Systems and methods for fluid capture

Abstract

In some embodiments, the present disclosure relates to methods of functionalizing a fluid trapping material with at least one functionalizing ligand comprising an amine group. In some embodiments, the present disclosure relates to a system comprising a substrate and a fluid trapping material formed on one or more surfaces of the substrate. The fluid capture material includes a sorbent material incorporating one or more fluids including water, carbon dioxide, sulfur oxides, alcohols, or a combination thereof. The fluid capture material also includes one or more binder materials, wherein the binder materials are optionally at least partially cross-linked. The fluid capture material optionally includes at least one aperture. The fluid capture material is functionalized with at least one functionalization ligand comprising an amine group.

Description

[0001] Related applications

[0002] This application claims priority to international application PCT / US2023 / 021542, filed May 9, 2023, the contents of which are incorporated herein by reference in their entirety. Background Technology

[0003] The subject matter disclosed herein relates to techniques for capturing one or more target fluids. More specifically, the subject matter disclosed herein relates to forming fluid-capturing materials or coatings using combinations or mixtures of binders and adsorbents. The fluid-capturing material optionally includes at least one pore. The fluid-capturing material is functionalized with at least one functionalized ligand comprising an amine group.

[0004] Some industrial systems may generate multiple fluids, such as water and carbon dioxide (CO2), during their operation. In some cases, the fluids may be discharged as exhaust gases or otherwise remain unused. Certain components of industrial systems (e.g., substrates) may include coatings capable of capturing or extracting fluids. In some cases, it may be desirable to extract fluids, such as CO2 and water, directly from the air. Summary of the Invention

[0005] The following outlines certain embodiments equivalent to the scope of the originally filed claims. These embodiments are not intended to limit the scope of the invention, but rather are intended only to provide a brief overview of the possible forms of the invention. In practice, the systems and methods of the invention may include various forms that may be similar to or different from the embodiments set forth below.

[0006] In one embodiment, this disclosure relates to a method for functionalizing a system. The system includes a substrate and a fluid trapping material formed on one or more surfaces of the substrate. The method includes functionalizing the fluid trapping material with at least one functionalizing ligand comprising an amine group.

[0007] In one embodiment, this disclosure relates to a method. The method includes providing an adsorbent material configured to bind one or more fluids, the one or more fluids including water, carbon dioxide, sulfur oxides, alcohols, or combinations thereof. The method also includes providing one or more binder materials, wherein the one or more binder materials optionally contain components capable of forming crosslinked polymers. Additionally, the method includes optionally providing a crosslinking agent. Additionally, the method includes optionally providing a pore precursor. Furthermore, the method includes generating an adsorbent-binder material based on the adsorbent material, one or more binder materials, optionally a crosslinking agent, and optionally a pore precursor. Furthermore, the method includes: applying the adsorbent-binder material to a substrate; forming a fluid trapping material using the adsorbent-binder material applied to the substrate; optionally removing the pore precursor to form at least one pore in the fluid trapping material; and functionalizing the fluid trapping material with at least one functionalized ligand containing an amine group.

[0008] In one embodiment, this disclosure relates to a system. The system includes a substrate and a fluid trapping material formed on one or more surfaces of the substrate. The fluid trapping material includes: an adsorbent material configured to bind one or more fluids including water, carbon dioxide, sulfur oxides, alcohols, or combinations thereof; and one or more binder materials, wherein the binder materials are optionally at least partially crosslinked. The fluid trapping material optionally includes at least one pore. The adsorbent material is functionalized with at least one functionalized ligand comprising an amine group. Attached Figure Description

[0009] These and other features, aspects, and advantages of the invention will be better understood when the following detailed description is read with reference to the accompanying drawings, in which the same reference numerals denote the same parts throughout the drawings, wherein:

[0010] Figure 1 This is a flowchart of an embodiment of a method for capturing a target fluid using a fluid capture system having one or more substrates, according to the present disclosure;

[0011] Figure 2 It is in accordance with this disclosure for use in Figure 1 A flowchart of an implementation scheme for using a combination of binders and adsorbents in a fluid capture system to produce a fluid capture material;

[0012] Figure 3 It is coated with according to this disclosure Figure 2 A cross-sectional view of an embodiment of a substrate for a fluid trapping material;

[0013] Figure 4It is a graph depicting the carbon dioxide (CO2) concentration versus time of a fluid flow guided to a substrate having a fluid trapping material according to the present disclosure;

[0014] Figure 5 This is a visual flowchart illustrating the operational aspects of a fluid trapping system having one or more substrates coated with a fluid trapping material according to the present disclosure;

[0015] Figure 6 It is a graph depicting the weight increase of a substrate with a fluid trapping material exposed to a fluid flow over time, according to the present disclosure;

[0016] Figure 7 The image is a scanning electron microscope (SEM) image of a cross-section of a film including wax crystals after casting, according to the present disclosure.

[0017] Figure 8 This is a SEM image of a cross-section of a film produced after casting and using wax crystals, according to this disclosure, wherein the wax crystals have been removed; and

[0018] Figure 9 It is in accordance with this disclosure for the purpose of including [the following] Figure 1 A flowchart of an implementation scheme for functionalizing fluid trapping materials using a combination of binders and adsorbents in a fluid trapping system. Detailed Implementation

[0019] One or more specific embodiments of this disclosure will now be described. To provide a concise description of these embodiments, not all features of the actual implementation may be described in the specification. It should be understood that, as in any engineering or design project, numerous implementation-specific decisions must be made in the development of any such implementation to achieve the developer's specific objectives, such as complying with system-related and business-related constraints, which may vary from implementation to implementation. Furthermore, it should be understood that such development work may be complex and time-consuming, but remains a routine task of design, fabrication, and manufacturing for those skilled in the art who benefit from this disclosure.

[0020] When describing the elements of various examples of this disclosure, the articles “a,” “the,” and “the” are intended to mean that one or more elements are present. The terms “comprising,” “including,” and “having” are intended to be inclusive and mean that additional elements may exist in addition to those listed. Furthermore, it should be understood that references to “a single example” or “example” in this disclosure are not intended to be construed as excluding the existence of additional examples that also include the listed features.

[0021] In the context of this invention, the terms “about” or “approximately” are intended to indicate that the indicated value is not precise and that the actual value may differ from the indicated value without substantially altering the manner in which the relevant operation is performed. For example, the terms “about” or “approximately” as used herein are intended to convey a suitable value within a particular manufacturing or operating tolerance (e.g., ±10%, ±5%, ±1%, ±0.5%), as will be understood by those skilled in the art.

[0022] As generally discussed herein, certain systems (e.g., gas turbines) that generate one or more fluids (e.g., water and / or CO2) may include one or more substrates having a surface coating that incorporates the one or more fluids, thereby extracting or capturing the one or more fluids from a source fluid (e.g., exhaust gas stream, ambient air stream, etc.). For example, these systems may include combustion systems that utilize a fuel source (e.g., fossil fuels). Thus, one or more substrates of these combustion systems may include a surface coating capable of extracting carbon dioxide. As another non-limiting example, these systems may include water capture systems that typically include a surface coating capable of extracting water from ambient air. As another non-limiting example, these systems may include CO2 capture systems that typically include a surface coating capable of extracting CO2 from ambient air. In some embodiments, it may be desirable to capture at least a portion of these fluids, such as to address the guidance (e.g., government regulation) and / or utilize the one or more fluids, rather than not capturing them, such as by discharging or otherwise releasing these fluids into the surrounding airspace or other adjacent environment.

[0023] This disclosure relates to techniques for improving the efficiency of capturing or extracting certain fluids from a fluid stream by forming a fluid-capturing material or fluid-capturing coating using an adsorbent material (e.g., an adsorbent component) and optionally a crosslinkable binder material, and optionally crosslinking the binder material (e.g., using a crosslinking agent). As described in more detail herein, the adsorbent material typically comprises a material capable of binding certain fluids, such as carbon dioxide (CO2), water (H2O), oxygen (O2), or other gas molecules that can be formed due to a decomposition reaction (e.g., combustion). For example, the adsorbent material may comprise a metal-organic framework (MOF) and / or a covalent organic framework (COF). In some embodiments, the adsorbent material may comprise a polymeric resin, silica, zeolite, and other materials capable of capturing fluids as discussed herein. The binder material may comprise one or more materials that can prevent, reduce, or mitigate the decomposition or dissolution of the adsorbent material (i.e., improve stability). As described in more detail herein, it is now recognized that using an adsorbent material and optionally crosslinking a binder material to form a fluid-capturing material can provide improved fluid binding capacity (e.g., in a reversible or irreversible manner) compared to conventional fluid-binding materials or coatings. As described in more detail in this article, it is now recognized that the adsorbents of fluid trapping materials can be functionalized.

[0024] Typically, the adsorbent can be any suitable adsorbent known in the art that promotes the functionalization of the adsorbents described herein. In some embodiments, the adsorbent is selected from the group consisting of: coordination framework compounds, metal-organic framework (MOF) compounds, porous coordination polymers (PCP), covalent organic framework (COF) compounds, zeolite imidazole ester framework (ZIF) compounds, crystalline porous materials, crystalline open frameworks, network chemical compositions, silica particles, zeolites, silica-alumina-phosphate (SAPO), aluminum-phosphate (AlPO), polyaromatic frameworks (PAF), activated carbon, molecular organic solids, and combinations thereof.

[0025] As used herein, MOF compounds are a class of compounds comprising metal ions or clusters that coordinate with organic ligands to form one-dimensional, two-dimensional, or three-dimensional structures. The metal ions or clusters act as junctions and are bound via multidirectional organic ligands that act as connectors within the network structure. MOF compounds possess modular properties that allow for tunable synthesis, providing fine chemicals and structural control. Properties such as porosity, stability, particle morphology, and conductivity can be tailored for specific applications.

[0026] In many embodiments, the adsorbent is a MOF metal or a MOF compound containing a metal cluster and a MOF linker.

[0027] In some embodiments, the MOF metal can be any suitable MOF metal known in the art that promotes the functionalization of the adsorbents described herein. In other embodiments, the MOF metal is a metal selected from the group consisting of: alkali metals, alkaline earth metals, transition metals, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, their ions, their hydrates, their salts, their halides, their fluorides, their chlorides, their bromides, their iodides, their nitrates, their acetates, their sulfates, their phosphates, their carbonates, their oxides, their formates, their carboxylates, and combinations thereof. In some embodiments, the MOF metal includes Mg.

[0028] In some embodiments, the MOF-containing metal cluster can be any suitable MOF-containing metal cluster known in the art that promotes the functionalization of the adsorbent described herein. In some embodiments, the MOF-containing metal cluster includes MOF metal nodes and linker struts, wherein the MOF metal and the linker are each defined as described herein. In other embodiments, the MOF-containing metal cluster includes MOF metal-oxygen clusters.

[0029] In some embodiments, the MOF linker can be any suitable MOF linker known in the art that facilitates the functionalization of the adsorbents described herein. Typically, the geometry and connectivity of the linker contribute to the structure of the resulting MOF compound. Adjusting the linker geometry, length, ratio, and functional groups can tune the size, shape, and internal surface properties of the MOF compound for targeted applications.

[0030] In at least some embodiments, the MOF linker is a linker selected from the group consisting of: polytopic linker, two-sided linker, three-sided linker, four-sided linker, five-sided linker, six-sided linker, seven-sided linker, eight-sided linker, hybrid linker, asymmetric linker, metallic linker, N-heterocyclic linker, and combinations thereof.

[0031] In at least some embodiments, the MOF linker is a linker selected from the group consisting of: faceted linkers, 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc), and 4,4'-dioxobiphenyl-3,3'-dicarboxylic acid ester (dobpdc). 4- ), 4,4”-dioxo-[1,1':4',1”-terphenyl]-3,3”-dicarboxylic acid ester (dotpdc) 4- ), 2,5-dioxophenyl-1,4-dicarboxylic acid ester (dobdc) 4- ), 4,6-dihydroxyisophthalic acid (m-dobdc) 4-), 3,3'-dioxo-biphenyl-4,4'-dicarboxylic acid ester (para-carboxylic acid ester-dobpdc 4- 4,4'-[oxaloylbis(imino)]bis(2-hydroxybenzoic acid) (H4ODA), 4,4'-[1,4-phenylenebis-(carbonylimino)]bis(2-hydroxybenzoic acid) (H4TDA), 4,4'-dihydroxyazobenzene-3,3'-dicarboxylic acid (H4OSA), their protonated, partially and completely deprotonated forms, and combinations thereof. As another example, in at least some embodiments, the MOF linker is a linker selected from the group consisting of: dicarboxylic acid esters (e.g., terephthalic acid), tricarboxylic acid esters (e.g., 1,3,5-benzenetricarboxylic acid), azolates, tetrazolates, and combinations thereof.

