Metal-organic frame (MOF) composition, method for preparing the same, and method for using the same

Abstract

Metal-organic framework (MOF) compositions, methods for preparing them, and methods for using them are disclosed herein. MOF compositions comprise multiple metal nodes, multiple organolinkers, multiple organoligands, and metal salts such as metal halides. These MOF compositions can capture target chemicals in a gaseous stream. The target chemical may be ammonia.

Description

Technical Field

[0001] Description of Research and Development Funded by the Federal Government

[0001] This invention was made with government support under contract number N68335 - 21 - C - 0653 awarded by the United States Navy. The government has certain rights in this invention.

[0002] Cross - Reference to Related Applications

[0002] This application claims the priority of U.S. Patent Provisional Application No. 63 / 471,783, filed on June 8, 2023, the entire content of which is incorporated herein by reference.

[0003]

[0003] Metal - organic framework (MOF) compositions, methods for preparing MOF compositions and materials containing MOF compositions, and methods of using them are disclosed herein. The MOF compositions include a plurality of metal nodes, a plurality of organic linkers, a plurality of organic ligands, and metal salts such as metal halides. These compositions can capture target chemical substances in an air stream. In one embodiment, the target chemical substance may be ammonia.

Background Art

[0004]

[0004] Adsorbent materials are well - known and are used in several applications such as air filtration, gas supply, etc. One particular use of adsorbents is the removal or reduction of target chemical substances in various air streams. An important use is the removal of Toxic Industrial Compounds (TICs) present in air streams including air flow.

[0005]

[0005] TICs can be classified as either basic compounds or base-forming compounds, or acidic compounds or acid-forming compounds. Typically, adsorbents exhibit adsorption capacity for various TICs. The capacity for each target chemical or TIC depends on the properties of the adsorbent, and therefore, a material may function well for adsorbing one TIC but not for adsorbing multiple TICs. For example, the MOF adsorbent Zr-BDC-NH2 has been shown to have high adsorption capacity for NO2 but only slight capacity for ammonia. The ammonia filtration capacity of Zn-BDC-NH2 can be enhanced by impregnating the MOF with a metal chloride salt, as shown in US20210379559A1, to achieve good adsorption capacity for both NO2 and NH3. Another MOF adsorbent, MOF-808, has been shown to have moderate NO2 removal capacity. Filters that need to mitigate multiple TICs are routinely needed in a wide range of industries. These technologies typically utilize multiple adsorbents. In other words, the ability to mitigate one TIC may be sufficient to mitigate a target TIC in a particular airflow, but not high enough to mitigate another TIC in the same airflow. This necessitates the use of multiple adsorbents to mitigate two or more TICs in an airflow such as air.

[0006]

[0006] There is a need for adsorbent materials that can adsorb or reduce one or more TICs from fluid flows, in particular from air flows such as air flows, industrial air flows, off-gas flows, or polluting air flows. In some cases, it would be even more desirable to provide adsorbent materials that can adequately adsorb or reduce two or more TICs from such fluid flows.

[0007]

[0007] US2019 / 0091503 discloses that MOFs such as UiO-66 can be impregnated with metal compounds such as metal hydroxides or metal hydrides, thereby dispersing the metal compounds either on the surface of the MOF or within its pores. The '503 publication application states that these impregnated metal compounds have catalytic properties that can destroy chemical weapons (CWAs) such as sarin.

[0008]

[0008] Solvent-assisted ligand incorporation (SALI) has been used to functionalize channels in metal-organic framework (MOF) materials such as NU-1000, which have phosphonate-terminated ligands that result in zirconium(IV) coordination sites that are unstable to substitution.

[0009]

[0009] In one embodiment, a type of MOF composition having enhanced adsorption to a basic material, specifically to ammonia, is disclosed herein.

[0010] In another embodiment, a type of MOF composition is disclosed herein that is expected to maintain good adsorption capacity for acidic compounds such as nitrogen dioxide or chlorine, while enhancing adsorption capacity for basic compounds such as ammonia. [Overview of the Initiative] [Means for solving the problem]

[0010]

[0011] In one embodiment, a metal-organic structure (MOF) composition comprises: a plurality of metal nodes, each having at least two coordination sites; a plurality of organic linkers, wherein the metal nodes are connected by organic linkers bonded at one or more coordination sites on the metal nodes to form a first metal-organic structure; a plurality of organic ligands, each containing a coordination group bonded to the coordination sites of the metal nodes, wherein each organic ligand further contains at least one functional group; and a metal salt that interacts with the structure to result in the metal-organic structure composition. Materials and articles containing the disclosed metal-organic structure composition are also disclosed herein.

[0011]

[0012] The metal node may include a metal oxocluster comprising at least two metal atoms M selected from Zr, V, Al, Fe, Cr, Co, Ti, Hf, Cu, Zn, Ni, In, Ce, and mixtures thereof. The organic linker comprises at least two groups that can bond to the metal node, such as carboxylic acid groups. In one embodiment, the organic linker may be selected from the group consisting of 1,3,5-benzenetricarboxylic acid, 1,4-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, their functionalized derivatives, and combinations thereof.

