in this example. Each of the 9 features 1712 has a related row 1702 and a related column 1704. The features 1712 include 6 primary ( "primary") features 1712A and 3 secondary ( "secondary") features 1712B, similar to the examples shown in FIGS. 16B - 16C. Each cell of the matrix contains the correlation coefficient calculated between the two features that intersect at that cell. For example, the correlation coefficient between the BET surface area and the PCC capacity is - 0.12.

[0217] Additional aspects of the present invention are shown in the following embodiment sections.

[0218] [Embodiment Item 1] A power generation system comprising a collection system used for collecting carbon dioxide, a controller configured to operate the collection system, and a modeling system including a processor, wherein the processor performs the steps of identifying a model training data set, each instance of the model training data set identifying an adsorbent used in the collection system, a carbon capture performance value of the adsorbent, and a plurality of primary feature values related to 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 two or more of the plurality of primary features; determining a plurality of correlation values including correlation values between each of the plurality of primary features and each of the one or more secondary features; identifying a first subset of the model training data set based on the plurality of correlation values; determining statistical significance for 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 for each instance of the second subset of the model training data set is less than a predetermined threshold; generating a transfer function based on the second subset of the model training data set; and determining one or more promising adsorbents to be used in the collection system based on the carbon capture performance value using the transfer function, and the controller operates the collection system using one or more promising adsorbents determined by the modeling system.

[0219] [Embodiment Item 2] The power generation system according to Embodiment Item 1, wherein the step of generating one or more secondary features based on one or more of the plurality of primary features includes performing univariate data analysis on the plurality of primary features.

[0220] [Embodiment Item 3] The step of determining a plurality of correlation values includes generating a correlation matrix including a plurality of cells, where the plurality of cells are arranged in a plurality of rows and a plurality of columns regarding a plurality of primary features and one or more secondary features, and each of the plurality of cells includes one of the plurality of correlation values, according to the power generation system described in Embodiment Item 1 or Embodiment Item 2.

[0221] [Embodiment Item 4] The processor of the modeling system is configured to select an initial feature set from a plurality of primary features and one or more secondary features, according to the power generation system described in any one of Embodiment Items 1 to 3.

[0222] [Embodiment Item 5] Selecting the initial feature set includes receiving a user input indicating a selection of one or more features from among the plurality of primary features and one or more secondary features from the user, according to the power generation system described in any one of Embodiment Items 1 to 4.

[0223] [Embodiment Item 6] Selecting the initial feature set includes selecting one or more features from among the plurality of primary features and one or more secondary features, and each of the one or more features has a correlation coefficient greater than a predetermined threshold value, according to the power generation system described in any one of Embodiment Items 1 to 5.

[0224] [Embodiment Item 7] Each of the one or more features has one or more PCC performance data values greater than a predetermined threshold value, according to the power generation system described in any one of Embodiment Items 1 to 6.

[0225] [Embodiment Item 8] The processor of the modeling system is configured to determine the r-squared and related adjusted r-squared values for each combination of each instance of a second subset of the model training dataset, determine the value of the difference between the r-squared value and the related adjusted r-squared value for each combination of each instance of the second subset of the model training dataset, identify a third subset of the model training dataset based on the value of the difference, and for each instance of the second subset of the model training dataset, the value of the difference is greater than a predetermined threshold. The power generation system according to any one of Embodiment Items 1 to 7.

[0226] [Embodiment Item 9] For each instance of the second subset of the model training dataset, the value of the difference is less than a predetermined threshold. The power generation system according to any one of Embodiment Items 1 to 8.

[0227] [Embodiment Item 10] The plurality of primary features includes at least the carbon capture capacity and the isosteric heat of adsorption value. The power generation system according to any one of Embodiment Items 1 to 9.

[0228] [Embodiment Item 11] One or more secondary features are based on one or more of the selectivity ratio, pore volume, and isosteric heat of adsorption value. The power generation system according to any one of Embodiment Items 1 to 10.

[0229] [Embodiment Item 12] A method for selecting one or more promising sorbents used in the operation of a carbon dioxide capture system, the method comprising the steps of identifying a model training dataset, each instance of the model training dataset identifying a sorbent used in the capture system, a carbon capture performance value of the sorbent, and a plurality of primary feature values related to 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 two or more of the plurality of primary features; determining a plurality of correlation values including correlation values between each of the plurality of primary features and each of the one or more secondary features; identifying a first subset of the model training dataset based on the plurality of correlation values; determining statistical significance for each instance of the first subset of the model training dataset; identifying a second subset of the model training dataset based on the statistical significance, the statistical significance for each instance of the second subset of the model training dataset being less than a predetermined threshold; generating a transfer function based on the second subset of the model training dataset; and using the transfer function to determine one or more promising sorbents to be used in the capture system based on the carbon capture performance value, wherein a controller operates the capture system using the one or more promising sorbents determined by the modeling system.

[0230] [Embodiment Item 13] The method according to Embodiment Item 12, wherein the step of generating one or more secondary features based on one or more of the plurality of primary features includes performing univariate data analysis on the plurality of primary features.

[0231] [Embodiment Item 14] The method according to Embodiment Item 12 or Embodiment Item 13, wherein the step of determining a plurality of correlation values includes generating a correlation matrix including a plurality of cells, the plurality of cells being arranged in a plurality of rows and a plurality of columns related to the plurality of primary features and the one or more secondary features, each of the plurality of cells including one of the plurality of correlation values.

[0232] [Embodiment Item 15] The method according to any one of Embodiment Items 12 to 14, further comprising selecting an initial feature set from a plurality of primary features and one or more secondary features.

[0233] [Embodiment Item 16] The method according to any one of Embodiment Items 12 to 15, wherein selecting the initial feature set includes receiving user input from a user indicating selection of one or more features from among the plurality of primary features and one or more secondary features.

[0234] [Embodiment Item 17] The method according to any one of Embodiment Items 12 to 16, wherein selecting the initial feature set includes selecting one or more features from among the plurality of primary features and one or more secondary features, and each of the one or more features has a correlation coefficient greater than a predetermined threshold.

[0235] [Embodiment Item 18] The method according to any one of Embodiment Items 12 to 17, further comprising determining an r-squared and a related adjusted r-squared value for each combination of each instance of a second subset of the model training data set, determining a difference value between the r-squared value and the related adjusted r-squared value for each combination of each instance of the second subset of the model training data set, and identifying a third subset of the model training data set based on the difference value.

[0236] [Embodiment Item 19] The method according to Embodiment Item 18, wherein the step of identifying the third subset of the model training data set is such that the difference value is greater than a predetermined threshold for each instance of the second subset of the model training data set.

[0237] [Embodiment Item 20] The step of identifying a third subset of the model training data set, for each instance of the second subset of the model training data set, the method according to embodiment item 18, wherein the value of the difference is less than a predetermined threshold.

[0238] Solid Sorbent Materials In one aspect, a functionalized sorbent is provided. The functionalized sorbent includes a sorbent and one or more functionalized ligands containing an aminosilicon group. The sorbent has an average particle length of 3 μm or less. In another aspect, the sorbent has an average particle length of 2 μm or less. In another aspect, the sorbent has an average particle length of 1 μm or less.

[0239] This time, due to one or more of the decrease in the particle diameter of the sorbent, the increase in the aspect ratio of the sorbent, and the aqueous synthesis of the sorbent, 2 the finding that a sorbent with a significantly improved CO absorption rate was obtained.

[0240] Generally, the sorbent comprises an appropriate particle size known in the art that contributes to the functionalized sorbents described herein. In some embodiments, the sorbent has an average particle length of 3 μm or less, 2.9 μm or less, 2.8 μm or less, 2.7 μm or less, 2.6 μm or less, 2.5 μm or less, 2.4 μm or less, 2.3 μm or less, 2.2 μm or less, 2.1 μm or less, 2 μm or less, 1.9 μm or less, 1.8 μm or less, 1.7 μm or less, 1.6 μm or less, 1.5 μm or less, 1.4 μm or less, 1.3 μm or less, 1.2 μm or less, 1.1 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, 0.2 μm or less, or 0.1 μm or less. In some embodiments, the sorbent has an average particle length of 3 μm or more, 2.9 μm or more, 2.8 μm or more, 2.7 μm or more, 2.6 μm or more, 2.5 μm or more, 2.4 μm or more, 2.3 μm or more, 2.2 μm or more, 2.1 μm or more, 2 μm or more, 1.9 μm or more, 1.8 μm or more, 1.7 μm or more, 1.6 μm or more, 1.5 μm or more, 1.4 μm or more, 1.3 μm or more, 1.2 μm or more, 1.1 μm or more, 1 μm or more, 0.9 μm or more, 0.8 μm or more, 0.7 μm or more, 0.6 μm or more, 0.5 μm or more, 0.4 μm or more, 0.3 μm or more, 0.2 μm or more, or 0.1 μm or more.

[0241] Generally, the sorbent has an appropriate aspect ratio known in the art that contributes to the functionalized sorbents described herein. In this application, the aspect ratio is the ratio of the average particle length of the sorbent to the average particle width of the sorbent. In some embodiments, the sorbent has an aspect ratio in the range of about 0 to about 1. In some embodiments, the sorbent has an aspect ratio of 1 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, or 0.1 or less. In some embodiments, the sorbent has an aspect ratio of 0.9 or more, 0.8 or more, 0.7 or more, 0.6 or more, 0.5 or more, 0.4 or more, 0.3 or more, 0.2 or more, 0.1 or more, or 0 or more.

[0242] All particle size measurements used were the average determined from the particle size distribution by individually measuring the particle length and particle width in SEM images or by a software package. Since how the measurement is made is not actually important, it is thought not necessary to include details of the method used.

[0243] In some embodiments, the particle size is an individual particle size. Individual particle size measurements can be made by suitable means known in the art, such as by measuring the particle size in SEM images.

[0244] In some embodiments, the particle size measurement value is an average particle size measurement value. Average particle size measurements can be made by suitable means known in the art, such as by analyzing particle size distribution information.

[0245] Generally, the particle size of the sorbent can be controlled, altered, or reduced by suitable techniques known in the art that are applicable to the functionalized sorbents described herein. In some embodiments, techniques suitable for controlling, altering, or reducing the particle size include mechanical grinding (e.g., grinding in a mortar), microfluidizer, dry milling, wet milling, chemical particle size reduction (e.g., introduction of crystal growth inhibitors), acoustic cavitation, hydrodynamic cavitation, and combinations thereof.

[0246] Generally, the sorbent can be in a suitable form known in the art that is applicable to the functionalized sorbents described herein. In some embodiments, the sorbent is in a form selected from the group consisting of powders, pellets, composites, composites mixed with binders, films, coatings, packed beds, columns, monoliths, and combinations thereof.

[0247] The exemplary embodiments described herein include sorbent systems. Generally, the sorbent system can be a suitable sorbent system known in the art that is applicable to the functionalized sorbents described herein. In some embodiments, the sorbent system includes a functionalized sorbent and a binder as an optional component. In some embodiments, the sorbent system is disposed on a polymer film.