[0032] As another example, in at least some embodiments, the MOF linker is a dicarboxylic acid linker selected from the group consisting of: 1,4-butanedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenediacarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenediacarboxylic acid, p-benzenediacarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline. Phosphoro-3,4-dicarboxylic acid, Quinoline-2,4-dicarboxylic acid, Quinoxaloline-2,3-dicarboxylic acid, 6-chloroquinoxaloline-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-methylimidazolium-4,5-dicarboxylic acid, Thiophene-3,4-dicarboxylic acid, 2-isopropylimidazolium-4,5-dicarboxylic acid, Tetrahydropyran-4,4-dicarboxylic acid, Perylene-3,9-dicarboxylic acid, Perylene dicarboxylic acid, Pluriol E 200-Dicarboxylic acid, 3,6-dioxanedicarboxylic 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)phenyl-2,5-dicarboxylic acid, 1,1'-dinathyl-8,8'-dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-aniline-anthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquine Phosphoro-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, phenylindane dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, o-hydroxybenzophenone dicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazine dicarboxylic acid, 5,6-dimethyl-2,3-pyrazine dicarboxylic 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-sulfon-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2'-3'-diphenyl-p-terphenyl-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene 2,8-Dicarboxylic acid, 5-tert-butyl-1,3-benzenedilic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazolium dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexadecanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedilic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4'-dihydroxydicarboxylic acid Benzyl-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorescein-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedilic 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-pyrazole dicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecane dicarboxylic acid, 5,6-dehydronorbornene-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridine dicarboxylic acid, and combinations thereof.

[0033] 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, gold tricarboxylic acid, and combinations thereof.

[0034] As another example, in at least some embodiments, the MOF linker is a tetracarboxylic acid linker selected from the group consisting of: 1,1-dioxide-perylene[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, 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-hexaoxane-2,3,11,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, and combinations thereof.

[0035] In this exemplary embodiment, the MOF linker is 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid (H4dobpdc) and / or 4,4'-dioxobiphenyl-3,3'-dicarboxylic acid ester (dobpdc). 4- In some embodiments, dobpdc includes 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid, its monocarboxylic acid ester form, its dicarboxylic acid ester form, its monophenol salt form, its diphenol salt form, and combinations thereof.

[0036] In some implementations, the MOF connector is one or more of the following connectors:

[0037]

[0038]

[0039]

[0040] and / or

[0041]

[0042] In some embodiments, the MOF compound is a MOF compound of the MOF-74 family. In some embodiments, the MOF compound is a MOF compound of the MOF-274 family. In some embodiments, the MOF compound is a MOF compound of the MOF-303 family. In some embodiments, the MOF compound is Mg2(dobpdc).

[0043] In some embodiments, the functionalized adsorbent comprises at least one functionalized ligand containing an amine group. In some embodiments, the functionalized adsorbent comprises at least one functionalized ligand not containing an amine group.

[0044] In some embodiments, the functionalized adsorbent is a functionalized MOF compound of formula (I).

[0045] (Formula I),

[0046] in:

[0047] M is a MOF metal or a metal-containing cluster;

[0048] L is the MOF connector;

[0049] F A It is at least one functionalized ligand containing an amino organosilicon group;

[0050] F B It is at least one functionalized ligand that does not contain an amino organosilicon group;

[0051] x is a value in the range of 1 to 6;

[0052] y is a value in the range of 1 to 6;

[0053] a is a value greater than 0 and less than or equal to 2; and

[0054] b is a value in the range of 0 to 2.

[0055] In some embodiments, the functionalized adsorbent includes at least one functionalized ligand, wherein the at least one functionalized ligand comprises at least one functionalized ligand containing an amino organosilicon group. Typically, the at least one functionalized ligand containing an amino organosilicon group may comprise any such suitable ligand that promotes the functionalized adsorbent described herein. The at least one functionalized ligand containing an amino organosilicon group may comprise only one functionalized ligand containing an amino organosilicon group, or may comprise two or more functionalized ligands, each containing an amino organosilicon group.

[0056] In some embodiments, the functionalized adsorbent includes at least one functionalized ligand, wherein the at least one functionalized ligand comprises at least one functionalized ligand that does not contain an amino organosilicon group. In some embodiments, the functionalized adsorbent further includes at least one functionalized ligand that does not contain an amino organosilicon group. Typically, the at least one functionalized ligand that does not contain an amino organosilicon group may comprise any such suitable ligand that promotes the functionalized adsorbent described herein. The at least one functionalized ligand that does not contain an amino organosilicon group may comprise only one functionalized ligand that does not contain an amino organosilicon group, or it may comprise two or more functionalized ligands that each does not contain an amino organosilicon group.

[0057] In some embodiments, the at least one functionalized ligand not containing an amino organosilicon group is selected from the group consisting of: amine ligands, monoamine ligands, diamine ligands, triamine ligands, tetraamine ligands, pentamine ligands, hexamine ligands, polyamine ligands, alkylamine ligands, and amino alcohol ligands. Exemplary ligands include, but are not limited to, ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, 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, and N-(2-aminoethyl) -1,3-propanediamine, bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane (spermine), 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.

[0058] In some embodiments, the functionalized adsorbent comprises a mixture of at least two different functionalized ligands. In some embodiments, the mixture of at least two different functionalized ligands comprises at least one functionalized ligand that does not contain an amino organosilicon group. In some embodiments, the mixture of at least two different functionalized ligands comprises at least one functionalized ligand that does not contain an amino organosilicon group and at least one functionalized ligand that contains an amino organosilicon group. Typically, the at least one functionalized ligand containing an amino organosilicon group and the at least one functionalized ligand that does not contain an amino organosilicon group can be present in any suitable ratio known in the art that promotes the functionalized adsorbent described herein. In some embodiments, the ratio is selected from the group consisting of molar ratio, weight ratio, and volume ratio. In some embodiments, the at least one functionalized ligand containing an amino organosilicon group and the at least one functionalized ligand that does not contain an amino organosilicon group are present in a ratio ranging from about 10:1 to about 1:10. In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group and the at least one functionalized ligand not comprising an amino organosilicon group are present in a ratio ranging from about 9:1 to about 1:9. In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group and the at least one functionalized ligand not comprising an amino organosilicon group are present in a ratio ranging from about 8:1 to about 1:8. In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group and the at least one functionalized ligand not comprising an amino organosilicon group are present in a ratio ranging from about 7:1 to about 1:7. In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group and the at least one functionalized ligand not comprising an amino organosilicon group are present in a ratio ranging from about 6:1 to about 1:6. In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group and the at least one functionalized ligand not comprising an amino organosilicon group are present in a ratio ranging from about 5:1 to about 1:5. In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group and the at least one functionalized ligand not comprising an amino organosilicon group are present in a ratio ranging from about 4:1 to about 1:4. In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group and the at least one functionalized ligand not comprising an amino organosilicon group are present in a ratio ranging from about 3:1 to about 1:3. In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group and the at least one functionalized ligand not comprising an amino organosilicon group are present in a ratio ranging from about 2:1 to about 1:2. In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group and the at least one functionalized ligand not comprising an amino organosilicon group are present in a ratio of about 1:1.

[0059] In some embodiments, the presence of the at least one functionalized ligand containing an amino organosilicon group is lower than the presence of the at least one functionalized ligand not containing an amino organosilicon group.

[0060] In some embodiments, the at least one functionalized ligand containing an amino organosilicon group and the at least one functionalized ligand not containing an amino organosilicon 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.

[0061] In many embodiments, the at least one functionalized ligand containing an amino organosilicon group can be any suitable at least one functionalized ligand containing an amino organosilicon group known in the art that promotes the functionalized adsorbent described herein.

[0062] In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group comprises at least one amine selected from the group consisting of primary amines, secondary amines, tertiary amines, and combinations thereof. In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group comprises at least one primary amine or at least one secondary amine.

[0063] In some embodiments, the at least one functionalized ligand containing an amino organosilicon group comprises at least one amine selected from the group consisting of monoamines, diamines, triamines, tetraamines, pentamines, hexamines, polyamines, and combinations thereof.

[0064] In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group comprises at least one amino organosilicon selected from the group consisting of: linear amino organosilicon, cyclic amino organosilicon, branched amino organosilicon, 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, polyoctahedral silsesquioxane, and combinations thereof.

[0065] In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group has a symmetrical structure. In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group has an asymmetrical structure.

[0066] In some embodiments, when the at least one functionalized ligand containing an amino organosilicon group comprises a disiloxane group, the at least one functionalized ligand containing an amino organosilicon group comprises the same amine on both sides of the disiloxane group. In some embodiments, when the at least one functionalized ligand containing an amino organosilicon group comprises a disiloxane group, the at least one functionalized ligand containing an amino organosilicon group comprises a different amine on either side of the disiloxane group.

[0067] In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group is an amino-substituted siloxane of formula (II), (III), (IV), (V), (VI), or (VII).

[0068] (Formula II)

[0069] (Formula III)

[0070] (Form IV)

[0071] (Form V)

[0072] (Form VI)

[0073] (Equation VII)

[0074] in:

[0075] R1, R2, R3, R4, R9, R 10 R 13 R 14 and R 18 Each is independently selected from the group consisting of: hydrogen, substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, aryl, phenyl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0076] R5, R6, R 11 R 15 and R 17 Each is independently selected from the group consisting of: direct bonds, substituted or unsubstituted C1-C6 straight-chain alkyl groups, substituted or unsubstituted C3-C6 branched alkyl groups, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl.

[0077] R7, R8, R 12 and R16 Each is independently selected from the group consisting of: direct bonds, substituted or unsubstituted C1-C6 straight-chain alkyl groups, substituted or unsubstituted C3-C6 branched alkyl groups, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, and substituents of formula (VIII).

[0078] (Formula VIII);

[0079] in:

[0080] Tilde keys indicate the bonding positions with formula (II), (III), (IV), (V), (VI), or (VII);

[0081] R 19 R 20 R 21 R 22 R 23 and R 24 Each is independently selected from the group consisting of: hydrogen, substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, substituted or unsubstituted straight-chain heteroalkyl, substituted or unsubstituted C1-C6 straight-chain heteroalkyl, substituted or unsubstituted branched heteroalkyl, substituted or unsubstituted C3-C6 branched heteroalkyl, aryl, heteroaryl, methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl;

[0082] R 25 and R 26 Each is independently selected from the group consisting of: hydrogen, substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C1-C3 straight-chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl and substituted or unsubstituted C4-C6 cycloalkyl, or when combined, R 25 and R 26 Forming a monocyclic ring selected from the group consisting of heterocyclic alkyl and heteroaryl groups;

[0083] R 27 R 28 and R 29Each is independently selected from the group consisting of: direct bonds, substituted or unsubstituted C1-C6 straight-chain alkyl groups, substituted or unsubstituted C3-C6 branched alkyl groups, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, ethers, -OCH2CH2-, -OCH2CH2CH2-, -OCH2CH2CH2CH2-, -NHCH2CH2-, -NHCH2CH2CH2- and -NHCH2CH2CH2CH2-;

[0084] R 30 Select from the group consisting of: hydrogen, substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted C1-C6 straight-chain alkyl, substituted or unsubstituted C1-C3 straight-chain alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted C3-C6 branched alkyl, methyl, ethyl, propyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C4-C6 cycloalkyl, heterocyclic alkyl and heteroaryl;

[0085] j is an integer in the range of 0 to 20;

[0086] k is an integer in the range of 0 to 20;

[0087] m is an integer in the range of 0 to 20; and

[0088] n is an integer in the range of 0 to 20.

[0089] In some embodiments, the at least one functionalized ligand comprising an amino organosilicon group is selected from the group consisting of:

[0090] ,

[0091] ,

[0092] ,

[0093] ,

[0094] ,

[0095] ,

[0096] ,

[0097] ,

[0098] ,

[0099] ,

[0100] ,

[0101] , , , , , , , ,

[0102] ,

[0103] ,

[0104] ,

[0105] ,

[0106] ,

[0107] ,

[0108] ,

[0109] ,

[0110] ,

[0111] ,

[0112] ,

[0113] ,

[0114] ,and

[0115] .