[0248] In some embodiments, the sorbent system includes one or more contactors. In some embodiments, the sorbent system includes two or more contactors. In some embodiments, the sorbent system includes a contactor for the adsorption cycle and a contactor for the desorption cycle. The contactor can be a suitable contactor known in the art that contributes to the functionalized sorbent described herein. In some embodiments, the sorbent is incorporated within one or more channels of the contactor. In some embodiments, the contactor is made from the sorbent itself. In some embodiments, the contactor is coated with the sorbent system. In some embodiments, the contactor includes two or more sorbent coatings, one or more of which are the sorbent system.

[0249] In some embodiments, the sorbent system includes a frame. The frame can be a suitable frame known in the art that contributes to the functionalized sorbent described herein. The frame can be included within the contactor or between two contactors. The frame consists of one piece or two or more pieces. In some embodiments, the frame is an air frame. In some embodiments, the configuration is selected from the group consisting of a polygonal configuration, a rectangular configuration, a square configuration, a circular configuration, an asymmetric configuration, and combinations thereof. In some embodiments, the sorbent system is mounted to the frame.

[0250] In some embodiments, the sorbent system includes one or more concentrators. The concentrator can be a suitable concentrator known in the art that contributes to the functionalized sorbent described herein. The concentrator can be a passive concentrator or an active concentrator.

[0251] In some embodiments, the sorbent system includes one or more components configured to drive a fluid flow. The component configured to drive the fluid flow can be a suitable component known in the art that contributes to the functionalized sorbent described herein and is configured to drive a fluid flow. In some embodiments, the component configured to drive the fluid flow is selected from the group consisting of a pump, a fan, and combinations thereof.

[0252] In some embodiments, the sorbent system includes one or more components configured to change the temperature. The component configured to change the temperature can be a component known in the art suitable for changing the temperature that contributes to the functionalized sorbent described herein. In some embodiments, the component configured to change the temperature is selected from the group consisting of heaters, coolers, and combinations thereof.

[0253] In some embodiments, the sorbent system includes one or more components configured to convey a fluid. The component configured to convey the fluid can be a component known in the art suitable for conveying the fluid that contributes to the functionalized sorbent described herein. In some embodiments, the component configured to convey the fluid is selected from the group consisting of pipes, porous pipes, plastic porous pipes, polymer porous pipes, metal porous pipes, composite porous pipes, and combinations thereof.

[0254] Generally, the functionalized sorbent can be used according to suitable purposes known in the art that contribute to the use of the functionalized sorbent described herein. In some embodiments, the functionalized sorbent is used in a sorbent system. In some embodiments, the functionalized sorbent is used in a carbon capture sorbent system. In some embodiments, the functionalized sorbent is used in a moisture sorbent system. In some embodiments, the functionalized sorbent is used in a carbon capture sorbent system in the presence of water. In some embodiments, the functionalized sorbent is used for gas capture. In some embodiments, the functionalized sorbent is used for post-combustion capture of CO 2 and / or direct air capture of CO 2

[0255] The exemplary embodiments described herein include methods of manufacturing a sorbent system. Generally, the functionalized sorbent is manufactured by suitable synthetic methods known in the art that contribute to the functionalized sorbent described herein.

[0256] ​In many embodiments, a method of manufacturing an adsorbent system includes manufacturing an adsorbent having an average particle length of 3 μm or less and, as an optional step, functionalizing the adsorbent with one or more functionalized ligands containing an aminosilicone group. In some embodiments, a method of manufacturing an adsorbent system includes manufacturing an adsorbent having an average particle length of less than 2 μm and, as an optional step, functionalizing the adsorbent with one or more functionalized ligands containing an aminosilicone group. In some embodiments, a method of manufacturing an adsorbent system includes manufacturing an adsorbent having an average particle length of less than 1 μm and, as an optional step, functionalizing the adsorbent with one or more functionalized ligands containing an aminosilicone group.

[0257] In some embodiments, a method of manufacturing an adsorbent system includes functionalizing the adsorbent with two or more functionalized ligands each containing an aminosilicone group, the aminosilicone groups being different from each other. In some embodiments, a method of manufacturing an adsorbent system further includes functionalizing the adsorbent with one or more functionalized ligands that do not contain an aminosilicone group. In some embodiments, a method of manufacturing an adsorbent system includes controlling the ratio of one or more functionalized ligands containing an aminosilicone group to one or more functionalized ligands that do not contain an aminosilicone group.

[0258] In some embodiments, a method of manufacturing an adsorbent system further includes annealing the functionalized adsorbent. Excess ligands can be removed by annealing the adsorbent system. In some embodiments, annealing the functionalized adsorbent includes annealing the functionalized adsorbent at an elevated temperature. In some embodiments, annealing the adsorbent includes annealing the adsorbent at a temperature of about 50°C to about 400°C. In some embodiments, annealing the adsorbent includes annealing the adsorbent at a temperature of about 100°C to about 300°C. In some embodiments, annealing the adsorbent includes annealing the adsorbent at a temperature of about 150°C to about 250°C.

[0259] Figure 34 is a flowchart 3410 of an exemplary method. In this exemplary embodiment, the flowchart 3410 of the method shows exemplary steps of the method embodiments described in the present application and does not limit the method embodiments. In the exemplary embodiment, the method includes forming (3412) a mixture including a sorbent precursor, a crystal growth inhibitor, a solvent as an optional component, and a non-solvent as an optional component. The method also includes reacting (3414) the mixture. In some embodiments, the sorbent has an average particle length of 3 μm or less. In some embodiments, the sorbent has an average particle length of 2 μm or less. In some embodiments, the sorbent has an average particle length of 1 μm or less.

[0260] The formation of the mixture (3412) can be performed by appropriate means known in the art. In some embodiments, all components are added simultaneously. In some embodiments, one or more components are added at a different time point from the other components.

[0261] In some embodiments, the sorbent precursor includes a MOF linker and a MOF metal or a metal-containing cluster. The sorbent precursor may be formed before the formation of the mixture (3412) and added as a single component to the mixture, or may be formed in situ in the mixture during the formation of the mixture (3412). For example, the MOF linker may be separately deprotonated and then added, or may be deprotonated in situ. Similarly, the MOF metal or the metal-containing cluster may be pre-formed and then added, or may be formed in situ.

[0262] In some embodiments, the solvent comprises an aqueous solvent. In some embodiments, the solvent comprises water. The use of an aqueous solvent provides several advantages. In particular, the use of an aqueous solvent provides advantages in terms of scalability, safety, cost, and waste treatment as compared to at least some known methods for producing MOF compounds. Further, MOF compounds prepared in an aqueous solvent are generally easier to purify, e.g., by solvent washing, than MOF compounds produced by known methods. This improved purification results from the relatively easy removal of solvent molecules (e.g., water) from the MOF compounds described herein as compared to the removal of strongly bound solvent molecules (e.g., dimethylformamide (DMF)) utilized in the production of the same MOF compounds by known methods. Further purified MOF compounds do not contain strongly bound solvent molecules that would reduce gas absorption, surface area, and / or overall pore volume. Finally, purification is improved because a less toxic purification method is required.

[0263] 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.

[0264] Generally, an antisolvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, the antisolvent is a liquid system component included in the reaction mixture. In some embodiments, the antisolvent is a solvent in which one of the components of the reaction mixture has limited solubility. In some embodiments, the antisolvent is selected from the group consisting of organic solvents, aqueous solvents, and combinations thereof.

[0265] In some embodiments, the crystal growth inhibitor is selected from the group consisting of salicylic acid, 4-fluorosalicylic acid, 4,4'-biphenol, 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC), 2,2'-bipyridine-5,5'-dimethanol (BPYDM), benzoic acids, biphenols, bipyridines, and combinations thereof.

[0266] Figure 35 is a flowchart 3510 of an exemplary method. In this exemplary embodiment, flowchart 3510 of the method shows exemplary steps of an embodiment of the method described in this application and does not limit the embodiment of the method. In the exemplary embodiment, the method includes forming (3512) a mixture including a sorbent, one or more functionalized ligands including an aminosilicone group, one or more functionalized ligands not including an aminosilicone group as an optional component, a solvent as an optional component, and a non-solvent as an optional component. The method also includes functionalizing (3514) the sorbent.

[0267] In some embodiments, functionalizing (3514) the sorbent includes stirring the mixture.

[0268] In some embodiments, functionalizing (3514) the sorbent includes functionalizing (114) the sorbent in the presence of an inert gas.

[0269] In some embodiments, functionalizing (3514) the sorbent includes functionalizing (3514) the sorbent at a temperature in the range of about 0 °C to about 100 °C. In some embodiments, functionalizing (3514) the sorbent includes functionalizing (3514) the sorbent at a temperature in the range of about 20 °C to about 80 °C. In some embodiments, functionalizing (3514) the sorbent includes functionalizing (3514) the sorbent at a temperature in the range of about 20 °C to about 60 °C.

[0270] In some embodiments, functionalizing (3514) the sorbent includes functionalizing (3514) the sorbent over a period of about 1 minute to about 7 days. In some embodiments, functionalizing (3514) the sorbent includes functionalizing (3514) the sorbent over a period of about 1 hour to about 3 days.

[0271] In some embodiments, the sorbent is desolvated before functionalization (3514). In some embodiments, the sorbent is dried before functionalization (3514).

[0272] In some embodiments, the sorbent is annealed after functionalization (3514). In some embodiments, annealing of the sorbent includes annealing the sorbent at an elevated temperature. In some embodiments, annealing of the sorbent includes annealing the sorbent at a temperature of about 50 °C to about 400 °C. In some embodiments, annealing of the sorbent includes annealing the sorbent at a temperature of about 100 °C to about 300 °C. In some embodiments, annealing of the sorbent includes annealing the sorbent at a temperature of about 150 °C to about 250 °C.

[0273] 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.

[0274] Generally, a non-solvent is a substance that cannot dissolve a given component of a solution or mixture. In some embodiments, the non-solvent is a liquid system component included in the reaction mixture. In some embodiments, the non-solvent is a solvent in which one of the components of the reaction mixture has only limited solubility. In some embodiments, the non-solvent is selected from the group consisting of organic solvents, aqueous solvents, and combinations thereof.

[0275] In some embodiments, the non-solvent aids in functionalization. In some embodiments, the selectivity of functionalization is controlled by relative solubility. For example, one or more of the sorbent or amine may have different solubilities in the liquid system reaction mixture compared to another adsorbent or amine or functionalized sorbent. Thus, relative solubility introduces reaction and / or reagent limitations.

[0276] In many embodiments, the method may include suitable process steps known in the art that contribute to the success of the methods described herein. Such process steps include, but are not limited to, washing, drying, filtering, purifying, separating, centrifuging, and combinations thereof. In some embodiments, the method further includes washing the functionalized sorbent. In some embodiments, the method further includes purifying the functionalized sorbent. In some embodiments, purification includes distillation, vacuum distillation, and / or the use of heat.

[0277] Exemplary embodiments described herein include a method of collecting one or more gases.