[0116] The disclosed fluid trapping material or coating can be formed by crosslinking a binder material capable of forming a crosslinked polymer. In at least some cases, the disclosed fluid trapping material may include a portion (e.g., by mass percentage) of a crosslinked polymer (e.g., a crosslinked binder material). For example, such a portion may be less than 20% by mass, between 1% and 15% by mass, between 5% and 10% by mass, or less than 10% by mass of the total mass of the fluid trapping material. Typically, the crosslinked polymer can be formed using thermal techniques, radiation techniques (e.g., irradiation with ultraviolet (UV) light), and / or chemical techniques (e.g., via free radical polymerization or condensation reaction using a crosslinking agent). In embodiments using a crosslinking agent, the fluid trapping material may also include the crosslinking agent. That is, the crosslinking agent may be present in the fluid trapping material. It is currently recognized that fluid trapping materials comprising cross-linked polymers (e.g., fluid trapping materials formed using cross-linked polymers) can produce fluid trapping materials with a relatively large amount of adsorbent (e.g., a relatively small amount of binder material (e.g., less than 15% by mass, less than 12% by mass, less than 10% by mass, less than 8% by mass, less than 5% by mass) compared to fluid trapping materials formed using uncross-linked and / or non-cross-linked binders or polymers). Therefore, increasing the amount of adsorbent material improves the fluid binding capacity of the fluid trapping material by having a larger amount of adsorbent material in the fluid trapping material. Furthermore, by forming the fluid trapping material with a cross-linked polymer, the disclosed fluid trapping material can have improved adhesion or bonding to substrates (e.g., metal substrates, polymer substrates (e.g., glass-filled nylon), polymer composite substrates, etc.) and improved stability or resistance to dissolution.

[0117] With this in mind, Figure 1 This is a flowchart of an embodiment of a method 10 for capturing or extracting fluid from a fluid stream. As illustrated, the fluid capture system 12 receives fluid from a fluid source 14. Typically, the fluid source 14 may include an exhaust fluid stream (e.g., an exhaust gas stream) and / or ambient air. As described herein, the fluid source 14 may include one or more target fluids (e.g., one or more target gases) that may be desired to capture or otherwise extract or separate from the exhaust fluid stream. For example, it may be desirable to capture certain combustion products. That is, in some cases, it may be desirable to capture CO2 to reduce the amount of CO2 emitted into the environment (e.g., according to certain regulations). Additionally or alternatively, it may be desirable to capture H2O to reduce the moisture content of the air stream. As another non-limiting example, it may be desirable to capture certain sulfur oxides (SO4) produced by exhaust gases. x This can be advantageous. In any case, the fluid capture system 12 typically receives fluid from the fluid source 14, and one or more substrates 16 of the fluid capture system 12 extract one or more target fluids 18 from the fluid source 14, thereby generating a purified gas stream 20.

[0118] In some embodiments, the fluid capture system 12 may be provided as part of a gas turbine system, a chemical production system, or other systems that generate a fluid flow (e.g., a gas flow, an exhaust gas flow) containing gas molecules that may be desired to be captured. As illustrated, the fluid capture system 12 may include one or more substrates 16. As described herein, the substrate 16 may include a coating formed of one or more semi-permeable materials (e.g., materials capable of allowing certain gases to permeate through the substrate) capable of binding certain fluids (i.e., target fluid 18 or gas). For example, the coating may be a fluid capture material formed using an adsorbent material and a binder material capable of forming a cross-linked polymer.

[0119] As described herein, fluid trapping materials can improve the amount of target fluid 18 extracted from fluid source 14 and / or may have improved stability compared to certain coatings used for extracting fluid from fluid source 14. To illustrate this, Figure 2 This is a flowchart of an embodiment of a method 30 for generating air contact with a fluid trapping material.

[0120] To begin method 30, at block 32, an adsorbent-binder material 38 is generated using adsorbent material 34, binder material 36, optionally crosslinking agent 37, and pore precursor 35. Generally, the use of adsorbent material 34, binder material 36, optionally crosslinking agent 37, and pore precursor 35 may include forming a mixture, such as a solution or slurry comprising adsorbent material 34, binder material 36, and optionally pore precursor 35 in a suitable solvent capable of dissolving at least a portion of the adsorbent material and / or binder material. Examples of such solvents include, but are not limited to, toluene, ethyl acetate, ethanol, 2-(2-butoxyethoxy)ethyl acetate, water, isopropanol, methyl ethyl ketone, or any combination thereof (i.e., for miscible solvents). As discussed herein, crosslinking agent 37 may include certain chemical crosslinking agents. Therefore, crosslinking agent 37 may also be added to the mixture of adsorbent material 34 and binder material 36. In some embodiments, at least one of crosslinking agent 37 and pore precursor 35 may be added after the formation of the mixture of adsorbent material 34 and binder material 36. For example, in embodiments where the binder material 36 is a polymer material, at least one of the crosslinking agent 37 and the pore precursor 35 may be added after a time period corresponding to a suitable degree of polymerization of the binder material 36 (e.g., after initiating polymerization of the binder material 36). However, in some embodiments, at least one of the crosslinking agent 37 and the pore precursor 35 may be added before initiating polymerization of the binder material 36.

[0121] The adsorbent material 34 is typically a material capable of adsorbing fluids such as water and / or CO2. In some embodiments, the adsorbent material 34 may comprise a metal-organic framework (MOF) and / or a covalent organic framework (COF). For example, the adsorbent material may comprise MOFs capable of adsorbing fluids as described herein, such as iron-based MOFs, zirconium-based MOFs (e.g., MOF-808, such as MOF-808-Gly), aluminum-based MOFs (e.g., MOF-303, MIL-160), zeolite imidazole ester frameworks (ZIFs), amine-containing MOFs, other MOFs, amine-containing COFs, ZIFs, silica, etc. In some embodiments, the adsorbent material 34 may comprise a polymeric resin, silica, zeolite, or a combination thereof.

[0122] The binder material 36 may comprise one or more oligomer or polymer materials, polymerizable monomers or oligomers, or combinations thereof. In at least some embodiments, the binder material 36 may improve the affinity of the adsorbent material 34 for a gas or gases and / or improve the stability (e.g., thermal stability) of the adsorbent material 34. In some embodiments, the binder material 36 may comprise materials that form polymers having a thermal stability of about 200°C. In some embodiments, the binder material 36 may comprise silicone-containing polymers or binders (e.g., siloxanes or silanes, such as aminopropyl silsesquioxane, aminoethylaminopropyl silsesquioxane, alkoxysilane), vinyl polymers (e.g., polyvinyl esters, such as polyvinyl acetate; polyvinyl alcohol) and their copolymers such as polyvinyl butyral. In some embodiments, the binder material 36 may comprise polysaccharides (e.g., ethyl cellulose, starch, and alkyl cellulose), and nitrogen-containing polymers (e.g., polyethyleneimine (PEI)). In some embodiments, the binder material 36 may comprise combinations of the aforementioned polymers (i.e., two, three, four, or more than four of these polymers). For example, the binder material 36 may be a “hybrid binder mixture.” As mentioned herein, a “hybrid binder mixture” may include a mixture or blend of different types of binder materials, such as a mixture of organic polymers and silsesquioxane binders, or other combinations of binder materials described herein. In at least some cases, the binder material 36 may be selected to enhance the adsorption of the target fluid onto a coating (e.g., a fluid trapping material) created using the adsorbent material 34. For example, in embodiments using PEI as the binder material, the PEI may include PEI-low (e.g., M... W Between approximately 20,000 g / mol and 25,000 g / mol, and M n Between approximately 8,000 g / mol and 12,000 g / mol) or PEI-high (e.g., M WBetween approximately 70,000 g / mol and 80,000 g / mol, and M n Between approximately 55,000 g / mol and 65,000 g / mol.

[0123] As described herein, the binder material 36 can be a crosslinkable polymer material. That is, it is now recognized that the formation of a fluid trapping material in which at least a portion of the polymer portion of the adsorbent-binder material 38 is a crosslinked polymer can reduce the likelihood of decomposition and / or dissolution of the adsorbent material 34. Furthermore, the use of a crosslinked polymer allows the fluid trapping material to have a relatively large amount of adsorbent material bound to the target fluid 18, and thus a higher fluid binding capacity compared to coatings formed without crosslinked polymers. In other words, conventional techniques for combining adsorbent material 34 and binder material 36 can produce fluid-binding materials with a relatively low fluid binding capacity compared to the adsorbent material (e.g., due to a dilution effect or knockdown effect). It is now recognized that crosslinking the binder material 36 can produce a fluid trapping coating or fluid trapping material with a relatively high binding capacity compared to not crosslinking the binder material 36. Furthermore, the binding capacity of the disclosed fluid trapping coating or material (i.e., including cross-linked binder materials) may be approximately equal to the binding capacity of the adsorbent material 34 itself (e.g., adsorbent material 34 in powder form).

[0124] In one embodiment, the binder material 36 comprises a self-crosslinking material. For example, the binder material 36 may comprise silanol (SiOH) functional groups and / or alkoxysilane (SiOR) functional groups. It should be noted that binder materials 36 containing such functional groups can undergo intermolecular condensation reactions that result in crosslinking of the binder material 36 upon heating. For example, it is currently recognized that amine-containing components (e.g., amine-containing MOFs) can cause certain binder materials 36 (e.g., epoxy resins) to crosslink. As another non-limiting example, amine-containing components can crosslink certain Si-O polymeric structures, such as silsesquioxanes, thereby forming crosslinked Si-O polymeric structures (e.g., amine-impregnated silica).

[0125] In one embodiment, the binder material comprises a polyvinyl alcohol polymer. Suitable polyvinyl alcohol polymers include, but are not limited to, polyvinyl alcohol homopolymers and polyvinyl alcohol copolymers. In one embodiment, the binder polymer composition comprises a polyvinyl alcohol-polyvinylamine copolymer (PVA-PVAm) containing a first crosslinkable functional group and a second crosslinkable functional group. Although polyvinyl alcohol derivatives are suitable for the practice of this invention, other polymeric materials may also be used in the binder polymer composition, including, but not limited to, polyacrylates, polymethacrylates, polyhydroxyethyl methacrylates, and functionalized polyarylenes containing amines, carboxylic acids, amides, hydroxyl moieties, etc. In one embodiment, the binder polymer composition for preparing the fluid trapping material comprises at least one polymer with a number average molecular weight greater than about 2,500 Daltons. In another embodiment, the binder polymer composition for preparing the fluid trapping material comprises at least one polymer with a number average molecular weight in the range of greater than 2,500 Daltons to about 500,000 Daltons. In yet another embodiment, the binder polymer composition for preparing the fluid trapping material comprises at least one hydrophilic polymer with a number average molecular weight in the range of about 75,000 Daltons to about 250,000 Daltons. Number-average molecular weight can be determined using a variety of techniques known to those skilled in the art, including 1 H-NMR spectroscopy and gel permeation chromatography (GPC).

[0126] As described above, the adhesive material 36 may comprise a mixture of crosslinkable polymeric materials. For example, the adhesive material 36 may comprise a mixture of polyvinyl alcohol (PVA) and polyacrylic acid (PAA). For example, the mixture may comprise 10% by weight of PVA and 90% by weight of PAA, 30% by weight of PVA and 70% by weight of PAA, 50% by weight of PVA and 50% by weight of PAA, 70% by weight of PVA and 30% by weight of PAA, or 90% by weight of PVA and 10% by weight of PAA.

[0127] In some embodiments, the binder material 36 may be dissolved in a solvent to a specific viscosity. For example, in embodiments where the binder material 36 comprises ethyl cellulose, the binder material 36 may comprise a 7-15 cP solution in a 6% toluene-ethanol solution. When dissolved in a 1:1 toluene-2-(2-butoxyethoxy)ethyl acetate solvent, the resulting slurry may comprise 30% solids and 11% binder. As another non-limiting example, in embodiments where the binder material 36 comprises ethyl cellulose, the binder material 36 may comprise a solution of approximately 300 cP in a 5% toluene-ethanol solution.

[0128] Generally, the amount of crosslinking agent 37 can be less than the amount of binder material 36. In some embodiments, the ratio of crosslinking agent 37 added to binder material 36 to form adsorbent-binder composite material 38 can be less than about 1 / 3, less than about 1 / 4, less than about 1 / 5, or less than about 1 / 6. For example, adsorbent-binder composite material 38 can be formed by combining a 10% by mass solution of binder material 36 and a 2% by mass solution of crosslinking agent 37 (i.e., the ratio of crosslinking agent 37 to binder material 36 is 1 / 5).