[0278] FIG. 36 is a flowchart 3610 of an exemplary method. In an exemplary embodiment, the flowchart 3610 of the method shows exemplary steps of an embodiment of the methods described herein and is not limiting of the embodiments of the method. The method includes receiving (3612) a gas source comprising one or more gases with a functionalized sorbent, the functionalized sorbent including a sorbent and one or more functionalized ligands including an aminosilicone group. In some embodiments, the functionalized sorbent includes two or more functionalized ligands each including an aminosilicone group, the aminosilicone groups being different from each other. In some embodiments, the functionalized sorbent further includes one or more functionalized ligands that do not include an aminosilicone group. The method also includes collecting (3614) an amount of one or more gases with the functionalized sorbent. The sorbent has an average particle length of 1 μm or less.

[0279] In some embodiments, the method includes (I) a step of receiving (3612) a gas source comprising one or more gases with a functionalized sorbent, the functionalized sorbent including a sorbent and one or more functionalized ligands including an aminosilicone group, and (II) a step of collecting (3614) an amount of one or more gases with the functionalized sorbent.

[0280] Generally, the gas source can be a suitable gas source known in the art that contributes to the methods described in this application. In some embodiments, the gas source is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, steam, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0281] Generally, the one or more gases can be suitable gases known in the art that contribute to the methods described in this application. In some embodiments, the one or more gases are selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, steam, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0282] In some embodiments, the one or more gases are present in the feed gas in an amount in the range of from about 0.001% (v / v) to about 40% (v / v). In some embodiments, the one or more gases are present in the feed gas in an amount in the range of from about 0.001% (v / v) to about 15% (v / v). In some embodiments, the one or more gases are present in the feed gas in an amount in the range of from about 0.001% (v / v) to about 10% (v / v). In some embodiments, the one or more gases are present in the feed gas in an amount in the range of from about 0.001% (v / v) to about 5% (v / v). In some embodiments, the one or more gases are present in the feed gas in an amount in the range of from about 0.001% (v / v) to about 1% (v / v). In some embodiments, the one or more gases are present in the feed gas in an amount greater than 10% (v / v).

[0283] In some embodiments, the one or more gases are present in the feed gas in an amount in the range of from about 100 ppmv to about 1000 ppmv. In some embodiments, the one or more gases are present in the feed gas in an amount in the range of from about 300 ppmv to about 5000 ppmv.

[0284] In some embodiments, the one or more gases do not contain steam.

[0285] In some embodiments, the one or more gases include water vapor. In some embodiments, the one or more gases include water vapor in an amount in the range of from about 0.001% (v / v) to about 25% (v / v). In some embodiments, the one or more gases include water vapor in an amount in the range of from about 0.01% (v / v) to about 20% (v / v). In some embodiments, the one or more gases include water vapor in an amount in the range of from about 0.5% (v / v) to about 15% (v / v). In some embodiments, the one or more gases include water vapor in an amount in the range of from about 0.5% (v / v) to about 4% (v / v). In some embodiments, the one or more gases include water vapor in an amount in the range of from about 4% (v / v) to about 15% (v / v).

[0286] In some embodiments, the one or more gases are present in the feed gas in an amount in the range of from about 0.001% (v / v) to about 10% (v / v) and in the presence of water vapor. In some embodiments, the one or more gases are present in the feed gas in an amount in the range of from about 0.001% (v / v) to about 5% (v / v) and in the presence of water vapor. In some embodiments, the one or more gases are present in the feed gas in an amount in the range of from about 0.001% (v / v) to about 1% (v / v) and in the presence of water vapor. In some embodiments, the one or more gases are present in the feed gas in an amount greater than about 10% (v / v) and in the presence of water vapor. In some embodiments, water vapor is present in an amount in the range of from about 0.001% (v / v) to about 25% (v / v). In some embodiments, water vapor is present in an amount in the range of from about 0.01% (v / v) to about 20% (v / v). In some embodiments, water vapor is present in an amount in the range of from about 0.5% (v / v) to about 10% (v / v).

[0287] In some embodiments, collecting (3614) an amount of the one or more gases with a functionalized sorbent includes adsorbing an amount of the one or more gases with the functionalized sorbent. In some embodiments, collecting (3614) an amount of the one or more gases with a functionalized sorbent includes adsorbing an amount of the one or more gases with the functionalized sorbent in the presence of water vapor.

[0288] In some embodiments, the amount of one or more gases collected (3614) by the functionalized sorbent is in the range of about 1% (v / v) to about 100% (v / v) of one or more gases present in the feed gas. In some embodiments, the amount of one or more gases collected (3614) by the functionalized sorbent is in the range of about 10% (v / v) to about 90% (v / v) of one or more gases present in the feed gas. In some embodiments, the amount of one or more gases collected (3614) by the functionalized sorbent is in the range of about 20% (v / v) to about 80% (v / v) of one or more gases present in the feed gas. In some embodiments, the amount of one or more gases collected (3614) by the functionalized sorbent is in the range of about 30% (v / v) to about 70% (v / v) of one or more gases present in the feed gas. In some embodiments, the amount of one or more gases collected (3614) by the functionalized sorbent is in the range of about 40% (v / v) to about 60% (v / v) of one or more gases present in the feed gas.

[0289] In some embodiments, the amount of one or more gases collected (3614) by the functionalized sorbent is in the range of about 1% (v / v) to about 25% (v / v) of one or more gases present in the feed gas. In some embodiments, the amount of one or more gases collected (3614) by the functionalized sorbent is in the range of about 1% (v / v) to about 20% (v / v) of one or more gases present in the feed gas. In some embodiments, the amount of one or more gases collected (3614) by the functionalized sorbent is in the range of about 1% (v / v) to about 15% (v / v) of one or more gases present in the feed gas. In some embodiments, the amount of one or more gases collected (3614) by the functionalized sorbent is in the range of about 1% (v / v) to about 10% (v / v) of one or more gases present in the feed gas. In some embodiments, the amount of one or more gases collected (3614) by the functionalized sorbent is in the range of about 1% (v / v) to about 5% (v / v) of one or more gases present in the feed gas.

[0290] In some embodiments, the amount of one or more gases captured (3614) by the functionalized sorbent is in the range of about 80% (v / v) to about 100% (v / v) of one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (3614) by the functionalized sorbent is in the range of about 85% (v / v) to about 100% (v / v) of one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (3614) by the functionalized sorbent is in the range of about 90% (v / v) to about 100% (v / v) of one or more gases present in the feed gas. In some embodiments, the amount of one or more gases captured (3614) by the functionalized sorbent is in the range of about 95% (v / v) to about 100% (v / v) of one or more gases present in the feed gas.

[0291] In some embodiments, the feed gas is adjusted to change the amount of water vapor. In some embodiments, changing the amount of water vapor includes increasing the amount of water vapor. In some embodiments, changing the amount of water vapor includes decreasing the amount of water vapor. In some embodiments, increasing the amount of water vapor includes adding or injecting water vapor into the feed gas. In some embodiments, decreasing the amount of water vapor includes removing water vapor from the feed gas by evaporation, condensation, and / or pre-adsorption. In some embodiments, changing the amount of water vapor includes exhaust gas recirculation (EGR) and / or mixing.

[0292] In many embodiments, the functionalized sorbent, feed gas, one or more gases, or combinations thereof are at a specific temperature. Each temperature can be changed to facilitate the methods described herein. Each temperature can have a uniform temperature profile, a gradient temperature profile, a discrete temperature profile, or combinations thereof.

[0293] In some embodiments, the method includes an adsorption cycle. In some embodiments, the method includes a desorption cycle. In some embodiments, one or more of the functionalized sorbent, the feed gas, one or more gases, or combinations thereof are at a temperature in the range of about 0 °C to about 150 °C during the gas adsorption cycle. In some embodiments, one or more of the functionalized sorbent, the feed gas, one or more gases, or combinations thereof are at a temperature in the range of about 60 °C to about 250 °C during the gas desorption cycle.

[0294] In some embodiments, the method includes controlling the temperature. The temperature can be controlled for the functionalized sorbent, the feed gas, one or more gases, or combinations thereof.

[0295] Exemplary embodiments described herein include a method of recovering one or more gases from a gas source.

[0296] Figure 37 is a flowchart 3710 of an exemplary method. In this exemplary embodiment, the flowchart 3710 of the method shows the basic method steps of the exemplary embodiments described herein and does not limit the embodiments of the method. The method includes receiving (3712) a gas source containing one or more gases with a functionalized sorbent, the functionalized sorbent including a sorbent and one or more functionalized ligands including an aminosilicone group. In some embodiments, the functionalized sorbent includes two or more functionalized ligands each including an aminosilicone group, and the aminosilicone groups are different from each other. In some embodiments, the functionalized sorbent further includes one or more functionalized ligands that do not include an aminosilicone group. The method also includes collecting (3714) an amount of one or more gases with the functionalized sorbent. The method also includes releasing (3716) one or more gases from the functionalized sorbent. The sorbent has an average particle length of 1 μm or less.

[0297] In some embodiments, the method comprises: (I) a step (3712) of exposing a gas source containing one or more gases to a functionalized sorbent, the functionalized sorbent comprising a sorbent and one or more functionalized ligands containing an aminosilicone group; (II) a step (3714) of collecting an amount of one or more gases with the functionalized sorbent; and (III) a step (3716) of releasing one or more gases from the functionalized sorbent.

[0298] In some embodiments, the step (3716) of releasing one or more gases from the functionalized sorbent comprises releasing one or more gases from the functionalized sorbent with a purge gas. In some embodiments, the step (3716) of releasing one or more gases from the functionalized sorbent comprises causing a change in temperature or pressure with the functionalized sorbent.

[0299] In some embodiments, one or more gases are released (3716) from the functionalized sorbent into a receiving gas. In some embodiments, the receiving gas is selected from the group consisting of air, N 2 , vapor, and combinations thereof. In some embodiments, the receiving gas is removed from the presence of the functionalized sorbent after receiving one or more gases. In some embodiments, the receiving gas has a higher concentration of one or more gases than the source gas.

[0300] Additional aspects of the disclosed technology are set forth in the following embodiment clauses.

[0301] [Embodiment Clause 1] A functionalized sorbent comprising: a sorbent; one or more functionalized ligands containing an aminosilicone group; and having an average particle length of 3 μm or less for the sorbent.

[0302] [Embodiment Clause 2] The functionalized sorbent according to Embodiment Clause 1, further comprising one or more functionalized ligands not containing an aminosilicone group.

[0303] [Embodiment Clause 3] The functionalized sorbent according to Embodiment Item 1 or Embodiment Item 2, wherein one or more functionalized ligands containing an aminosilicone group and one or more functionalized ligands not containing an aminosilicone group are present in a ratio in the range of about 10:1 to about 1:10.

[0304] [Embodiment Item 4] The functionalized sorbent according to any one of Embodiment Items 1 to 3, wherein the functionalized sorbent is a functionalized MOF compound of the following formula (A-I). M x L y F A a F B b (Formula A-I) In the formula, M is a MOF metal or a metal-containing cluster, L is a MOF linker, F A is one or more functionalized ligands containing an aminosilicone group, F B is one or more functionalized ligands not containing an aminosilicone group, x is a numerical value in the range of 1 to 6, y is a numerical value in the range of 1 to 6, a is a numerical value greater than 0 and less than or equal to 2, b is a numerical value in the range of 0 to 2.

[0305] [Embodiment Item 5] The functionalized sorbent according to any one of Embodiment Items 1 to 4, wherein the MOF metal or the metal-containing cluster contains a metal selected from the group consisting of an alkali metal, an alkaline earth metal, a transition metal, Mg, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, ions thereof, hydrates thereof, salts thereof, halides thereof, fluorides thereof, chlorides thereof, bromides thereof, iodides thereof, nitrates thereof, acetates thereof, sulfates thereof, phosphates thereof, carbonates thereof, oxides thereof, formates thereof, carboxylates thereof, and combinations thereof.

[0306] [Embodiment Item 6] The MOF linker is a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H 4 dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc 4- ), 4,4''-dioxid-[1,1':4',1''-terphenyl]-3,3''-dicarboxylate (dotpdc 4- ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4- ), 4,6-dihydroxyisophthalic acid (m-dobdc 4- ), 3,3'-dioxidobiphenyl-4,4'-dicarboxylate (para-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), dicarboxylates, terephthalic acid, tricarboxylates, 1,3,5-benzenetricarboxylic acid, azolates, tetraazolates, 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, 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, diimidodicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-carboxylic acid, 4,4’-diamino-1,1’-diphenyl-3,3’-dicarboxylic acid, 4,4’-diaminodiphenyl-3,3’-dicarboxylic acid, benzidine-3,3’-dicarboxylic acid, 1,4-bis-(phenylamino)benzene-2,5-dicarboxylic acid, 1,1’-dinaphthyl-8,8’-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4’-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7,-Hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-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'-bipyridine-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenonedicarboxylic acid, Pluriol E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diaminodiphenyl ether diimide dicarboxylic acid, 4,4'-diaminodiphenylmethane diimide dicarboxylic acid, 4,4'-diaminodiphenylsulfone diimide dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2'-3'-diphenyl-p-terphenyl-4,4”-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosanedicarboxylic 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-dichlorofluorbine-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-f]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurintricarboxylic acid, 1,1-dioxide-peryl[1,12-bcd]thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-Naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3’,4,4’-benzophenonetetracarboxylic acid, tetrahydrofuran tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, polytopic linker, ditopic linker, tritopic linker, tetratopic linker, pentatopic linker, hexatopic linker, heptatopic linker, octatopic linker, mixed linker, asymmetric linker, metallo linker, N-heterocyclic linker, protonated forms thereof, partially or fully deprotonated forms, and combinations thereof, a functionalized sorbent according to any one of Embodiment Items 1 to 5, comprising a linker selected from the group consisting of.,

[0307] [Embodiment Item 7] The functionalized sorbent according to any one of Embodiment Items 1 to 6, wherein the sorbent has an aspect ratio greater than 0.2.

[0308] [Embodiment Item 8] The functionalized sorbent according to any one of Embodiment Items 1 to 7, wherein the sorbent has an average particle length of less than 1 μm.

[0309] [Embodiment Item 9] One or more functionalized ligands containing an aminosilicon group are aminosubstituted siloxanes of the following formula (A-II), formula (A-III), formula (A-IV), formula (A-V), formula (A-VI) or formula (A-VII), a functionalized sorbent according to any one of Embodiment Items 1 to 8.

[0310] [Chemical formula]

[0311] [Chemical formula] Wherein, R 1 , R 2 , R3 , R 4 , R 9 , R 10 , R 13 , R 14 and R 18 are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl, and are selected from the group consisting of 3 -C 6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl, and are selected from the group consisting of R 5 , R 6 , R 11 , R 15 and R 17 are each independently a direct bond, substituted or unsubstituted C 1 -C 6 linear 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, and are selected from the group consisting of R 7 , R 8 , R 12 and R 16 are each independently a direct bond, substituted or unsubstituted C 1 -C 6 linear 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 and a substituent of the following formula (A-VIII), and are selected from the group consisting of

[0312] [Chemical] In the formula, The combination of waveforms indicates the combination position with formula (A-II) or formula (A-III) or formula (A-IV) or formula (A-V) or formula (A-VI) or formula (A-VII), R 19 , R 20 , R 21 , R 22 , R 23 and R 24 are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C 3 -C 6 branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted C 1 -C 6 linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C 3 -C 6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl, and are selected from the group consisting of, R 25 and R 26 are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C 1 -C 6 linear alkyl, substituted or unsubstituted C 1 -C 3 linear alkyl, substituted or unsubstituted branched 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 R 25 and R 26 together form a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl, R 27 , R 28and R 29 are each independently a direct bond, a substituted or unsubstituted C 1 -C 6 linear alkyl, a 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 selected from the group consisting of R 30 is hydrogen, a substituted or unsubstituted linear alkyl, a substituted or unsubstituted C 1 -C 6 linear alkyl, a substituted or unsubstituted C 1 -C 3 linear alkyl, a substituted or unsubstituted branched alkyl, a substituted or unsubstituted C 3 -C 6 branched alkyl, methyl, ethyl, propyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted C 3 -C 6 cycloalkyl, a substituted or unsubstituted C 4 -C 6 selected from the group consisting of cycloalkyl, heterocycloalkyl and heteroaryl, j is an integer from 0 to 20, k is an integer from 0 to 20, m is an integer from 0 to 20, n is an integer from 0 to 20.

[0313] [Embodiment Item 10] The functionalized sorbent according to any one of Embodiment Items 1 to 9, wherein the functionalized ligand of 1 or more contains an aminosilicon group selected from the group consisting of the following.

[0314] [Chemical Formula]

[0315] [Chemical Formula]

[0316] [Chemical Formula]

[0317] [Chemical Formula]

[0318] [Chemical Formula]

[0319] [Chemical Formula]

[0320] [Embodiment Item 11] A sorbent system containing the functionalized sorbent according to any one of Embodiment Items 1 to 10.

[0321] [Embodiment Item 12] A method for producing a sorbent, the method comprising: forming a mixture containing a sorbent precursor, a crystal growth inhibitor, a solvent as an optional component, and a non-solvent as an optional component, and reacting the above mixture A method comprising the above sorbent having an average particle length of 3 μm or less.

[0322] [Embodiment Item 13] The method according to Embodiment Item 12, wherein the sorbent precursor comprises a MOF linker and a MOF metal or metal-containing cluster.

[0323] [Embodiment Item 14] The method according to Embodiment Item 12 or Embodiment Item 13, wherein the solvent comprises an aqueous solvent.

[0324] [Embodiment Item 15] The method according to any one of Embodiment Items 12 to 14, wherein the crystal growth inhibitor is selected from the group consisting of salicylic acid, 4-fluorosalicylic acid, 4,4'-biphenol, 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC), 2,2'-bipyridine-5,5'-dimethanol (BPYDM), benzoic acids, biphenols, bipyridines, and combinations thereof.

[0325] [Embodiment Item 16] A method for producing a functionalized sorbent, the method comprising: (I) A mixture comprising: A sorbent produced by the method according to any one of Embodiment Items 12 to 15, One or more functionalized ligands containing an aminosilicone group, Optionally, one or more functionalized ligands not containing an aminosilicone group, Optionally, a solvent, and Optionally, a non-solvent Forming a mixture comprising; (II) Functionalizing the sorbent A method comprising.

[0326] [Embodiment Item 17] A method for collecting one or more gases, the method comprising: (I) Exposing a gas source containing one or more gases to a functionalized sorbent, wherein the functionalized sorbent is: A sorbent having an average particle length of 3 μm or less, and one or more functionalized ligands containing an aminosilicon group comprising the step of (II) collecting an amount of one or more gases with the functionalized sorbent comprising the method.

[0327] [Embodiment Item 18] The method according to Embodiment Item 17, wherein the gas source is selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0328] [Embodiment Item 19] The method according to Embodiment Item 17 or Embodiment Item 18, wherein the one or more gases are selected from the group consisting of air, flue gas, post-combustion gas, natural gas, syngas, carbon dioxide, carbon monoxide, water vapor, hydrogen, nitrogen, oxygen, methane, olefin gas, nitrogen oxides, sulfur dioxide, ammonia, hydrogen sulfide, and combinations thereof.

[0329] [Embodiment Item 20] A method for recovering one or more gases, the method comprising collecting one or more gases by the method according to any one of Embodiment Items 17 to 19 (III) releasing one or more gases from the functionalized sorbent comprising the method.

[0330] [Examples] Without further explanation, it is believed that a person skilled in the art can utilize the present invention to its fullest extent from the above description. The following examples are merely illustrative and do not limit the present disclosure. The starting materials for the following examples are not necessarily prepared by the specific preparation work described in the procedure in another embodiment. In addition, the numerical ranges described herein include all values ​​from the lower limit to the upper limit. For example, when a range is described as 10 to 50, values ​​such as 12 to 30, 20 to 40, and 30 to 50 are explicitly described in this specification. The starting materials for the following examples are not necessarily prepared by the specific preparation work described in the procedure in another embodiment. In addition, the numerical ranges described herein include all values ​​from the lower limit to the upper limit. For example, when a range is described as 10 to 50, values ​​such as 12 to 30, 20 to 40, or 30 to 50 are explicitly intended to be recited in this specification. These are merely examples of what is specifically intended, and it is understood that all possible combinations of numerical values ​​between the described lower limit and upper limit are explicitly described in this specification.

[0331] Carbon Dioxide Capture System Using Functionalized Sorbents and Water Management Example A1 . Comparison of Moisture Isotherms H as a function of relative humidity measured by DVS mass spectrometry at 25 °C for sorbents functionalized with AEAM, spermidine, a hybrid amine with spermine:AEAM = 0.65:0.35 ("hybrid compound 1"), and a hybrid amine with spermine:AEAM = 0.32:0.46 ("hybrid compound 2") 2 The O adsorption capacity is shown in Figure 5. This figure shows the moisture adsorption isotherm as well as the H 2 This indicates that the relative humidity at which the knee point for monolayer adsorption of O occurs varies with the chemical structure of the functionalized sorbent. As shown in Figure 5, all sorbents except AEAM have moisture sorption isotherms with shapes closest to type IV, and H 2 The plateau region up to the knee point, corresponding to monolayer coverage and adsorption of O, is contained at a relative humidity of about 30% for the two hybrid compounds and about 35% for spermidine.

[0332] Example A2 . Moisture Adsorption Isotherm of Hybrid Compound 1 The H 2 O adsorption capacity of hybrid compound 1 (spermine: AEAM = 0.65:0.35) is shown in Fig. 6 as a function of relative humidity at various temperatures. The H 2 O adsorption capacity of hybrid compound 1 (spermine: AEAM = 0.65:0.35) measured by the DVS measurement method is shown in Fig. 7 as a function of H 2 O partial pressure (kPa) at various temperatures. These figures show that although they vary as a function of absolute H 2 O partial pressure, the shape of the moisture isotherm and the relative humidity at which the knee point of monolayer adsorption of H 2 O occurs remain almost the same even when the temperature changes.