[0129] It should be noted that, at least in some cases, crosslinking agent 37 can also be adhesive material 36. That is, crosslinking agent 37 can be a polymer capable of crosslinking. For example, PAA can be used as a crosslinking agent for PVA.

[0130] As described herein, crosslinking agent 37 crosslinks the binder material 36. In some embodiments, the degree of crosslinking (i.e., crosslinking density, which refers to the density of chains or segments connecting two parts of the polymer network, rather than the density of crosslinking junctions) may be greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, or greater than 90%.

[0131] The amounts of binder material 36 and adsorbent material 34 relative to adsorbent-binder material 38 (e.g., adsorbent-binder composite material) may include less than 50% binder material, less than 40% binder material, less than 30% binder material, less than 20% binder material 36, less than 15% binder material 36, or less than 10% binder material 36.

[0132] A wide variety of crosslinking agents can be used to react with binders, and these crosslinking agents can be monomers, oligomers, or polymers, or combinations thereof. In some embodiments, crosslinking agent 37 may include chemical crosslinking agents such as epoxy resins, acid anhydrides, etc. In some embodiments, crosslinking agent 37 may include one or more materials, such as nanoparticles, micron-sized particles, or larger particles, or molecular precursors that can form particles. For example, the crosslinking agent may include silica particles, such as colloidal silica; or tetraalkoxysilanes that can form silica particles. In some embodiments, crosslinking agent 37 may include particles with different size distributions. That is, crosslinking agent 37 may include particles with a first size distribution and a second size distribution. For example, crosslinking agent 37 may have a micron-sized distribution. In some embodiments, crosslinking agent 37 may have a nanon-sized distribution and a micron-sized distribution (i.e., a bimodal size distribution). In at least some cases, a bimodal size distribution can improve abrasion resistance. In embodiments where crosslinking agent 37 includes particles with different size distributions, the mixture of particles may vary. For example, the mixture may include 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, etc., of nano-sized particles and 90 wt%, 80 wt%, 70 wt%, 60 wt%, 50 wt%, 40 wt%, 30 wt%, etc., of micron-sized particles. In embodiments where the crosslinking agent 37 comprises particles (e.g., micron-sized particles, nanoparticles, or larger particles), the particles may have a shape distribution. For example, the crosslinking agent 37 may comprise 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% spherical micron-sized particles. In at least some cases, the combination of particle shape (e.g., spherical) and different size distributions can improve the properties of the resulting fluid trapping material discussed herein.

[0133] In some embodiments, the crosslinking agent 37 comprises functional groups sensitive to the formation of free radicals induced by exposure to high-energy irradiation (e.g., ultraviolet light or electron beams) and / or heat. Those skilled in the art will appreciate that the structure of a free radical is understood to determine its reactivity, and the structure of the crosslinking agent can be selected to provide higher or lower levels of chemical reactivity for free radicals generated by such crosslinkable functional groups under irradiation or heat exposure. In one embodiment, the crosslinking agent comprises functional groups capable of forming secondary or tertiary aliphatic or cycloaliphatic free radicals. In another alternative embodiment, the crosslinking agent comprises functional groups capable of forming aromatic free radicals (e.g., benzyl free radicals). Other crosslinkable functional groups include methacrylates, acrylates, acrylamides, vinyl ketones, styrenes, vinyl ethers, vinyl groups, allyl groups, benzyl groups, and groups containing tertiary carbon-hydrogen bonds, such as isobutyl groups.

[0134] Suitable crosslinking agents 37 include, but are not limited to, methacrylates, acrylates, and vinyl ketones. These agents can covalently bond with the adhesive material or form crosslinked polymers themselves when exposed to high-energy radiation or heat. For example, suitable crosslinking agents include, but are not limited to, the following reagents: acryloyl chloride, (2E)-2-butenoyl chloride, maleic anhydride, 2(5H)-furanone, methyl acrylate, 5,6-dihydro-2H-pyran-2-one, ethyl acrylate, methyl crotonate, allyl acrylate, vinyl crotonate, ethyl 2-isocyanate methacrylate, methacrylic acid, methacrylic anhydride, methacryloyl chloride, glycidyl methacrylate, 2-ethylacryloyl chloride, 3-methylenedihydro-2(3H)-furanone, 3-methyl-2(5H)-furanone, methyl 2-methacrylate, trans-2-methoxyacrylate, citraconic anhydride, itaconic anhydride, (2E)-2-methyl-2-butenoic acid methyl ester, ethyl 2-methacrylate, ethyl 2-cyanoacrylate, dimethyl... Lemon anhydride, allyl 2-methacrylate, ethyl (2E)-2-methyl-2-butenoate, ethyl 2-ethyl acrylate, methyl (2E)-2-methyl-2-pentenoate, 2-hydroxyethyl 2-methacrylate, methyl 2-(1-hydroxyethyl)acrylate, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(diethoxymethylsilyl)propyl methacrylate, 3-(trichlorosilyl)propyl 2-methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-tris(trimethylsiloxy)silylpropyl methacrylate, 6-dihydro-1H-cyclopenta(c)furan-1,3(4H)-dione, methyl 2-cyano-3-methylcrotonate, trans-2,3-dimethacrylic acid, and N-(hydroxymethyl)acrylamide.

[0135] Suitable vinyl and allyl reagents that can be used as crosslinking agents include, but are not limited to, allyl bromide, allyl chloride, diene ketone, 5-methylene dihydro-2(3H)-furanone, 3-methylene dihydro-2(3H)-furanone, 2-chloroethyl vinyl ether and 4-methoxy-2(5H)-furanone.

[0136] Suitable isocyanate reagents that can be used as crosslinking agents include, but are not limited to, vinyl isocyanate, allyl isocyanate, furfuryl isocyanate, 1-ethyl-4-isocyanate phenylene, 1-ethyl-3-isocyanate phenylene, 1-(isocyanate methyl)-3-methylbenzene, 1-isocyanate methyl-3,5-dimethylbenzene, 1-bromo-2-isocyanate ethane, (2-isocyanate ethyl)benzene, 1-(isocyanate methyl)-4-methylbenzene, 1-(isocyanate methyl)-3-methylbenzene, 1-(isocyanate methyl)-2-methylbenzene, etc.

[0137] Suitable styrene reagents that can be used as crosslinking agents include, but are not limited to, 3-vinylbenzaldehyde, 4-vinylbenzaldehyde, 4-vinylbenzyl chloride, trans-cinnamoyl chloride, phenyl maleic anhydride, 4-hydroxy-3-phenyl-2(5H)-furanone, etc.

[0138] Suitable epoxide reagents that can be used as crosslinking agent 37 include, but are not limited to, glycidyl methacrylate, glycidyl vinyl ether, 2-(3-butenyl)ethylene oxide, 3-vinyl-7-oxabicyclo[4.1.0]heptane, limonene oxide, etc.

[0139] In some embodiments, the crosslinking agent 37 may include multiple (e.g., two, three, or more than three) different types of functional groups that can promote the formation of the fluid trapping material 44. Generally, the crosslinking agent 37 may include a first functional group that reacts with the binder material 36 and a crosslinkable second functional group. For example, the crosslinking agent 37 may include anhydride and acrylate functional groups, epoxide and acrylate functional groups, isocyanate and methacrylate functional groups, etc. As a non-limiting example, the binder material 36 may include poly(vinyl alcohol) and the crosslinking agent 37 may include ethyl 2-isocyanate methacrylate (2-IEM), which includes both isocyanate and methacrylate functional groups. As another non-limiting example, the binder material 36 may include poly(vinyl butyral) and the crosslinking agent 37 may include 2-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane.

[0140] Generally, the pore precursor 35 can be any suitable pore precursor known in the art that facilitates the system according to this disclosure. As used herein, a "pore precursor" is a precursor material provided in the fluid trapping material 44 that is removed from the fluid trapping material 44 to leave at least one pore in its location. The pore precursor allows control over the porosity of the fluid trapping material 44 and produces enhanced porosity. The enhanced porosity subsequently results in enhanced diffusion of gas into or within the fluid trapping material 44.

[0141] The enhanced porosity may be in the form of at least one of the following: increased average porosity, increased porosity near the substrate, increased porosity near the interface between the air and fluid trapping material 44, and increased porosity near the edge of the fluid trapping material 44.

[0142] The enhanced porosity is provided by at least one pore formed from a pore precursor. This at least one pore has sufficient size and shape to produce enhanced gas diffusion.

[0143] The available size and shape of the pores depend on the membrane thickness, adsorbent size, adsorbent shape, and other relevant factors. In some embodiments, the at least one pore has an average cross-sectional area ranging from about 5 µm to about 500 µm.

[0144] In some embodiments, the at least one hole has an average cross-sectional shape selected from a group consisting of symmetrical shapes, asymmetrical shapes, amorphous shapes, spheres, cylinders, cubes, octahedrons, needles, and combinations thereof.

[0145] In some implementations, the increased porosity results in a reduced membrane density.

[0146] Generally, porosity can be measured using any suitable method known in the art. In some embodiments, porosity is measured via ellipsometry. The percentage porosity within the MOF film can be calculated using the following formula:

[0147]

[0148] Where η fram,A,V and η fram,V These are the volume-weighted average refractive indices of MOF membranes with and without internal solvent filtration, respectively; and

[0149] η a It is the measured refractive index of a membrane permeated by a high-boiling-point solvent (which is typically dimethylformamide), and η vac It is the refractive index of vacuum and is estimated to be 1.

[0150] In some implementations, the pore precursor is selected from the group consisting of waxes, salts, non-reactive gas-generating substances, thermally unstable polymers, and combinations thereof.

[0151] In some embodiments, the hole precursor has an average cross-sectional shape selected from a group consisting of symmetrical shapes, asymmetrical shapes, amorphous shapes, spheres, cylinders, cubes, octahedrons, needles, and combinations thereof.

[0152] In some embodiments, the pore precursor is non-reactive. Non-reactive pore precursors do not react with binder material 36, adsorbent-binder material 38, or crosslinking agent 37. When the pore precursor reacts with any of the binder material 36, adsorbent-binder material 38, and crosslinking agent 37, they become irremovable from the fluid trapping material 44.

[0153] In some implementations, the pore precursor is a wax with low viscosity, which melts upon heating and flows out from the fluid trapping material 44 without assistance.

[0154] In some embodiments, the pore precursor is a modified wax. In some embodiments, the pore precursor is a wax modified with a block copolymer. Compared to unmodified wax, the modified wax has a modified size or shape.

[0155] In some embodiments, the pore precursor is a wax insoluble in the slurry or solvent blend according to the present disclosure. In some embodiments, the pore precursor is a wax soluble in the slurry or solvent blend, such that the wax undergoes phase separation upon drying. In some embodiments, the pore precursor is a wax selected from the group consisting of dihexadecanyl fumarate, paraffin wax, dimethyl eicosanoate, and combinations thereof.

[0156] In some embodiments, the pore precursor is a solvent-soluble salt. The solvent is applied to the fluid trapping material 44 containing the salt, causing the salt to dissolve in the solvent and flow out of the fluid trapping material 44.

[0157] In some embodiments, the pore precursor is a non-reactive gas-generating substance, wherein the non-reactive gas is selected from the group consisting of N2, CO2, H2, and combinations thereof.

[0158] In some embodiments, the pore precursor is a non-reactive gas-generating substance selected from the group consisting of azo compounds, azobisisobutyronitrile ([(CH3)2C(CN)]2N2), carbamates, β-ketocarboxylic acids, and combinations thereof.

[0159] Generally, the pore precursor can be any suitable β-ketocarboxylic acid known in the art for promoting the functionalization of the adsorbents described herein. In some embodiments, the pore precursor is a β-ketocarboxylic acid selected from the group consisting of: acetoacetic acid, malonic acid, sodium malonate, disodium malonate monohydrate, lithium acetoacetate, methylmalonic acid, monomethyl malonic acid, methyl potassium malonate, 1,3-propanone dicarboxylic acid, dimethylmalonic acid, methyl acetoacetate, monoethyl malonic acid, ethyl potassium malonate, ethylmalonic acid, oxaloacetic acid, monotert-butyl malonate, butylmalonic acid, diethylmalonic acid, cyclopropane-1,1-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, dihydroxyfumarate hydrate, cyclohexane-1,1-dicarboxylic acid, (1S)-(+)-ketopine, 4-hydroxy-6-methyl-2-pyranone, 2-oxo-3-piperidinecarboxylic acid, and combinations thereof.