[0333] Example A3 . Adsorption Performance of Hybrid Compound 1 Using the DVS measurement method, the CO 2 and H 2 O adsorption performance of hybrid compound 1 (spermine: AEAM = 0.65:0.35) measured at 40 °C under 4.5 vol% CO 2 is shown in Fig. 8 as a function of relative humidity. This figure suggests that CO 2 adsorption is affected by relative humidity. The knee point of monolayer adsorption of H 2 O seems to be like a critical threshold as shown for hybrid compound 1 in Fig. 5. Since the DVS gravimetric method is based on the measurement of changes in deposited mass, it cannot distinguish the individual components in a binary system (for example, CO 2 and H 2 O) in this case, so the individual amounts of CO 2 adsorption and H 2 O adsorption cannot be accurately calculated. To quantitatively evaluate CO 2 and H 2 adsorption separately, a breakthrough test apparatus and an analyzer equipped with individual sensors designed for CO 2 and H 2 O should be used.

[0334] Example A4 .Adsorption Performance of Hybrid Compound 1 as a Function of Temperature, Moisture Content, and Relative Humidity Using the DVS measurement method, 4.5 vol% CO 2 adsorption performance of hybrid compound 1 (spermine: AEAM = 0.65:0.35) measured below 2 is shown in Fig. 9 as a function of water pressure (kPa) at various temperatures. The H 2 O adsorption capacity of hybrid compound 1 (spermine: AEAM = 0.65:0.35) measured using the DVS measurement method is shown in Fig. 10 as a function of water pressure (kPa) at various temperatures. The CO 2 adsorption performance of hybrid compound 1 (spermine: AEAM = 0.65:0.35) measured using the DVS measurement method is shown in Fig. 11 as a function of relative humidity at various temperatures. 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 controlling temperature and moisture content. These figures 2 further suggest that CO 2 adsorption is affected by relative humidity. The knee point of the monolayer adsorption of H 2 O appears to be like a critical threshold, as shown for hybrid compound 1 in Fig. 5. Similarly, to 2 quantitatively evaluate CO 2 and H 2 O adsorption separately, a breakthrough test apparatus and an analysis apparatus equipped with individual sensors designed for CO

[0335] Example A5 . Comparison of Adsorption Capacity The dry CO 2 and wet CO with a relative humidity of 30% 2 of hybrid compound 1 (spermine: AEAM = 0.65:0.35) measured at 40 °C using the DVS measurement method 2 adsorption isotherms are shown in Fig. 12A. This figure shows that the adsorption capacity of hybrid compound 1 increases under wet conditions with a relative humidity of 30% compared to dry conditions.

[0336] Individual CO 2 and H 2 ​​Using a breakthrough test device equipped with an O sensor, at 25 °C and 400 ppmv CO 2 The dry CO of hybrid compound 3 (spermine: AEAM = 0.69:0.23) measured under DAC compliance conditions at a concentration of 2 and wet CO at various relative humidities 2 for CO 2 adsorption is shown in Figure 12B. Figure 12B also shows the isotherm of pure H 2 O adsorption of hybrid compound 3. This figure shows that, at least under test conditions suitable for DAC applications, as shown for hybrid compound 3 in Figure 12B, (1) wet CO 2 has increased CO 2 adsorption compared to dry CO 2 (relative humidity 0%), (2) the amount of CO 2 adsorption is affected by the actual relative humidity, and (3) CO 2 adsorption appears to flatten out in harmony with the knee point of monolayer H 2 O adsorption when the lowest relative humidity is reached, quantitatively demonstrating this.

[0337] An exemplary system using a functionalized chemisorbent in the presence of water to contribute to the optimization of carbon dioxide adsorption and desorption by an adsorbent bed will be described below. The exemplary system described in the present application provides at least several advantages over conventional design processes, including changes in temperature and / or moisture relative humidity within the adsorbent bed, improvements in the efficiency and performance of carbon dioxide adsorption and desorption due to changes in the functionalized sorbent within the adsorbent bed, and / or improvements in the performance of the capture system by adjusting the temperature and moisture relative humidity within one or more adsorption modules within the adsorbent bed based on the functionalized sorbent within one or more adsorption modules.

[0338] Synthesis of Aminoalkyl-Substituted Disiloxanes Example B1 . Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2-Aminoethylaminomethyl)Tetramethyldisiloxane Using 4 Equivalents of Ethylenediamine 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 the headspace was purged with N 2It was purged. Chloromethyldimethylethoxysilane (240 mL, 1.48 mol) was placed in a dropping funnel and added dropwise to ethylenediamine over 1 hour, and the reaction exothermed to 90 - 100 °C. After another 1 hour passed, when the reaction was completed 1 it was determined by 1H NMR, and at that time 300 mL of water was added dropwise to the reaction mixture over 30 minutes, generating heat. The reaction mixture was cooled to room temperature with stirring, and when it reached room temperature, 300 mL of chloroform was added dropwise. The resulting mixture was stirred vigorously for 1 hour, and then the organic layer was isolated and the aqueous layer was extracted with a minimum amount of chloroform. The organic layers were combined and dried under reduced pressure at room temperature. The resulting substance was then purified by vacuum distillation. The first fraction was collected at 40 - 80 °C and 380 mTorr, but it mainly contained cyclic by-products and some product. The remaining substance (167 g, yield 81%) was 1 over 75% pure according to 1H NMR spectroscopy. 1 1H NMR (CDCl 3 3) δ: 2.80 (t, 4H, H 2 2NCH 2 2CH 2 2), 2.65 (t, 4H, H 2 2NCH 2 2), 2.05 (s, 4H, SiCH 2 2), 1.30 (brs, 6H, NH&NH 2 2), 0.12 (s, 12H, SiCH 3 3)2.

[0339] Example B2 . Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(3-Aminopropylaminomethyl)Tetramethyldisiloxane The same procedure as in Example B1 was followed, but 1,3-propanediamine (52 mL, 0.62 mol), chloromethyldimethylethoxysilane (25 mL, 0.15 mol), 40 mL of water and 40 mL of chloroform were used in a 250 mL three-necked flask. The resulting substance was then purified by vacuum distillation. The first fraction was collected at 40 - 65 °C, but it mainly contained cyclic by-products and some product. The remaining substance (17.6 g, yield 74%) was 1 over 95% pure according to 1H NMR spectroscopy. 1 1H NMR (CDCl 3 3) δ: 2.75 (t, 4H, H2 NCH 2 CH 2 CH 2 ), 2.65 (t, 4H, H 2 NCH 2 ), 2.05 (s, 4H, SiCH 2 ), 1.60 (mult, 4H, H 2 NCH 2 CH 2 ), 1.30 (brs, 6H, NH&NH 2 ), 0.12 (s, 12H, SiCH 3 ).

[0340] Example B3 . Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2-Methyl-3-aminopropylaminomethyl)Tetramethyldisiloxane The same procedure as in Example B1 was followed, but 2-methyl-1,3-propanediamine (2.84 mL, 0.028 mol), chloromethyldimethylethoxysilane (1.14 mL, 0.0071 mol), 2 mL of water and 2 mL of chloroform were used in a 15 mL flask. The resulting substance was then purified by vacuum distillation. The first fraction was collected at 110 °C and mainly contained cyclic by-products and some product. The remaining substance (0.60 g, 51% yield) was 1 found to be over 95% pure by 1H NMR spectroscopy. 1 1H NMR (CDCl 3 3) δ: 2.8 - 2.5 (overlap mult, 8H, H 2 NCH 2 CH(CH 3 )CH 2 ), 2.05 (mult, 4H, SiCH 2 ), 1.75 (mult, 2H, H 2 NCH 2 CH), 1.95 (brs, 6H, NH&NH 2 ), 0.90 (δ, 6H, H 2 NCH 2 CHCH 3 ) 0.12 (s, 12H, SiCH 3

[0341] Example B4 . Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2,2-Dimethyl-3-aminopropylaminomethyl)Tetramethyldisiloxane The same procedure as in Example B1 was followed, but 2,2-dimethyl-1,3-propanediamine (3.41 mL, 0.028 mol), chloromethyldimethylethoxysilane (1.12 mL, 0.0071 mol), 2 mL of water and 2 mL of chloroform were used in a 15 mL flask. The resulting substance was then purified by vacuum distillation. The first fraction was collected at 80 - 90 °C and mainly contained cyclic by-products and some product. The remaining substance (0.95 g, 74% yield) was 1 found to be over 95% pure by 1H NMR spectroscopy. 1 1H NMR(CDCl 3 3) δ: 3.10 (brs, 6H, NH&NH 2 2), 2.67 (s, 4H, H 2 2NCH 2 2), 2.60 (s, 4H, H 2 2NCH 2 2C(CH 3 3)2CH 2 2), 2.15 (s, 4H, SiCH 2 2), 0.95 (s, 12H, H 2 2NCH 2 2C(CH 3 3)2), 0.19 (s, 12H, SiCH 3 3)。

[0342] Example B5 . Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2-Aminoethylaminomethyl)Tetramethyldisiloxane Using 8 Equivalents of Ethylenediamine 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 the headspace was purged with N 2 2. Chloromethyldimethylethoxysilane (240 mL, 1.48 mol) was placed in a dropping funnel and added dropwise to the ethylenediamine over 1 hour, and the reaction exothermed to 90 - 100 °C. After a further 1 hour, the reaction was complete as 1Determined by \(^1H\) NMR, 300 mL of water was then added dropwise to the reaction mixture over 30 minutes, and heat was generated. The reaction mixture was cooled to room temperature with stirring, and when room temperature was reached, 300 mL of chloroform was added dropwise. The resulting mixture was stirred vigorously for 1 hour, and then the organic layer was isolated and the aqueous layer was extracted with a minimal amount of chloroform. The organic layers were combined and dried under reduced pressure at room temperature. The resulting material was then purified by vacuum distillation. The first fraction was collected at 40 - 80 °C and 380 mTorr and mainly contained cyclic by-products and some product. The remaining material (326 g, 79% yield) was 1 greater than 90% pure by \(^1H\) NMR spectroscopy. 1 \(^1H\) 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 (brs, 6H, NH&NH 2 ), 0.12 (s, 12H, SiCH 3 ).

[0343] Example B6 . Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2-Aminoethylaminomethyl)Tetramethyldisiloxane Using 10 Equivalents of Ethylenediamine 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 the headspace was purged with N 2 . Chloromethyldimethylethoxysilane (97 mL, 0.59 mol) was placed in a dropping funnel and added dropwise to the ethylenediamine over 1 hour, and the reaction exothermed to 90 - 100 °C. After an additional 1 hour, when the reaction was complete, 1It was determined by \(^1H\) NMR, and at that time, 300 mL of water was added dropwise to the reaction mixture over 30 minutes, generating heat. The reaction mixture was cooled to room temperature with stirring, and when it reached room temperature, 300 mL of chloroform was added dropwise. The resulting mixture was stirred vigorously for 1 hour, and then the organic layer was isolated, and the aqueous layer was extracted with a minimal amount of chloroform. The organic layers were combined and dried under reduced pressure at room temperature. The resulting substance was then purified by vacuum distillation. The first fraction was collected at 40 - 80 °C and 380 mTorr, but it mainly contained cyclic by-products and some product. The remaining substance (117 g, 70% yield) was 1 found to be over 95% pure by \(^1H\) NMR spectroscopy. 1 \(^1H\) NMR (CDCl 3 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 (brs, 6H, NH&NH 2 ), 0.12 (s, 12H, SiCH 3 ).

[0344] Comparative Example B1 . Attempted Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2-Aminoethylaminomethyl)Tetramethyldisiloxane from 1,3-Bis(Chloromethyl)Tetramethyldisiloxane Ethylenediamine (13 g, 0.216 mol, 10 eq) was added to a 50 ml three-necked round-bottom flask equipped with a nitrogen blanket, magnetic stirrer, condenser and addition funnel. This was heated in an oil bath to a set oil temperature of 110 °C. When the temperature of the oil bath was stabilized, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane (5 g, 0.0216 mol) was added dropwise over 2 hours. The reaction was stirred overnight and the reaction was cooled. 1 \(^1H\) NMR analysis was performed to check if the reaction was complete. The reaction mixture was placed in a 250 mL separatory funnel and partitioned between chloroform and 10% NaOH, washed three times with deionized water and once with saturated sodium chloride, and then dried over anhydrous potassium chloride. After filtration, chloroform was stripped off with a rotary evaporator to obtain a colorless transparent viscous liquid. 1By \(^1\)H NMR analysis, a mixture of products containing the cyclic by-product 2,2,6,6-tetramethyl-1-oxa-4-aza-2,6-disilacyclohexane-4-ethanamine was confirmed. The desired 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane was not formed.

[0345] Comparative Example B2 . Attempted Synthesis of Aminomethyl-Substituted Disiloxane 1,3-Bis(2-Aminoethylaminomethyl)Tetramethyldisiloxane from 1,3-Bis(Iodomethyl)Tetramethyldisiloxane Ethylenediamine (13 g, 0.216 mol, 10 equiv) was added to a 50 mL three-necked round-bottom flask equipped with a nitrogen blanket, magnetic stir bar, condenser, and addition funnel. 1,3-Bis(iodomethyl)-1,1,3,3-tetramethyldisiloxane (10.16 g, 0.0216 mol) was added dropwise over 2 h. The reaction was stirred overnight at room temperature. 1 \(^1\)H NMR analysis was performed to check if the reaction was complete. The reaction mixture was placed in a 250 mL separatory funnel and partitioned between chloroform and 10% NaOH, washed three times with deionized water and once with saturated sodium chloride, and then dried over anhydrous potassium chloride. After filtration, stripping of the chloroform on a rotary evaporator gave a colorless, transparent, viscous liquid. 1 By \(^1\)H NMR analysis, clear formation of the cyclic by-product 2,2,6,6-tetramethyl-1-oxa-4-aza-2,6-disilacyclohexane-4-ethanamine was confirmed. The desired 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane was not formed. For 2,2,6,6-tetramethyl-1-oxa-4-aza-2,6-disilacyclohexane-4-ethanamine 1 \(^1\)H NMR (CDCl 3 \(_3\)) δ: 2.70 (t, 2H, CH 2 \(_2\)), 2.40 (t, 2H, CH 2 \(_2\)), 1.75 (overlap s, 4H + 2H, SiCH 2 \(_2\)NCH 2 \(_2\)Si + H 2 \(_2\)N), 0.10 (s, 12H, SiCH 3 \(_3\)).

[0346] Solid Sorbent Materials In these examples, MOF-274[Mg 2 (dobpdc)] is used as a specific example. However, this example is not limited to MOF-274 and is widely applicable to other materials or methods according to the present disclosure.

[0347] Characterization technology Particle size A scanning electron microscope (SEM) is used for the characterization of the average particle shape and particle size. The aspect ratio is defined as the ratio of the average particle length to the average particle width.

[0348] CO absorption amount by the dynamic moisture sorption measurement device (DVS) gravimetric method 2 and 2 H CO 2 and H 2 The performance of O adsorption was investigated using the dynamic vapor sorption (DVS) gravimetric method. The gases used in the experiments shown in this case were CO 2 and water, respectively. The DVS Vacuum measurement device is designed to accurately measure the mass change of the sample when adsorbing water and gas molecules with precisely controlled concentrations. The sample is placed in a sample container suspended from a microbalance (usually an empty container is suspended as a "control" on the opposite side of the microbalance). DVS Vacuum simultaneously controls and measures the inflow and outflow of the sorption mass while recording the mass change of the sample. The main device, the microbalance (UltraBalance (trademark)), is housed in a precisely temperature-controlled enclosure (referred to as an incubator). This ensures a very stable instrument baseline and accurate vapor generation control at the experimental temperature.

[0349] As shown below, a two-cycle sequential adsorption test protocol was developed. At the start of each test, the sorbent material was 10 -5Subject it to an activation (or regeneration) step at 120 °C under a vacuum of less than mbar for 30 to 90 minutes. Introduce water at a set partial pressure at a predetermined temperature under vacuum without interference from the carrier gas. Use the Ultra Precision Microbalance from Surface Measurement Systems to directly and continuously measure the weight of the sample with a resolution of 0.1 μg. All sorption measurements in this case were carried out using a mass balance mode where the mass balance criterion was set to a mass change per minute (dm / dt < 0.0035).

[0350] O absorption amount 2 CO absorption amount by breakthrough test device 2 and CO 2 and H 2 The performance of O adsorption can also be investigated using a self-made breakthrough test device. This test device includes a sample chamber that houses a test sample in either the form of sorbent powder or a coated form (i.e., a sorbent-binder film on a substrate), and separate calibrated CO 2 and relative humidity (RH) sensors placed both at the gas inlet in front of the sample chamber and at the gas outlet behind the sample chamber. This test device can measure the individual breakthrough curves for CO 2 under preset RH dry or wet CO 2 and H 2 O. The absorption amount can be calculated by integrating the breakthrough curve over time.

[0351] H 2 O absorption amount 2 CO and H CO 2 The absorption amount or capacity is expressed in grams of CO 2 adsorbed per gram of sorbent (gCO 2 / g sorbent). The CO 2 absorption amount can be regarded as an exponential growth over time and can be expressed by the following equation.

[0352] [Number] Wherein, Q max and Q (t) are, respectively, the parallel absorption amount and the absorption amount at a given adsorption time t (min), and k is the characteristic of exponential growth in units of 1 / min. The term of k is used to compare the kinetics or rate of CO 2 absorption. The larger k is, the faster the CO 2 absorption rate becomes.

[0353] O absorption amount and rate . Example C1 First, the MOF is synthesized by an aqueous preparation method and washed three times with water and three times with isopropyl alcohol. The reaction can be carried out using a non-aqueous solvent such as a dimethylformamide (DMF) / methanol (MeOH) mixture, an aqueous solvent, or both, as disclosed in PCT / US2022 / 082243. Then, this substance is dried by vacuum filtration to obtain a solventate substance of about 70 - 75%. To prepare the supporting material, this is desolvated in a vacuum oven at 120 °C overnight to reduce the alcohol content to 0.5 - 1 equivalent of isopropyl alcohol (IPA) per metal site. This is to protect the open metal sites from oxidation and remove excess solvent from the pores of the MOF. As shown in Figure 18, by determining how much residual solvent is present in the MOF by 1 1H NMR (for example, Mg 2 (dobpdc) 1 (alcohol) x ), the exact molar amount of the MOF can be determined. Therefore, by adding ~4 equivalents of amine in a polar solvent, a substance with the composition of Mg 2 (dobpdc) 1 (amine) x can be formed. Figure 19 shows the SEM image of an exemplary MOF-274 (sample ID#A2111) manufactured according to a standard aqueous preparation method.

[0354] General procedure for MOF and sorbent synthesis Example C2. To digest the amine-added MOF, 10 mg of the material is added to 20 μL of 35% DCl (D 2O), 200 μL of D 2 O and 600 μL of DMSO-d 6 were added to the vial. The vial was sonicated to dissolve the structure, 1 and 1H NMR was performed. The loading amount was determined by the 4 1H NMR integration ratio of the structure ligand peak (H 1 dobpdc) and the amine peak.

[0355] General analytical method for amine content by NMR . Example C3 The particle diameter or length of the rod-shaped crystals is not limited, but can be decreased by a number of methods, including mechanical grinding such as grinding in a mortar, use of a microfluidizer, use of dry or wet milling, or chemical means such as introduction of a crystal growth inhibitor. Table 1 summarizes the particle diameter and aspect ratio of MOF-274 prepared according to an embodiment.

[0356]

Table 1

[0357] Particle size reduction . Example C4 Mg 2 (dobpdc) was first synthesized by heating and dissolving x moles of H 4 dobpdc, y moles of a synthetic crystal growth inhibitor, and 4x + 2y moles of NaOH in water at 60 °C. Examples of the synthetic crystal growth inhibitor include, but are not limited to, salicylic acid (SA), 4-fluorosalicylic acid (FSA), 4,4'-biphenol (BP), 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC), and 2,2'-bipyridine-5,5'-dimethanol (BPYDM). The number of moles of the crystal growth inhibitor can be 0.1 - 50 mol% relative to 99.9 - 50 mol% of H 4 dobpdc. To this deprotonated solution of the linker and the crystal growth inhibitor, an aqueous solution of a Mg 2+ salt (the counter anion is NO 3 -, Cl - , Br - , SO 4 2- , OAc - , O 2- , Otf - (any one of) is added to make a solution. Mg 2+ The addition of the Mg salt may be carried out rapidly (e.g., less than 1 minute) or may be added dropwise over a long period of time (e.g., more than 1 hour). The temperature is raised to 97 °C and refluxed for 12 - 16 hours under N 2 The white precipitate is washed three times with water and three times with isopropyl alcohol and solvated and stored until use later.

[0358] General procedure for small-scale synthesis of MOF-274 using a crystal inhibitor . Exemplary procedure for small-scale synthesis of MOF-274 using salicylic acid as a crystal inhibitor Mg 2 (dobpdc) was prepared on a 300 mL scale. First, the linker, crystal growth inhibitor, and base were added to a 500 mL round-bottom flask and heated to dissolve in water. In this example, the solution was stirred and heated to 60 °C under N 2 in the flask until it became clear, and sodium hydroxide (76 mmol, 3.04 g), H 4 dobpdc (18 mmol, 4.94 g), and salicylic acid (2 mmol, 0.276 g) were dissolved in water (220 mL). Then, in a separate container, Mg(NO 3 ) 2 hexahydrate (45 mmol, 11.54 g) was dissolved in 80 mL of water and quickly added to the deprotonated linker solution to precipitate the MOF. The mixture was reacted for 12 - 16 hours while gently refluxing at 97 °C under atmospheric pressure in an open flask. In this reaction, the MOF compound Mg 2 (dobpdc)(salicylic acid) x was formed, washed three times with water and three times with isopropanol, and stored in alcohol. For surface area measurement, the material was activated at 250 °C to obtain the highest absorption amount. In this reaction, for each separate batch, 4.2 - 4.7 g (yield 72 - 81%) of Mg 2 (dobpdc)(salicylic acid e) xwas produced. The material was desolvated at 85 °C and can be normally supported as ordinary MOF-274. Shown in Fig. 20 are SEM images of exemplary MOF-274 produced using salicylic acid (left) and fluoro-salicylic acid (right) as crystal growth inhibitors.