[0160] In some embodiments, one or more additives may be added to form the adsorbent-binder material 38. For example, the additive may include a dispersant to promote the formation of a suspension, such as anionic dispersants, cationic dispersants, nonionic dispersants, defoamers, wetting agents, thickeners, or any combination thereof. Suitable anionic dispersants may include polymeric alkoxylates or phosphate esters. Suitable nonionic dispersants may include polyurethanes. Suitable cationic dispersants may include polyoxyethylene fatty ammonium sulfate. Generally, the amount of dispersant added may be less than the amount of binder material 36. For example, the adsorbent-binder material 38 may include 10% by weight of binder material 36 and 0.5% by weight of dispersant, 1% by weight of dispersant, or more than 1% by weight of dispersant. As another non-limiting example, the adsorbent-binder material 38 may include 15% by weight of binder material 36 and 1% by weight of dispersant, 3% by weight of dispersant, or more than 5% by weight of dispersant. As another non-limiting example, the adsorbent-binder material 38 may comprise 13% by weight of binder material 36 and 1% by weight of dispersant, 3% by weight of dispersant, or more than 5% by weight of dispersant. For example, in an exemplary adsorbent-binder material 38 where binder material 36 is aminopropylsilsesquioxane, binder material 36 may be formed using a binder solution having 13% binder and 2% dispersant. The dispersant may include polyethyleneimine (PEI), such as PEI-low (e.g., M... W Between approximately 20,000 g / mol and 25,000 g / mol, and M n Between approximately 8,000 and 12,000) or PEI-high (e.g., M W Between approximately 70,000 g / mol and 80,000 g / mol, and M n Between approximately 55,000 and 65,000.

[0161] At frame 40, adsorbent-adhesive material 38 is deposited, applied to, integrally formed therewith (e.g., during manufacturing), or otherwise attached thereto, such as to one or more surfaces of substrate 16, thereby forming a fluid-capturing coated substrate 42. In some embodiments, the substrate may comprise certain metal substrates (e.g., aluminum, titanium) or 3-D printed metal substrates. For example, substrate 16 may comprise a fluid contactor having a metal surface. In some embodiments, substrate 16 comprises a metal alloy (e.g., chromium-nickel-iron alloy or stainless steel). As referred to herein, a “fluid contactor” or “direct fluid contactor” means a structure configured to receive a flow of fluid, and such structure may comprise porous and / or semi-porous materials such that a portion of the fluid flow can permeate through the fluid contactor. In some embodiments, the fluid flow may comprise an ambient air flow. In some embodiments, the fluid flow may comprise a flue gas flow or exhaust gas flow from a power generation device (e.g., a gas turbine). Therefore, the adhesive material 36 may be selected to have relatively high adhesion to the metal surface.

[0162] In some embodiments, substrate 16 may be a polymer or polymer composite. Polyolefins (e.g., polyethylene, polypropylene, polymethylpentene, polystyrene, substituted polystyrene, poly(vinyl chloride) (PVC), polyacrylonitrile), polyamides, polyesters, polysulfones, polyethers, acrylic and methacrylic polymers, polystyrene, polyurethanes, polycarbonates, polyesters (e.g., polyethylene terephthalate, polybutylene terephthalate), polyethersulfones, polypropylene, polyethylene, polyphenylene sulfones, cellulose polymers, polyphenylene ethers, polyamides (e.g., nylon, polyphenylene terephthalamide), and combinations of two or more of the aforementioned polymers may be used as substrates. Fluoropolymers that can be used as substrates include, but are not limited to, ePTFE, polyvinylidene fluoride (PVDF), poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP), poly(ethylene-alternating-tetrafluoroethylene) (ETFE), polychlorotrifluoroethylene (PCTFE), poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP), and polyvinyl fluoride (PVF).

[0163] Generally, depositing adsorbent-binder material 38 onto substrate 16 may include curing the adsorbent-binder material 38, including crosslinking agent 37, to form a fluid trapping material 44 or coating, which is a polymer and adsorbent composite material. In other words, fluid trapping material 44 refers to adsorbent-binder material 38, wherein binder material 36 is crosslinked by one or more crosslinking agents 37. As described herein, crosslinking of adsorbent-binder material 38 can provide a material and / or coating (i.e., fluid trapping material 44) with relatively high structural integrity compared to non-crosslinked adsorbent-binder material 38. Furthermore, crosslinking of adsorbent-binder material 38 can provide a material and / or coating with relatively high binding capacity to fluids.

[0164] It should be noted that, at least in some cases, the adsorbent-binder material 38 may be deposited multiple times on the substrate 16. It is recognized that, at least in some cases, depositing relatively thick layers (e.g., greater than 1 mm, greater than 2 mm, or greater than 5 mm) can result in one or more cracks in the fluid trapping material 44 (e.g., the fluid trapping material or fluid trapping coating). Therefore, to facilitate the reduction, prevention, or mitigation of cracking (e.g., mud cracking), depositing multiple layers to ultimately form a fluid trapping material 44 with a desired thickness (e.g., between 0.1 mm and 0.9 mm, between 1.1 mm and 1.3 mm, between 0.1 mm and 2.0 mm, between 2.5 mm and 3.5 mm) may be advantageous. For example, the fluid trapping material 44 may comprise three layers with a total thickness of 1.2 mm. As another non-limiting example, the fluid trapping material may comprise six layers with a total thickness of 3 mm. For example, to deposit multiple layers, method 30 may include depositing a first amount of adsorbent-binder material 38, curing the first amount of adsorbent-binder material to form a first layer, and repeating the method once or more to form one or more additional layers, thereby forming a fluid trapping material having multiple layers (e.g., 2, 3, 4, 5, 6, 7). In some embodiments, the first layer of fluid trapping material 44 may be pre-wetted before the addition of a second layer. Generally, pre-wetting includes providing the first layer with a suitable solvent, such as toluene, ethanol, water, or combinations thereof. After pre-wetting the first layer, a second layer may be formed on top of the pre-wetted first layer. Generally, the second layer may be formed in a manner substantially similar to that described with respect to the first layer.

[0165] In some embodiments, the total thickness of the fluid trapping material or coating may be less than 1 mm. For example, the total thickness may be between 0.1 mm and 0.9 mm, between 0.2 mm and 0.8 mm, between 0.2 mm and 0.7 mm, between 0.3 mm and 0.6 mm, or between 0.4 mm and 0.5 mm. In some embodiments, each layer of the fluid trapping material 44 may have the same thickness, such that the thickness formed for each layer (e.g., as per...) Figure 2 The thickness (as described) is the total thickness / n, where "n" is the number of layers formed. In some embodiments, one or more layers of the fluid trapping material 44 may have different thicknesses. For example, each subsequently formed layer may have a thinner thickness than the preceding layer. Alternatively, each subsequently formed layer may have a thicker thickness than the preceding layer.

[0166] As described herein, fluid trapping material 44 can be deposited onto one or more surfaces of substrate 16, such as an air contactor. To illustrate this, Figure 3 A cross-sectional view is shown of a substrate 16 (i.e., a fluid-capturing coated substrate 42) including a fluid-capturing material 44. In the illustrated embodiment, the substrate 16 is formed using an additive printing process. Furthermore, as illustrated, the fluid-capturing material 44 includes one or more channels 46 that generally permeate a portion of the fluid-capturing material 44. Typically, the adsorbent material 34 is capable of forming a porous material. Therefore, one or more channels 46 may also be formed in the fluid-capturing material 44.

[0167] As illustrated, each channel 46 typically includes a wall 48 to which a fluid trapping material 44 is bonded. Thus, a gas flow passing through the channel of the fluid trapping coated substrate 42 can contact the fluid trapping material 44, and therefore promotes the binding of a target fluid (e.g., CO2) with the fluid trapping material 44.

[0168] At frame 41, the 41-pore precursor 35 is removed from the fluid trapping material 44 to form at least one pore in the fluid trapping material 44. Generally, the 41-pore precursor 35 can be removed from the fluid trapping material 44 by any suitable method known in the art that facilitates the system according to this disclosure. In some embodiments, the 41-pore precursor 35 is removed from the fluid trapping material 44 by a technique selected from the group consisting of heating, washing, solvent extraction, and combinations thereof.

[0169] As described herein, the disclosed fluid trapping material 44 may have a relatively high fluid binding capacity (e.g., water capacity and / or CO2 capacity). Table 1 shows the results of CO2 capacity measurements for certain substrates coated with fluid trapping material 44. Typically, the fluid trapping material 44 corresponding to Table 1 is applied by a scraper to a 2-inch × 2-inch Chromium Nickel Iron 718 specimen and the CO2 trapping performance (e.g., CO2 capacity) at 0.04 kPa is evaluated. Sampling of the MOF-binder composite is evaluated in an aluminum weighing pan to determine the film curing conditions, the initial structural integrity of the film, and environmental adsorption measurements. An exemplary method of coating the specimen with a slurry (i.e., adsorbent-binder material 38) requires mixing the MOF powder (i.e., adsorbent material 34) with a suitable binder material 36, wetting agent, additives, and solvent in a container. The mixture may be vortexed for 1-2 minutes and then sonicated at 72 kHz for 20 minutes in an ultrasonic bath. The slurry is then applied to the substrate 16 using a doctor blade with an appropriate gap (10-50 mils, 254µm-1270µm) and allowed to dry under ambient conditions. For coatings in aluminum trays, the slurry can be added to the tray using a plastic pipette, tilting the tray to cover the bottom, and allowed to dry under ambient conditions. Once dry, the tray or sample is cured and activated using appropriate conditions.

[0170] As described in this paper, fluid trapping materials can be functionalized. To illustrate this, Figure 9 This is a flowchart of an embodiment of a method 50 for functionalizing fluid trapping materials.

[0171] In method 50, the fluid trapping material 44 coated on the substrate 16 is functionalized 45 with at least one functionalized ligand containing an amine group. The fluid trapping material 44 is coated on the substrate 16 in the form of a pre-formed film. The fluid trapping material 44 is typically unfunctionalized or requires further functionalization or regenerative functionalization.

[0172] Compared to conventional functionalization methods, Method 50 offers several key advantages, including, but not limited to, a simplified amine loading method for generating novel functionalized coatings, separation of amine functionalization from composite material formation (which enables the creation of aqueous fluid trapping materials), and readjustment or regeneration of older fluid trapping materials to extend their lifespan and improve their performance. Furthermore, Method 50 avoids known problems associated with amine functionalization, including sensitivity to at least one of the following: heat, oxygen, moisture, and amine leaching from the solvent during slurry preparation.

[0173] Generally, fluid trapping materials can be functionalized according to any suitable functionalization method known in the art. In some embodiments, functionalizing the fluid trapping material with at least one functionalized ligand containing an amine group includes receiving at least one functionalized ligand containing an amine group at the fluid trapping material. In some embodiments, the at least one functionalized ligand containing an amine group is received in the form of a solution or a gas.

[0174] In some embodiments, functionalizing a fluid trapping material with at least one functionalized ligand containing an amine group includes functionalizing the fluid trapping material with at least one functionalized ligand containing an amine group using techniques selected from the group consisting of: solution impregnation, gas-phase wetting, and combinations thereof. In some embodiments, functionalizing the fluid trapping material can be performed under ambient pressure, under positive pressure, or under vacuum. In some embodiments, functionalizing a fluid trapping material with at least one functionalized ligand containing an amine group includes immersing the fluid trapping material in a solution containing at least one functionalized ligand having an amine group.

[0175] In some embodiments, the fluid trapping material is not functionalized before being functionalized with at least one functionalized ligand containing an amine group.

[0176] In some embodiments, the fluid trapping material has been at least partially functionalized at least once before being functionalized with at least one functionalizing ligand containing an amine group. In these embodiments, functionalizing the fluid trapping material with at least one functionalizing ligand containing an amine group can at least partially refresh the previous functionalization of the fluid trapping material. In some embodiments, the fluid trapping material is washed prior to functionalization to at least partially remove the previous functionalization.

[0177] Generally, fluid trapping materials can be functionalized at any suitable functionalization time known in the art. In some embodiments, the fluid trapping material is functionalized directly after it has been coated onto the substrate. In some embodiments, the fluid trapping material is functionalized after it has been cured on the substrate. In some embodiments, the fluid trapping material is functionalized after the system has been used to trap fluid.

[0178] Generally, fluid trapping materials can be functionalized at any suitable functionalization location known in the art. In some embodiments, the fluid trapping material is functionalized at locations selected from the group consisting of: the location of use, remote maintenance facilities, and combinations thereof.