[0359] Example C5 . Exemplary procedure for small-scale synthesis of MOF-274 using 4,4'-biphenol as a crystal inhibitor Mg 2 (dobpdc) was prepared on a 20 mL scale. First, the linker, crystal growth inhibitor, and base were added to a 20 mL scintillation vial and heated to dissolve in water. In this example, by stirring and heating to 60 °C until the solution became clear in the vial, sodium hydroxide (4 mmol, 0.160 g), H 4 dobpdc (0.9 mmol, 0.247 g), and 4,4'-biphenol (0.1 mmol, 0.019 g) were dissolved in water (10 mL). Then, in a separate container, Mg(NO 3 ) 2 hexahydrate (2 mmol, 0.512 g) was dissolved in 5 mL of water and quickly added to the deprotonated linker solution to precipitate the MOF. The mixture was reacted for 12 - 16 hours while gently refluxing at about 97 °C under atmospheric pressure in the vial. In this reaction, the MOF compound Mg 2 (dobpdc)(BP) x was produced, washed three times with water and three times with isopropanol, and stored in alcohol. For surface area measurement, the material was activated at 250 °C to obtain the highest absorption amount. In this reaction, based on the amount of inhibitor used, Mg 2 (dobpdc)(BP) x with a yield of 37 - 72% was produced. The material was desolvated at 85 °C and can be normally supported as ordinary MOF-274. Shown in Fig. 21 is the powder X-ray diffraction spectrum of MOF-274 synthesized using 4,4'-biphenol as a crystal growth inhibitor, and the MOF-274 phase is retained with 50 mol% input of BP. As shown in Fig. 22, the particle size clearly decreases with the introduction of 4,4'-biphenol.

[0360]

Table 2

[0361] Example C6 . Exemplary procedure for small-scale synthesis of MOF-274 using BPYDC as a crystal inhibitor Mg 2 (dobpdc) was prepared on a 20 mL scale. First, the linker, crystal growth inhibitor, and base were added to a 20 mL scintillation vial and heated to dissolve in water. In this example, by stirring and heating to 60 °C until the solution became clear in the vial, sodium hydroxide (4 mmol, 0.160 g), H 4 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). Then, in a separate container, Mg(NO 3 ) 2 hexahydrate (2 mmol, 0.512 g) was dissolved in 5 mL of water and quickly added to the deprotonated linker solution to precipitate the MOF. The mixture was reacted for 12 - 16 hours while gently refluxing at about 97 °C under atmospheric pressure in the vial. In this reaction, the MOF compound Mg 2 (dobpdc)(BPYDC) x was formed, washed three times with water and three times with isopropanol, and stored in alcohol. For surface area measurement, the material was activated at 250 °C to obtain the highest absorption amount. In this reaction, based on the amount of inhibitor used, Mg 2 (dobpdc)(BPYDC) x was formed in a yield of 68 - 74%. The material can be desolvated at 85 °C and normally supported as ordinary MOF-274. Shown in Figure 23 is the powder X-ray diffraction spectrum of MOF-274 synthesized using 2,2'-bipyridine-5,5'-dicarboxylic acid (BPYDC) as the crystal growth inhibitor. The MOF-274 phase is retained up to 50 mol% input of BPYDC. As shown in Figure 24, the particle size clearly decreases with the introduction of BPYDC.

[0362]

Table 3

[0363] Example C7 . Exemplary procedure for small-scale synthesis of MOF-274 using BPYDM as a crystal inhibitor Mg 2 (dobpdc) was prepared on a 20 mL scale. First, the linker, crystal growth inhibitor, and base were added to a 20 mL scintillation vial and heated to dissolve in water. In this example, by stirring and heating to 60 °C until the solution in the vial became clear, 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). Then, in a separate container, Mg(NO 3 ) 2 hexahydrate (2 mmol, 0.512 g) was dissolved in 5 mL of water and quickly added to the deprotonated linker solution to precipitate the MOF. The mixture was reacted for 12 - 16 hours while gently refluxing at about 97 °C under atmospheric pressure in the vial. In this reaction, the MOF compound Mg 2 (dobpdc)(BPYDM) x was produced, washed three times with water and three times with isopropanol, and stored in alcohol. For surface area measurement, the material was activated at 250 °C to obtain the highest absorption amount. In this reaction, based on the amount of inhibitor used, Mg 2 (dobpdc)(BPYDM) x was produced with a yield of 53 - 81%. Shown in Figure 25 is the powder X-ray diffraction spectrum of MOF-274 synthesized using 2,2'-bipyridine-5,5'-dimethanol (BPYDM) as the crystal growth inhibitor. With the introduction of BPYDM, initially the particle length of MOF-274 decreases. However, when the BPYDM loading is further increased, as shown in Figure 26, the particle length increases and the aspect ratio decreases.

[0364]

Table 4

[0365] Example C8 . Naked MOF example: CO 2 Improvement of absorption rate Comparative Example 1; The bare MOF sample with ID A2173 was prepared using an aqueous solvent (H 2 O) according to the general procedure described in Example 1.

[0366] Comparative Example 2; The bare MOF sample with ID A315B was prepared according to the general procedure of Example C5, but DMF, a non-aqueous solvent, was used.

[0367] Example 1; The bare MOF sample with ID A2177 was prepared using an aqueous solvent (H 2 O) according to the general procedure described in Example C1.

[0368] Example 2; The bare MOF sample with ID A316 was prepared according to the general procedure of Example C5, but salicylic acid (SA) as a crystal growth inhibitor and an aqueous solvent (H 2 O) were used.

[0369] Example 3; The bare MOF sample with ID A39C was prepared according to the general procedure of Example C5, but salicylic acid (SA) as a crystal growth inhibitor and an aqueous solvent (H 2 O) were used.

[0370] Table 2 summarizes the details of the particle size, aspect ratio, and CO absorption performance measured using the DVS measurement method under a dry CO concentration of 4.5% by volume. It can be seen that a MOF with a significantly improved CO absorption rate can be obtained by combining a decrease in particle size, an increase in aspect ratio, and the aqueous synthesis of MOF. 2 absorption amount measured using the DVS measurement method under 2 a dry CO concentration of 4.5% by volume. The combination of a decrease in particle size, an increase in aspect ratio, and the aqueous synthesis of MOF results in a significant improvement in the CO 2 absorption rate.

[0371]

Table 5

[0372] Example C9 . Example of sorbent; CO 2 Improvement of absorption rate Aqueous-synthesized MOF-274 [Mg 2(dobpdc) is used as a specific example. The exemplary sorbent material is synthesized using an aqueous solvent and further functionalized with a hybrid amine consisting of spermine and AEAM according to the disclosure of the present application and PCT / US2023 / 060396 and PCT / US2023 / 021542 to form MOF-274. Shown in Figure 27 are the chemical structures of aminosilicon, spermine, and some exemplary aminosilicones. The chemical structures of additional aminosilicones can be found in the present application and PCT / US2023 / 060396 and PCT / US2023 / 021542. MOF-274 synthesized according to the general procedure described in Example C1 generally contains hexagonal channels and has a thin and long rod-like shape of 1 to several microns (Fu et al., Science Advances, 2023, 9, 6 and US 2022 / 0266219).

[0373] A sorbent functionalized with spermine and AEAM using MOF-274 prepared according to Example C1 was used as a comparative example (hereinafter, Comparative Example 3) (GE115-A259). This MOF-274 (ID#A21) has a particle size of about 2.2 μm (Figure 28).

[0374] Shown in Figure 29 is an exemplary SEM image of an example (hereinafter, Example 4) (GE115-A272). The same batch of MOF is used for both GE115-A259 and GE115-A272. The only difference is that the MOF for GE115-A272 was ground in a mortar before amine loading to reduce the particle length from about 2.2 μm to about 0.8 μm. Shown in Figure 30 is an exemplary SEM image of another example (hereinafter, Example 5) (GE115-A279). The MOF used for GE115-A279 was mechanically pulverized before amine loading to reduce the particle length.

[0375] CO 2 and H 2 O absorption was measured at 25 °C, 50% RH, and 5000 ppmv CO 2 using the DVS measurement method. The amine loading amount, CO 2 absorption amount, and CO 2The details of the speed are summarized in Table 3. As is clear from the table, the examples with reduced particle length show the same CO 2 absorption amount, but the speed is significantly improved compared to the comparative examples.

[0376]

Table 6

[0377] Example C10 . Improvement of working capacity by adjusting the ratio of hybrid amine The aqueous synthesized MOF-274 [Mg2(dobpdc)] was used as an exemplary example with spermine, APAP (Figure 27; N 1 ,N 1 ’-((1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(propane-1,3-diamine)) and mixtures of their various ratios. MOF-274 was synthesized according to the procedure described in Example C4, and the average particle size was 0.4 μm. The CO 2 and H 2 O absorption amounts were measured using the breakthrough test apparatus shown in Figure 31 under DAC-compliant conditions (25 °C, 50% RH, and 400 ppmv CO 2 ). Figure 32 shows the absorption of dry CO 2 at 120 °C for a 100 mbar CO 2 concentration measured using the DVS gravimetric method, which is used as an indicator of desorption residue under a 100 mbar CO 2 partial pressure. Subtracting the desorption residue from the adsorption capacity estimates the working capacity of CO 2 absorption (Figure 33). The adsorbent modified with pure spermine (GE5-A2175) has the highest adsorption absorption amount and the highest desorption residue under DAC-compliant conditions, and the working capacity is 0.07 gCO 2 / g sorbent. The sorbent modified with pure APAP (GE281-111B1) has a significantly reduced desorption residue and adsorption capacity, and the working capacity is 0.01 gCO 2 / g serves as an adsorbent. The adsorbents (GE283-151A) and GE284-151B) modified with hybrid amine have a significantly increased working capacity compared to the adsorbents modified with pure spermine or pure APAP.

[0378]

Table 7

[0379] This time, by reducing the particle size of the adsorbent, increasing the aspect ratio of the adsorbent, and / or performing aqueous synthesis of the adsorbent, it was found that an adsorbent with a significantly improved CO 2 absorption rate can be obtained. Generally, the higher the CO 2 absorption rate, the greater the amount of CO 2 collected per unit time, and the collection cost and potential energy consumption are reduced.

[0380] Definition In this application, when referring to "exemplary or exemplary embodiments" or "an embodiment" of the present disclosure, it should not be construed as excluding the existence of additional embodiments having the described features.

[0381] Certain features of various embodiments of the present invention may be described in one drawing and not in another, but this is merely for convenience. In accordance with the principles of the present invention, the features described in one drawing can be combined with the features described in other drawings and / or recited in the claims.

[0382] Although the present invention has been described with respect to various specific embodiments, it will be apparent to those skilled in the art that the present invention can be practiced with modifications within the technical spirit and scope of the claims.

[0383] When introducing the components of the various embodiments disclosed in this application, those described in the singular mean that there is one or more of such components. The terms "comprise", "include" and "have" are inclusive and mean that additional components other than the described components may be present.