[0179] Other aspects of this disclosure are provided by the subject matter of the following provisions:

[0180] 1. A method for functionalizing a system, said system comprising:

[0181] substrate; and

[0182] Fluid trapping material, the fluid trapping material being formed on one or more surfaces of the substrate,

[0183] The method includes functionalizing the fluid trapping material with at least one functionalized ligand containing an amine group.

[0184] 2. The method according to the foregoing clause, wherein functionalizing the fluid trapping material with at least one functionalized ligand containing an amine group includes receiving the at least one functionalized ligand containing an amine group at the fluid trapping material.

[0185] 3. The method according to any of the preceding clauses, wherein the at least one functionalized ligand comprising an amine group is received in the form of a solution or a gas.

[0186] 4. The method according to any of the preceding clauses, wherein functionalizing the fluid trapping material with at least one functionalized ligand containing an amine group comprises techniques selected from the group consisting of solution impregnation, gas-phase wetting, and combinations thereof, wherein the techniques are performed at a pressure selected from the group consisting of ambient pressure, positive pressure, vacuum pressure, and combinations thereof.

[0187] 5. The method according to any of the preceding clauses, wherein the fluid trapping material is not functionalized prior to being functionalized with at least one functionalized ligand containing an amine group.

[0188] 6. The method according to any of the preceding clauses, wherein the fluid trapping material has been functionalized at least partially once before being functionalized with at least one functionalizing ligand containing an amine group.

[0189] 7. The method according to any of the preceding clauses, wherein the fluid capture material comprises at least one adsorbent selected from the group consisting of metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and combinations thereof.

[0190] 8. The method according to any of the preceding clauses, wherein the fluid trapping material comprises:

[0191] An adsorbent material configured to bind to one or more fluids, including water, carbon dioxide, sulfur oxides, alcohols, or combinations thereof; and

[0192] One or more adhesive materials, wherein the adhesive materials are optionally at least partially crosslinked;

[0193] The fluid trapping material optionally includes at least one pore.

[0194] 9. A method, the method comprising:

[0195] An adsorbent material is provided that is configured to bind to one or more fluids, said fluids including water, carbon dioxide, sulfur oxides, alcohols, or combinations thereof;

[0196] One or more adhesive materials are provided, wherein the one or more adhesive materials optionally include components capable of forming a crosslinked polymer;

[0197] A crosslinking agent may be provided optionally;

[0198] Optional bore precursor provided;

[0199] Adsorbent-binder materials are produced based on the adsorbent material, the one or more binder materials, optionally the crosslinking agent, and optionally the pore precursor;

[0200] The adsorbent-binder material is applied to the substrate;

[0201] The adsorbent-binder material applied to the substrate is used to form a fluid trapping material;

[0202] Optionally, the pore precursor is removed to form at least one pore in the fluid trapping material; and

[0203] The fluid trapping material is functionalized using at least one functionalized ligand containing an amine group.

[0204] 10. The method according to the foregoing clauses, wherein forming the fluid trapping material comprises:

[0205] The first layer of the fluid trapping material is formed using the adsorbent-binder material;

[0206] Optionally, the first layer is pre-wetted; and

[0207] A second layer is formed on the pre-wetted first layer.

[0208] 11. The method according to any of the preceding clauses, wherein the one or more adhesive materials comprise a first adhesive material and a second adhesive material, wherein the first adhesive material is different from the second adhesive material.

[0209] 12. The method according to any of the preceding clauses, wherein providing one or more adhesive materials includes providing a first amount of the one or more adhesive materials, wherein providing the crosslinking agent includes providing a second amount of the crosslinking agent, and wherein the ratio of the second amount to the first amount is less than 1 / 3, preferably less than 1 / 4.

[0210] 13. A system comprising:

[0211] substrate; and

[0212] A fluid trapping material formed on one or more surfaces of the substrate, wherein the fluid trapping material comprises:

[0213] An adsorbent material configured to bind to one or more fluids, including water, carbon dioxide, sulfur oxides, alcohols, or combinations thereof; and

[0214] One or more adhesive materials, wherein the adhesive materials are optionally at least partially crosslinked;

[0215] The fluid trapping material optionally includes at least one pore; and

[0216] The adsorbent material is functionalized with at least one functionalized ligand containing an amine group.

[0217] 14. The system according to the foregoing clauses, wherein the fluid trapping material comprises less than 15% by weight of the one or more binder materials.

[0218] 15. The system according to any of the preceding clauses, wherein the adsorbent material comprises a metal-organic framework (MOF), a covalent organic framework (COF), a polymeric resin, silica, zeolite, or a combination thereof.

[0219] 16. The system according to any of the preceding clauses, the system comprising a crosslinking agent, wherein the adhesive material is at least partially crosslinked with the crosslinking agent, and wherein the crosslinking agent comprises one or more of methacrylate reagents, acrylate reagents, vinyl ketone reagents, vinyl reagents, or allyl reagents.

[0220] 17. The system according to any of the preceding clauses, wherein the one or more adhesive materials comprise vinyl polymers, starch, alkyl cellulose, or combinations thereof.

[0221] 18. The system according to any of the preceding clauses, wherein the thickness of the fluid trapping material is between 0.1 mm and 3.5 mm.

[0222] 19. The system according to any of the preceding clauses, wherein the fluid trapping material comprises less than 20% by weight of the binder material.

[0223] 20. The system according to any of the preceding clauses, wherein the substrate is a fluid contactor.

[0224] Example

[0225] Without further detailed description, it is believed that those skilled in the art will be able to utilize the invention to its fullest extent using the foregoing description. Therefore, the following embodiments are to be interpreted as illustrative only and are not intended to limit the disclosure in any way. The starting materials used in the following embodiments need not be prepared by a specific preparation run, the procedure of which is described in other embodiments. It should also be understood that any numerical range described herein includes all values ​​from the lower limit to the upper limit. For example, if the range is stated as 10 to 50, it is intended that values ​​such as 12 to 30, 20 to 40, or 30 to 50, etc., be explicitly listed in this specification. These are merely embodiments of particular intent, and all possible combinations of values ​​between and including the listed minimum and maximum values ​​are considered to be explicitly stated in this application.

[0226] Fluid trapping materials.

[0227] Table 1 - CO2 Capacity of Some Fluid Capture Materials

[0228]

[0229] Table 1 shows examples of fluid trapping materials 44 that can be used to capture CO2. Generally, Table 1 shows the CO2 capacity of a control (e.g., Example 1) compared to samples comprising fluid trapping materials 44 formed using an adsorbent material (i.e., MOF-808-Gly) and a crosslinkable binder material (e.g., Examples 2 and 3). More specifically, Example 1 comprises the adsorbent material MOF-808-Gly in powder form, not deposited on the sample. Example 1 has a CO2 capacity of 0.3 mmol / g at 20°C and 20% RH in N2 with 400 ppm CO2.

[0230] Examples 2 and 3 illustrate fluid trapping materials 44 formed using an adsorbent material and a ultimately crosslinked binder material. More specifically, Example 2 is a fluid trapping material 44 having an adsorbent material 34 (e.g., MOF-808-Gly) and a crosslinkable binder material 36 (e.g., aminopropyl silsesquioxane). To prepare Example 2, 2.44 g of a 25% aqueous solution of aminopropyl silsesquioxane, 17.6 g of deionized water, and 0.12 g of Triton were used. ™X-100 and 5.1 g of MOF-808-Gly were mixed to prepare a slurry. After mixing, the slurry was coated onto a 2”×2” chromium-nickel-iron alloy sample, dried, and cured overnight under vacuum at 120°C. A high-quality coating with an equilibrium CO2 absorption rate (e.g., CO2 capacity) of 0.37 mmol / g was obtained when exposed to 400 ppm CO2 in a N2 gas stream at 20°C and 20% RH.

[0231] Example 3 is a fluid trapping material 44 comprising adsorbent material 34 (e.g., MOF-808-Gly), binder material 36 (e.g., PVA), and crosslinking agent 37 (e.g., PAA). To prepare Example 3, 1.55 g of an aqueous solution of 15% PVA (e.g., 88% hydrolyzed) and 3% PAA, 5.2 g of deionized water, and approximately 3 mg of Triton were used. ™ X-100 and 2.5 g of MOF-808-Gly were mixed to prepare a slurry. After mixing, the slurry was coated onto 2”×2” chromium-nickel-iron alloy samples, dried, and cured overnight under vacuum at 125°C. The results were obtained in AS... ™ A fluid trapping material that scored 3B in the D3359-17 adhesion test and had an equilibrium CO2 absorption rate of 0.38 mmol / g when exposed to 400 ppm CO2 in a N2 gas stream at 20°C and 75% RH. Generally, Examples 2 and 3 illustrate two crosslinked aqueous binder formulations used with MOF-808-Gly to form fluid trapping material 44, which has a CO2 binding capacity approximately equal to that of Example 1. Furthermore, the fluid trapping materials of Examples 2 and 3 exhibit good adhesion to the substrate.

[0232] In some embodiments, the fluid trapping material 44 can be formed using a non-aqueous solvent. For example, another embodiment of the fluid trapping material 44 (i.e., Example 4) typically comprises an adsorbent material 34 (e.g., MOF-808-Gly) and a crosslinkable silicone-containing binder material 36. First, a 0.2 g / mL solution of 1.2 mL of SPR100 in methyl ethyl ketone (MEK) is mixed with 94 mg of disilanol PDS-1615, 53 µL of alkoxysilane SIB1140.0, and 69 mg of Hypermer. ™-KD1 was mixed in vials. Separately, 3.0 g of MOF-808-Gly was mixed with 5 mL of isopropanol (IPA). The solution containing SPR100 was added to the MOF-808-Gly / IPA suspension. The SPR100 vial was rinsed with 2 × 0.5 mL MEK and added to the combined mixture. The slurry was further diluted with 2 mL IPA to obtain a viscosity suitable for coating. Then, 38 µL of trihexylamine was added to the slurry and the mixture was coated onto 2” × 2” chromium-nickel-iron alloy samples, dried, and cured under vacuum at 90 °C for 1 hr. The desired coating was obtained in AS... ™ A high-quality coating that received a score of 4A in the D3359-17 adhesion test.

[0233] As described above, in some embodiments, the fluid trapping material 44 is capable of binding water. Several embodiments of the fluid trapping material 44 according to this disclosure and the performance of such fluid trapping material 44 are described below.

[0234] A first embodiment of the water-binding fluid trapping material 44 may include an adsorbent material 34 (i.e., MOF-303), a binder material 36 (i.e., PVA), and a crosslinking agent (i.e., PAA) deposited on a metal substrate. More specifically, the first embodiment of the water-binding fluid trapping material 44 can be prepared by mixing 0.56 g of an aqueous solution of 15% poly(vinyl alcohol) [PVA, 88% hydrolyzed] and 3% poly(acrylic acid) [PAA], 2.0 g of deionized water, approximately 3 mg of AGITAN 351, 1.0 g of MOF-303, and 0.02 g of Tergitol 15-S-7 to form a slurry. After mixing, the slurry is coated onto a 2”×2” chromium-nickel-iron alloy sample and cured overnight at 125°C. A high-quality coating with good adhesion and an equilibrium water absorption rate of 26% to 28% by weight when tested in a humidity test chamber set to 20% RH and 25°C is obtained.

[0235] A second embodiment of the water-binding fluid trapping material 44 comprises an adsorbent material 34 (e.g., MOF-303), a binder material 36 (e.g., PVA), and a crosslinking agent (e.g., PAA) deposited on a glass-filled nylon sample (e.g., a glass-filled nylon substrate). More specifically, the second embodiment of the water-binding fluid trapping material 44 can be prepared by forming a slurry similar to that described above with respect to the first embodiment of the water-binding fluid trapping material 44 and coating the slurry onto a 2”×2” glass-filled polyamide (PA12) nylon sample. The coated sample is allowed to dry at room temperature and then cured overnight at 120°C. Once cooled to room temperature, the sample is immersed in water to release air bubbles and then patted dry. A second layer of slurry is then applied as previously described. This process is repeated once more. After final curing at 120°C, the coating weighs 0.9216 g and adheres well to the substrate. The equilibrium water absorption rate at 20% RH / 25°C is 28% by weight.

[0236] A third embodiment of the water-binding fluid trapping material 44 includes various binder materials 36. For example, the third embodiment of the water-binding fluid trapping material 44 may include binder materials 36 such as PVA, PAA, and poly(methyl / phenyl silsesquioxane). More specifically, the third embodiment of the water-binding fluid trapping material 44 can be prepared by mixing 1.78 g of an aqueous solution of 7.5% PVA [80% hydrolyzed] and 1.5% PAA with 3.5 g of deionized water, 0.02 g of DISPERBYK 190, approximately 3 mg of AGITAN 351, and 2.0 g of MOF-303. A solution of 0.08 g of Wacker MP-50E silicone emulsion diluted with 0.5 g of deionized water is added to the mixture. After mixing, the slurry is coated onto a 2”×2” glass-filled PA12 nylon sample. After drying at room temperature, the sample is cured at 120°C for 4 hours. After cooling, the sample was immersed in water to release air bubbles, patted dry, and then another layer of slurry was applied. This drying / curing process was then repeated as previously described. Two or more layers of slurry were then applied over the first two layers using the same procedure. The dried / cured coating weighed 1.4946 g at the end of the process. The coating adhered well and was free of cracks. The equilibrium water absorption rate at 20% RH / 25°C was 31% to 32% by weight.

[0237] A fourth embodiment of the water-bound fluid trapping material 44 includes an adsorbent material 34, such as MIL-160. To prepare the fourth embodiment of the water-bound fluid trapping material, 2.44 g of an aqueous solution of 13.5% PVA [88% hydrolyzed] and 4.5% PAA was mixed with 5.9 g of deionized water, 0.040 g of DISPERBYK 190, 0.030 g of AGITAN 351, 4.34 g of MIL-160, and 0.050 g of Tergitol 15-S-7. After mixing, the slurry was applied to a 2”×2” chromium-nickel-iron alloy sample. The sample was allowed to dry at room temperature and then overnight at 120°C. After cooling, the sample was immersed in water to release air bubbles and then gently patted dry. A second layer of slurry was applied as previously described and allowed to cure. The second layer did not adhere to the first layer but subsequently peeled off.

[0238] A fifth embodiment of the water-bound fluid trapping material 44 includes a variety of binder materials 36, such as silicone-containing binder materials, PVA, and PAA. It is recognized that using hybrid binder materials 36 (i.e., two, three, four, or more than four different or unique binder materials) can improve the adhesion properties of the fluid trapping material 44 or layer to the substrate and / or the adhesion properties of each layer of a multilayer coating. To prepare the fifth embodiment of the water-bound fluid trapping material, 8.0 g of an aqueous solution of 7.5% PVA (80% hydrolyzed) and 1.5% PAA was mixed with 9.0 g of deionized water, 0.10 g of DISPERBYK 2055, 0.015 g of AGITAN351, and 8.0 g of MIL-160. A solution of 0.08 g of Wacker MP-50E silicone emulsion diluted with 2.0 g of deionized water was added. After mixing, the slurry was used to coat a small chromium-nickel-iron alloy heat exchanger. After drying at room temperature, the sample was cured at 120°C for 2 hours. After cooling, the sample was immersed in water to release air bubbles, patted dry, and then another layer of slurry was applied. The drying / curing process was then repeated as previously described. Finally, a third layer was applied as previously described. After final curing overnight at 120°C, 3.1 g of well-adhesive coating was obtained. The equilibrium water absorption rate at 20% RH / 25°C was 30% to 32% by weight.

[0239] It was further recognized that crosslinking of the composite coating can improve the structural integrity of the fluid trapping material 44 or the coating. To illustrate the improved structural integrity based on the addition of crosslinking agent 37, two compositions of adsorbent material 34 and binder material 36 were prepared. The first composition was based on the disclosed fluid trapping material 44 and was therefore formed by crosslinking of binder material 36 (i.e., by adding PAA). In the second composition, binder material 36 was not crosslinked (i.e., no PAA was added). To prepare the first composition, a slurry was prepared by mixing 0.56 g of an aqueous solution of 13.5% poly(vinyl alcohol) [PVA, 88% hydrolyzed] and 4.5% poly(acrylic acid) [PAA], 1.4 g of deionized water, 0.02 g of DISPERBYK 190, and 1.0 g of MIL-160. After mixing, the slurry was coated onto a 1”×1” chromium-nickel-iron alloy sample, dried at room temperature, and cured overnight in a vacuum oven at 125°C. The sample was cooled to room temperature in a vacuum desiccator and then rapidly weighed. The sample was then immersed in 10 mL of deionized water and placed in an oven at 90°C for 2 hours. At the end of this time, the sample was removed and dried at 90°C for 1 hour, followed by drying in a vacuum oven at 125°C for 2 hours. Finally, the sample was cooled in a vacuum desiccator and weighed again as previously described. The weights were: (1) uncoated sample: 5.0038 g; (2) coated sample after curing: 5.3206 g (i.e., the coating weight was 0.3168 g); (3) coated sample after immersion / drying: 5.3087 g (i.e., the coating weight was 0.3049 g); and (4) the weight of the coating retained after immersion: 96.2%.

[0240] To prepare the second composition (i.e., without the use of crosslinking agent 37), a slurry was prepared by mixing 0.67 g of an aqueous solution of 15% poly(vinyl alcohol) [PVA, 88% hydrolyzed], 1.3 g of deionized water, 0.02 g of DISPERBYK 190, and 1.0 g of MIL-160. After mixing, the slurry was coated onto a 1”×1” chromium-nickel-iron alloy sample, dried at room temperature, and cured overnight in a vacuum oven at 125°C. The sample was cooled to room temperature in a vacuum desiccator and then rapidly weighed. It was then immersed in 10 mL of deionized water and placed in an oven at 90°C for 2 hours. Shortly after immersion in water, the coating began to crack and detach from the sample. At the end of this time, the sample was removed and dried at 90°C for 1 hour, followed by drying in a vacuum oven at 125°C for 2 hours. Finally, the sample was cooled in a vacuum desiccator and reweighed as previously described. The weights were: (1) uncoated sample: 5.0320 g; (2) coated sample after curing: 5.1974 g (i.e., coating weight is 0.1654 g); (3) coated sample after immersion / drying: 5.0573 g (i.e., coating weight is 0.0253 g); and (4) coating weight retained after immersion: 15.3%. Specifically, the first composition (i.e., the embodiment of fluid trapping material 44 including a crosslinking binder) contained PAA, and the cured film obtained in this case retained 96% of its mass after 2 hours in water at 90°C. Conversely, using the second composition (i.e., using PVA without any crosslinking agent), only 15% of that mass was retained after testing in the same manner.

[0241] As described herein, the fluid trapping material 44 can be formed using a crosslinking agent 37 having different types of functional groups that promote the formation of the fluid trapping material 44. In an example of preparing this composition, 0.30 g of poly(vinyl butyral) was dissolved in 6.0 g of isopropanol. Furthermore, 0.065 g of 2-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane, 3.0 g of amine-treated silica adsorbent, and 0.07 g of BYK9076 were then mixed in. The resulting slurry was coated onto an aluminum sample using a doctor blade. After drying at room temperature, the sample (e.g., the aluminum sample coated with the slurry) was placed in a 90°C oven for 1 hour to cure. The CO2 absorption rate was measured using 400 ppm CO2 in nitrogen under drying conditions at 25°C. The average value was determined to be 0.734 mol CO2 / kg coating (0.032 g / g).

[0242] Figure 4This is a graph with a y-axis corresponding to the amount of CO2 (ppm) and an x-axis corresponding to time (minutes (min)). In this embodiment, a fluid trapping material 44 is formed using a binder material 36 comprising PVA / PAA, as described in Table 1 for Example 3. Furthermore, the fluid trapping material 44 is subjected to a fluid flow of 50 standard cubic centimeters per minute (sccm) having 400 ppm CO2 and 75% RH. As roughly shown in the figure, CO2 is detected approximately 170 minutes after the fluid flow enters the fluid trapping material or coating.

[0243] As described herein, the fluid trapping material 44 is capable of trapping a target fluid, such as H2O. In such embodiments, it is now recognized that forming the fluid trapping material 44 capable of releasing the trapped fluid can be advantageous. To illustrate this, Figure 5 This is an example of a method used to capture target fluids (e.g., as described in...). Figure 1 A diagram of method 60 for the target fluid 18 and the subsequent controlled release of the target fluid (i.e., when it may be desirable to remove the target fluid 18). For example, in an embodiment where the target fluid 18 includes water, it may be desirable to extract water from a fluid source (such as air with a relatively high moisture content, e.g., greater than 500 ppm of water) using the disclosed fluid trapping material 44 and subsequently release the water to produce pure water.

[0244] Referring to method 60, at frame 62, a gas flow 64 is provided to a substrate 16 coated with fluid trapping material 44. Water in the gas flow 64 combines with the trapping coating, thereby producing a dry gas flow 66. At frame 68, a heat exchanger 70 is heated (e.g., using hot air at a temperature greater than 80°C, 85°C, 90°C, or 95°C). In any case, the water combined with the fluid trapping material 44 can be released as steam 72. At frame 74, a condenser 76 can receive and cool the steam 72, thereby producing water 78. At frame 80, heat can be recovered. In this way, the fluid trapping material 44 can be used to extract fluid and, in some embodiments, to release fluid.

[0245] As described herein, the fluid trapping material 44 may include a crosslinking agent 37 (i.e., a polymer used to crosslink the fluid trapping material 44). In some embodiments, the crosslinking agent 37 may include colloidal silica. Figure 6A graph is shown with an x-axis corresponding to time and a y-axis corresponding to the weight increase (%). In this graph, the relationship between the weight increase and time is shown for the gas-trapping coating formed by: PVA as a binder and MOF as an adsorbent (i.e., "PVA+MOF"); PVA as a binder and silica as a crosslinking agent and MOF as an adsorbent (i.e., "PVA+Silica+MOF"); and silica and starch as crosslinking agents and MOF as an adsorbent (i.e., "PVA+Silica+Starch+MOF"). As shown, the fluid-trapping material with crosslinking agents (i.e., thus having a crosslinked polymer composite matrix) exhibits a relatively high weight increase, which corresponds to more target fluid 18 being adsorbed onto the fluid-trapping material 44.

[0246] Enhanced porosity.

[0247] The porosity of a membrane can be controlled and enhanced by using pore precursors. For example, wax particles can be formulated into a MOF slurry, which is then cast into a membrane. These wax particles occupy spaces within the membrane, which, once removed, can then be transformed into channels or pores, or even interconnected voids. Wax particles can be removed by any suitable method, such as heating to melt them and / or by washing the membrane with a suitable solvent and / or by solvent extraction with a suitable solvent. Heating can melt wax, remove certain materials by sublimation, and / or decompose compounds capable of generating gas. Once the wax particles are removed, the membrane has increased porosity, which improves macropore diffusion.

[0248] Figure 7 SEM images depicting the cross-section of the film after casting and including wax (disixetaneous fumarate) crystals. Figure 8 SEM images depicting the cross-section of the film produced after casting and using wax crystals, where the wax crystals were removed after heating to 90°C, are shown. Figure 1 This demonstrates that a pore precursor (such as wax crystals) can be included in a cast film and subsequently removed to leave at least one pore.

[0249] Methods for preparing membranes.

[0250] Non-porous membrane.

[0251] First, 0.025 g of polyvinyl butyral resin (Butvar B98) was dissolved in 1.8 g of ethanol. Then, 0.025 g of clay was added to the solution, and the mixture was stirred for 15 minutes. Subsequently, 0.5 g of amine-functionalized MOF adsorbent was added, and the slurry was vortexed for several minutes before being coated onto 2-inch × 2-inch aluminum samples. The coated samples were air-dried in a fume hood for one hour, and then dried in a 90°C oven for one hour. The membrane density was measured to be 0.26 g / cm³. 3 .

[0252] A membrane with pores.

[0253] First, 0.025 g of polyvinyl butyral resin (Butvar B98) was dissolved in 1.8 g of ethanol. Then, 0.025 g of clay was added to the solution, and the mixture was stirred for 15 minutes. 0.1 g of wax (dimethyl eicosanoate) was added to the solution and mixed for one hour. 0.5 g of amine-functionalized MOF adsorbent was added, and the slurry was vortexed for several minutes before being coated onto 2-inch × 2-inch aluminum samples. The coated samples were air-dried in a fume hood for one hour, then immersed in heptane for 2 hours to remove the wax. The samples were then removed from the heptane, air-dried, and then dried in a 90°C oven for one hour. 1 ¹H NMR was used to confirm the complete removal of dimethyl eicosanoate from the membrane. The membrane density was measured to be 0.24 g / cm³. 3 .