[0384] Unless otherwise specified, approximate expressions such as "substantially", "essentially" and "about" as used in this specification indicate that the terms modified by them are not absolute or exact, but only approximate and obvious to those skilled in the art. Therefore, values modified by terms such as "about", "substantially" and "essentially" are not limited to their exact numerical values. In at least some cases, the approximate expression corresponds to the accuracy of the device for measuring the value. Further, unless otherwise specified, terms such as "first", "second" etc. in this application are merely labels and do not impose numerical, positional or hierarchical requirements on the things to which they are attached. Further, for example, in the case of "second", it does not require or exclude the existence of something such as "below the first" or "above the third".

[0385] Unless otherwise specified, approximate expressions such as "substantially", "essentially" and "about" as used in this specification indicate that the terms modified by them are not absolute or exact, but only approximate and obvious to those skilled in the art. Therefore, values modified by terms such as "about", "substantially" and "essentially" are not limited to their exact numerical values. In at least some cases, the approximate expression corresponds to the accuracy of the device for measuring the value. Further, unless otherwise specified, terms such as "first", "second" etc. in this application are merely labels and do not impose numerical, positional or hierarchical requirements on the things to which they are attached. Further, for example, in the case of "second", it does not require or exclude the existence of something such as "below the first" or "above the third".

[0386] In this specification, the present invention has been disclosed including the best mode, and has been described by way of examples in order to enable those skilled in the art to start manufacturing and using the device or system and practicing the method, so that they can practice the present invention. The scope of patentability of this disclosure is defined by the claims, and also includes other examples that are obvious to those skilled in the art. Such other examples belong to the technical scope described in the claims if they have components that have no literal difference from the claims or have equivalent components that have only an insubstantial difference from the literal meaning of the claims.

[0387] It will be apparent to those skilled in the art that some of the substituents of this disclosure are dependent on the presence of other substituents and are optional. For example, in Formula A-II, when R 9 is a direct bond, R 1 and R 2 are any substituents that do not exist in the compound. Similarly, in Formula A-II, when n is 0, the bond between R 9 and R 10 is a direct bond, and R 3 , R 4 and R 11 are any substituents that do not exist in the compound. Even if the substitution values are optional in certain embodiments, it does not limit the presence of substituents in other embodiments.

[0388] As used herein, the term "alkyl" includes straight-chain or branched alkyl such as methyl, ethyl, n-propyl and i-propyl, or various butyl, pentyl or hexyl isomers, whether used alone or in a compound name such as "haloalkyl". Alkyl defined by the number of carbon atoms (e.g., C 6 alkyl) is understood to have that number of carbon atoms and is not further limited.

[0389] As used herein, the term "heteroalkyl" refers to an alkyl chain in which one or more of the elements forming the backbone are other than carbon.

[0390] As used herein, "aminoalkyl" includes those in which the N-group is substituted with a straight-chain or branched alkyl.

[0391] As used herein, the terms "halogen" or "halide", whether used alone or in a compound name such as "haloalkyl", include fluorine, chlorine, bromine or iodine. Further, when used in a compound name such as "haloalkyl", the alkyl thereof is partially or completely substituted with the same or different halogen atoms. Specific examples of "haloalkyl" include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 . Terms such as "haloalkoxy" are defined in the same manner as the term "haloalkyl". Specific 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.

[0392] As used herein, the term "heterocyclic" refers to a ring in which one or more of the elements forming the ring skeleton are other than carbon. Unless otherwise specified, the heterocyclic ring may be saturated, partially saturated or completely unsaturated. A completely unsaturated heterocyclic ring satisfies the Hückel rule, and such a ring is also referred to as a "heteroaryl" or an aromatic heterocyclic ring. A "saturated heterocyclic ring" refers to a heterocyclic ring containing only single bonds between ring member atoms.

[0393] As used herein, the term "aminosilicon group" encompasses a functional group containing both a siloxane group (also referred to as a disiloxane group) containing an Si-O-Si bond and an amine group.

[0394] 1 The 1H NMR spectrum is shown in ppm on the low magnetic field side of tetramethylsilane, where "s" means singlet, "d" means doublet, "dd" means doublet of doublets, "ddd" means doublet of doublets of doublets, "t" means triplet, "m" means multiplet and "br s" means broad singlet.

[0395] The terms "software" and "firmware" as used in this application are interchangeable and include any computer program stored in memory for execution by a processor, including RAM memory, ROM memory, EPROM memory, EEPROM memory, and non-volatile RAM (NVRAM) memory. The above types of memory are merely illustrative and do not limit the types of memory that can be used for storing computer programs.

[0396] In this application, a processor may include any programmable system that includes a microcontroller, a reduced instruction set circuit (RISC), an application-specific integrated circuit (ASIC), a logic circuit, or any other circuit or system using a processor capable of performing the functions described in this application. The above examples are merely illustrative and do not limit the definition and / or meaning of the term "processor".

[0397] The systems and processes are not limited to the specific embodiments described in this application. Further, the components of each system and each process can be implemented separately and independently from the other components and processes described in this application. Each component and process can be used in combination with other assembly packages and processes.

[0398] As used herein, the term "non-transitory computer-readable medium" represents a tangible computer device embodied in a method or technology for short-term and long-term storage of information, such as computer-readable instructions, data structures, program modules and sub-modules, and other data, in any device. Thus, the methods described herein may be encoded, but not limited to, as executable instructions implemented on a tangible non-transitory computer-readable medium, including, but not limited to, a storage device and / or a memory device. When executed by a processor, such instructions cause the processor to execute at least a portion of the methods described herein. Further, as used herein, the term "non-transitory computer-readable medium" encompasses any tangible computer-readable medium, including, but not limited to, non-transitory computer storage devices, including volatile and non-volatile media, as well as firmware, physical and virtual memories, removable and non-removable media such as CD-ROMs, DVDs, and other digital sources such as networks or the Internet, and even digital means not yet developed, with the sole exception being a transitory propagation signal.

Claims

1. A functionalized sorbent, comprising: Sorbents, and One or more functionalized ligands containing aminosilicone groups. wherein said sorbent has an average particle length of 3 μm or less.

2. 10. The functionalized sorbent of claim 1, further comprising one or more functionalizing ligands that are free of aminosilicone groups.

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

10.

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

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

6. The MOF linker is a polytopic linker, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H ４ dobpdc), 4,4'-dioxidobiphenyl-3,3'-dicarboxylate (dobpdc ４－ ), 4,4″-dioxido-[1,1′:4′,1″-terphenyl]-3,3″-dicarboxylate (dotpdc ４－ ), 2,5-dioxidobenzene-1,4-dicarboxylate (dobdc ４－ ), 4,6-dihydroxyisophthalic acid (m-dobdc ４－ ), 3,3'-dioxide-biphenyl-4,4'-dicarboxylate (para-carboxylate-dobpdc ４－ ), 4,4'-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) (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), dicarboxylates, terephthalic acid, tricarboxylates, 1,3,5-benzenetricarboxylic acid, azolates, tetrazolates, 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methyl Quinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylene dicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-carboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis-(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-dinaphthyl 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7,8,1-trifluoro-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7,-Hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-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 E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diaminodiphenyletherdiimidedicarboxylic acid, 4,4'-diaminodiphenylmethanediimidedicarboxylic acid, 4,4'-diaminodiphenylsulfonediimidedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2'-3'-diphenyl-p-terphenyl-4,4"-dicarboxylic acid, diphenyl ether 4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-t-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-Pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorubin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid , heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, 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, carboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, aurintricarboxylic acid, 1,1-dioxide-perillo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene -1,12-sulfone-3,4,9,10-tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, meso-1,2,3,4-butane tetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzene tetracarboxylic acid, 1,2,11,12-dodecane tetracarboxylic acid, 1,2,5,6-hexane tetracarboxylic acid, 1,2,7,8-octane tetracarboxylic acid, 1,4,5,5. The functionalized sorbent of claim 4, comprising a linker selected from the group consisting of 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, polytopic linkers, ditopic linkers, tritopic linkers, tetratopic linkers, pentatopic linkers, hexatopic linkers, heptatopic linkers, octatopic linkers, mixed linkers, asymmetric linkers, metallolinkers, N-heterocyclic linkers, protonated forms thereof, partially or fully deprotonated forms thereof, and combinations thereof.

7. 10. The functionalized sorbent of claim 1, wherein the sorbent has an aspect ratio greater than 0.

2.

8. 2. The functionalized sorbent of claim 1, wherein the sorbent has an average particle length of less than 1 μm.

9. 2. The functionalized sorbent of claim 1, wherein the one or more functionalizing ligands comprising aminosilicone groups are amino-substituted siloxanes of the following formula (A-II), (A-III), (A-IV), (A-V), (A-VI) or (A-VII): 【Chemistry 1】 【Chemistry 2】 During the ceremony, R １ , R ２ , R ３ , R ４ , R ９ , R １０ , R １３ , R １４ and R １８ are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C １ -C ６ Linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C ３ -C ６ selected from the group consisting of branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R ５ , R ６ , R １１ , R １５ and R １７ Each independently is a direct bond, a substituted or unsubstituted C １ -C ６ Linear 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 is selected from the group consisting of alkyl, R ７ , R ８ , R １２ and R １６ Each independently is a direct bond, a substituted or unsubstituted C １ -C ６ Linear 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 is selected from the group consisting of alkyl and a substituent of the following formula (A-VIII): 【Chemistry 3】 During the ceremony, the wavy bond indicates the position of binding to formula (A-II) or formula (A-III) or formula (A-IV) or formula (A-V) or formula (A-VI) or formula (A-VII); R １９ , R ２０ , R ２１ , R ２２ , R ２３ and R ２４ are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C １ -C ６ Linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C ３ -C ６ Branched alkyl, substituted or unsubstituted linear heteroalkyl, substituted or unsubstituted C １ -C ６ Linear heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C ３ -C ６ selected from the group consisting of branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; R ２５ and R ２６ are each independently hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C １ -C ６ Linear alkyl, substituted or unsubstituted C １ -C ３ Linear alkyl, substituted or unsubstituted branched 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 R ２５ and R ２６ together form a monocyclic ring selected from the group consisting of heterocycloalkyl or heteroaryl; R ２７ , R ２８ and R ２９ Each independently is a direct bond, a substituted or unsubstituted C １ -C ６ Linear 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 - selected from the group consisting of R ３０ is hydrogen, substituted or unsubstituted linear alkyl, substituted or unsubstituted C １ -C ６ Linear alkyl, substituted or unsubstituted C １ -C ３ Linear alkyl, substituted or unsubstituted branched 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 selected from the group consisting of cycloalkyl, heterocycloalkyl, and heteroaryl; j is an integer from 0 to 20; k is an integer from 0 to 20; m is an integer from 0 to 20; n is an integer from 0 to 20.

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

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

12. 1. A method for producing a sorbent, the method comprising: (I) forming a mixture including a sorbent precursor, a crystal growth inhibitor, an optional solvent, and an optional non-solvent; and (II) Reacting the mixture wherein the sorbent has an average particle length of 3 μm or less.

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

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

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

Images