[0254] The CO2 absorbance of both non-porous and porous membranes was measured using a passthrough test apparatus at 25°C, 400 vppm CO2, and 50% RH. Kinetic characterization showed that the porous membrane required 7 minutes faster than the non-porous membrane to reach a complete equilibrium CO2 absorbance of 63%.

[0255] Amines are used to functionalize membranes containing adsorbents.

[0256] F1GE115-1003B: MOF-274 membranes were prepared as follows: 0.025 g of polyvinyl butyral resin (Butvar 79) and 0.005 g of epoxycyclohexylethyltrimethoxysilane (A-186) were dissolved in 0.875 g of isopropanol (IPA), and mixed with 0.0075 g of a VOC-free and solvent-free wetting and dispersing additive (DISPERBYK 2157) and 0.25 g of MOF-274 as an adsorbent. The mixed slurry was coated onto 1 inch × 1 inch aluminum samples, which were dried at room temperature and then cured overnight under vacuum at 120°C. After cooling, each sample was weighed, and the mass of MOF-274 in the membrane was determined using the mass of the composite material and the percentage of the binder. To functionalize the MOF-274-containing membrane, an amine mixture consisting of spermine and bis(aminoethylaminomethyl)disiloxane (AEAM) was dissolved in baijiu (Chinese white liquor) at 60°C. The molar ratio of adsorbent (MOF-274):spermine:AEAM was 1:0.65:0.75. The MOF-274-containing membrane was immersed in the amine solution at 60°C for 24 hours, then removed and washed with baijiu. The amine-functionalized MOF-274 membrane was dried under vacuum at 120°C for 2 days. After digestion with 600 µL of DMSO-d6, 200 µL of D2O, and 40 µL of 35% DCl, samples scraped from the amine-functionalized MOF-274-containing membrane were subjected to... 1 1H NMR analysis was performed to determine the amine loading ratio. 1 ¹H NMR (DMSO-d6, D₂O) δ 7.84 (dd, 2H), 7.66 (dd, 2H), 6.96 (dd, 2H), 3.20–3.17 (m, 3.68H), 2.97–2.86 (m, 7.23H), 2.37 (s, 1.62H), 1.93 (m, 2.5H), 1.65 (bs, 2.39H), 0.16 (s, 5.5H). The final MOF-274:spermine:AEAM ratio was measured to be 1:0.61:0.46.

[0257] F1GE115-1003BP: Use a similar process to FGE115-1003B, except that a 1-inch × 1-inch aluminum sample is primed with Butvar B79, A-186 epoxy silane IPA solution prior to coating. 1¹H NMR (DMSO-d6,D₂O) δ 7.83 (dd, 2H), 7.65 (dd, 2H), 6.96 (dd, 2H), 3.20–3.17 (m, 3.84H), 2.98–2.86 (m, 6.58H), 2.38 (s, 1.78H), 1.93 (m, 2.14H), 1.65 (bs, 2.2H), 0.16 (s, 5.9H). The final adsorbent MOF-274:spermine:AEAM ratio was measured to be 1:0.54:0.46.

[0258] F1GE159-1026A3: To prepare a membrane containing the adsorbent MOF-274, 0.025 g of polyvinyl butyral resin (Butvar 79) and 0.005 g of epoxycyclohexylethyltrimethoxysilane (A-186) were dissolved in 1.1875 g of IPA and mixed with 0.0075 g of a VOC-free and solvent-free wetting and dispersing additive (DISPERBYK 2157) and 0.25 g of MOF-274. A primer-coated 1-inch × 1-inch aluminum sample was coated with the mixed slurry, dried at room temperature, and then cured overnight under vacuum at 120°C. After cooling, each sample was weighed, and the mass of the adsorbent MOF 274 in the membrane was determined using the mass of the composite material and the percentage of the binder. To functionalize the membrane containing the adsorbent MOF-274, spermidine was dissolved in white wine at 60°C. The molar ratio of MOF-274 to spermidine was 1:1.2. The membrane containing the adsorbent MOF-274 was immersed in a spermidine solution at 60°C for 24 hours, then removed and washed with baijiu (Chinese liquor). The membrane was dried under vacuum at 120°C for 2 days. After digestion with 600 µL of DMSO-d6, 200 µL of D2O, and 40 µL of 35% DCl, the sample scraped from the amine-functionalized MOF-274 membrane was subjected to… 1 1H NMR analysis was performed to determine the amine loading ratio.

[0259] 1 H NMR (DMSO-d 6, D₂O) δ 7.85 (dd, 2H), 7.67 (dd, 2H), 6.97 (dd, 2H), 2.97–2.78 (m, 7.6H), 1.92 (m, 1.88H), 1.60 (m, 3.79H). The final MOF-274:spermine ratio was measured to be 1:0.95.

[0260] F2GE115-1101A1: To prepare the MOF-274 membrane, 0.025 g of polyvinyl butyral resin (Butvar 79) was dissolved in 0.5 g of ethanol and mixed with 0.025 g of hydrophilic bentonite nanoclay and 0.25 g of MOF-274. A 1 inch × 1 inch aluminum sample was coated with the mixed slurry, dried at room temperature, and then dried at 90 °C for 2 hours. After cooling, each sample was weighed, and the mass of MOF-274 in the membrane was determined using the mass of the composite material and the percentage of the binder. To functionalize the membrane containing the adsorbent MOF-274, an amine mixture consisting of spermine and AEAM was dissolved in liquor at 60 °C. The molar ratio of MOF-274:spermine:AEAM was 1:0.65:0.75. The MOF-274 membrane was immersed in the amine solution at 60 °C for 24 hours, then removed and washed with liquor. The membrane was dried under vacuum at 120°C for 2 days. After digestion with 600 µL of DMSO-d6, 200 µL of D2O, and 40 µL of 35% DCl, samples scraped from the amine-functionalized MOF-274 membrane were subjected to… 1 1H NMR analysis was performed to determine the amine loading ratio. 1 ¹H NMR (DMSO-d6, D₂O) δ 7.88 (dd, 2H), 7.71 (dd, 2H), 67.0 (dd, 2H), 3.19–3.16 (m, 3.27H), 2.97–2.85 (m, 5.52H), 2.37 (s, 1.55H), 1.91 (m, 1.97H), 1.64 (bs, 1.8H), 0.17 (s, 4.72H). The final MOF-274:spermine:AEAM ratio was measured to be 1:0.47:0.4.

[0261] Overview.

[0262] Therefore, this disclosure relates to a fluid trapping material or a fluid trapping material that provides improved fluid binding capacity and stability. The fluid trapping material or coating typically comprises an adsorbent material and a binder material. The fluid trapping material or coating also includes at least one pore formed by a pore precursor. As described herein, the resulting fluid trapping material or coating may comprise a crosslinked polymer formed from one or more binder materials and certain crosslinking agents such as ultraviolet light, polyacrylic acid, heat, or other additives (such as leveling agents, dispersants, etc.) or combinations thereof.

[0263] The technical effects of this invention include, but are not limited to, improving the capacity and / or capture efficiency of a substrate through a fluid trapping material. By providing the disclosed fluid trapping material, it is possible to reduce the amount of certain gases retained in the exhaust gas stream. Furthermore, by forming a fluid trapping material comprising a crosslinked polymer, a relatively larger amount of adsorbent material can be used compared to a binder material, thereby improving the fluid binding capacity of the fluid trapping material. Additionally, by forming a fluid trapping material comprising at least one pore, the porosity and gas diffusion capacity of the fluid trapping material are enhanced. Finally, the capacity and / or capture efficiency are enhanced through functionalization.

[0264] This written description uses examples to disclose the invention, including the best mode, and also enables any person skilled in the art to practice the invention, including making and using any device or system and performing any combination of methods. The patentable scope of the invention is defined by the claims and may include other examples that would occur to a person skilled in the art. Such other examples are contemplated within the scope of the claims if they have structural elements that are not different from the literal language of the claims, or if they include equivalent structural elements that are not substantially different from the literal language of the claims.

Claims

1. A method for functionalizing a system, said system comprising: substrate; and Fluid trapping material, the fluid trapping material being formed on one or more surfaces of the substrate, The method includes functionalizing the fluid trapping material with at least one functionalized ligand containing an amine group.

2. The method of claim 1, wherein functionalizing the fluid trapping material with at least one functionalized ligand containing an amine group comprises receiving the at least one functionalized ligand containing an amine group at the fluid trapping material.

3. The method of claim 1, wherein the at least one functionalized ligand comprising an amine group is received in the form of a solution or a gas.

4. The method of claim 1, wherein functionalizing the fluid trapping material with at least one functionalized ligand containing an amine group comprises using techniques selected from the group consisting of solution impregnation, gas phase wetting, and combinations thereof to functionalize the fluid trapping material with at least one functionalized ligand containing an amine group, wherein the techniques are performed under a pressure selected from the group consisting of ambient pressure, positive pressure, vacuum pressure, and combinations thereof.

5. The method of claim 1, wherein the fluid trapping material is not functionalized prior to being functionalized with at least one functionalized ligand containing an amine group.

6. The method of claim 1, wherein the fluid trapping material has been partially or fully functionalized at least once before being functionalized with at least one functionalized ligand containing an amine group.

7. The method of claim 1, wherein the fluid trapping material comprises at least one adsorbent selected from the group consisting of metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and combinations thereof.

8. The method of claim 1, wherein the fluid trapping material comprises: An adsorbent material configured to bind to one or more fluids, including water, carbon dioxide, sulfur oxides, alcohols, or combinations thereof; and One or more adhesive materials, wherein the adhesive materials are optionally at least partially crosslinked; The fluid trapping material optionally includes at least one pore.

9. A method, the method comprising: An adsorbent material is provided that is configured to bind to one or more fluids, said fluids including water, carbon dioxide, sulfur oxides, alcohols, or combinations thereof; One or more adhesive materials are provided, wherein the one or more adhesive materials optionally include components capable of forming a crosslinked polymer; A crosslinking agent may be provided optionally; Optional bore precursor provided; Adsorbent-binder materials are produced based on the adsorbent material, the one or more binder materials, optionally the crosslinking agent, and optionally the pore precursor; The adsorbent-binder material is applied to the substrate; The adsorbent-binder material applied to the substrate is used to form a fluid trapping material; Optionally, the pore precursor is removed to form at least one pore in the fluid trapping material; as well as The fluid trapping material is functionalized using at least one functionalized ligand containing an amine group.

10. The method of claim 9, wherein forming the fluid trapping material comprises: The first layer of the fluid trapping material is formed using the adsorbent-binder material; Optionally, the first layer is pre-wetted; as well as A second layer is formed on the pre-wetted first layer.

11. The method of claim 9, wherein the one or more adhesive materials comprise a first adhesive material and a second adhesive material, wherein the first adhesive material is different from the second adhesive material.

12. The method of claim 9, wherein providing one or more adhesive materials comprises providing a first amount of the one or more adhesive materials, wherein providing the crosslinking agent comprises providing a second amount of the crosslinking agent, and wherein the ratio of the second amount to the first amount is less than 1 / 3.

13. A system comprising: substrate; and A fluid trapping material formed on one or more surfaces of the substrate, wherein the fluid trapping material comprises: An adsorbent material configured to bind to one or more fluids, including water, carbon dioxide, sulfur oxides, alcohols, or combinations thereof; and One or more adhesive materials, wherein the adhesive materials are optionally at least partially crosslinked; The fluid trapping material optionally includes at least one pore; and The adsorbent material is functionalized with at least one functionalized ligand containing an amine group.

14. The system of claim 13, wherein the fluid trapping material comprises less than 15% by weight of the one or more binder materials.

15. The system of claim 13, wherein the adsorbent material comprises a metal-organic framework (MOF), a covalent organic framework (COF), a polymeric resin, silica, zeolite, or a combination thereof.

16. The system of claim 13, wherein the system comprises a crosslinking agent, wherein the adhesive material is at least partially crosslinked with the crosslinking agent, and wherein the crosslinking agent comprises one or more of a methacrylate reagent, an acrylate reagent, a vinyl ketone reagent, a vinyl reagent, or an allyl reagent.

17. The system of claim 13, wherein the one or more binder materials comprise vinyl polymers, starch, alkyl cellulose, or combinations thereof.

18. The system of claim 13, wherein the thickness of the fluid trapping material is between 0.1 mm and 3.5 mm.

19. The system of claim 13, wherein the fluid trapping material comprises less than 20% by weight of the one or more binder materials.

20. The system of claim 13, wherein the substrate is a fluid contactor.

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