[0012]

[0013] The coordinating group of the organic ligand may be selected from one or more of carboxylates, phosphonates, phosphonites, sulfonates, and sulfinates. The metal salt may be selected from halides, sulfates, carbonates, acetates, carboxylates, sulfonates, nitrates, or mixtures thereof. In a specific embodiment, the metal salt is a halide salt.

[0013]

[0014] A second embodiment of the present disclosure is a method for producing an MOF composition, comprising the steps of: synthesizing a first metal-organic structure including a metal node connected by an organolinker; contacting the first MOF with a first solution containing an organic ligand and an incorporation solvent to form a ligand-modified MOF; contacting the ligand-modified MOF with a second solution containing a metal salt and a salt-impregnation solvent; and separating the MOF from the solution to obtain the disclosed MOF composition. The MOF composition may be activated as needed.

[0014]

[0015] Further embodiments include a method for capturing a target chemical substance in a fluid stream, comprising the steps of preparing a solid adsorbent comprising an MOF composition disclosed herein, and contacting a fluid stream containing at least one target chemical substance with the solid adsorbent, thereby adsorbing at least a portion of the target chemical substance by the solid adsorbent. The at least one target chemical substance may be ammonia and may be present at a concentration of about 1 ppb to about 10%. The solid adsorbent comprises an MOF composition comprising a plurality of metal nodes, each having at least two coordination sites, a plurality of organic linkers, the metal nodes being connected by organic linkers bonded at one or more coordination sites on the metal nodes to form a metal-organic structure, a plurality of organic ligands, each having a coordination group bonded to the coordination sites of the metal nodes, each having at least one functional group, and a metal salt that interacts with the structure.

[0015]

[0016] These and other aspects of the present disclosure will become clearer with reference to the following detailed description and drawings. [Brief explanation of the drawing]

[0016] [Figure 1]

[0017] This figure shows the modification of MOF-808 with the organic ligand tartaric acid. [Figure 2]

[0018] This figure shows the modification of MOF-808 by the organic ligand gallic acid. [Figure 3]

[0019] This figure shows an overview of the initial steps of the overall process described herein, in which a metal salt is combined with an organic linker to form an MOF, and then the MOF is modified with an organic ligand bonded to the coordination site. Zr is shown as the metal M, 1,3,5-benzenetricarboxylic acid as the organic linker, and gallic acid as the organic ligand. [Modes for carrying out the invention]

[0017] definition

[0020] A metal-organic framework (MOF) is a coordination of a metal ion and at least a bidentate organic linker. An MOF comprises a corner atom or cluster of a metal ion, called a metal node, and an organic linker molecule that connects the metal nodes to form a structure with a high surface area, crystalline structure, and uniformly sized pores. Ligands are organic molecules attached to the metal nodes via coordinating groups on the ligand; unlike linkers, they do not link the metal nodes together to form a crystalline structure. In addition to coordinating groups, organic ligands have at least one functional group.

[0018]

[0021] As used herein, the terms “MOF composition” or “metal-organic structure composition” refer to a metal-organic structure of a metal node and a linker, and include the coordinated organic ligands and metal salts that interact with the structure as disclosed herein.

[0019]

[0022] As used herein, the term “material comprising MOF composition” refers to a composition comprising the MOF composition as defined above, and may include, but is not limited to, other components, one or more of the following: binders, other adsorbents, and other additives.

[0020]

[0023] In the context of the present disclosure, the term "derived from" or "derivative" means that the organic linker can be present in the structural material in a partially deprotonated or fully deprotonated form. Additionally, the organic linker can contain substituents or can contain a plurality of substituents independently of each other. Non-limiting examples of such substituents also include -OH, -NH2, -OCH3, -CH3, -NH(CH3), -N(CH3)2, -CN, and halides.

[0021]

[0024] As used herein, the term "modified" refers to a MOF structure having a functional organic ligand coordinated to the structure. For example, a MOF modified with gallic acid has gallic acid ligand molecules coordinated to the metal node-linker structure. A modified MOF is also referred to herein as a ligand-modified MOF.

[0022]

[0025] As used throughout the specification and claims, "substantially" means at least 70%, or at least 80%, or at least 90%, or at least 95%.

[0023] Detailed Description of the Present Disclosure

[0026] Metal-organic frameworks (MOFs) are a well-known type of material in which metal nodes are linked by organic linkers to form a crystalline structure having a high surface area and uniformly sized pores.

[0024]

[0027] Metal-organic structures can be referred to by appropriate names such as UiO-66 or MOF-808, or by their topology, i.e., network structure. These names and topologies are stored in a database accessible from the International Commission on Metal-Organic Frameworks (MOF Structures-Metal-Organic Frameworks-International Commission) (mof-international.org), linked from the International Commission on Metal-Organic Frameworks website.

[0025]

[0028] For example, the MOF UiO-66 contains a metal node containing a Zr6O4(OH)4 metal oxocluster, which is connected to coordination sites on the metal node via up to approximately 12 1,4-benzene-dicarboxylate (i.e., BDC) organic linkers, thereby forming a face-centered cubic lattice (fcu topology). Another MOF, MOF-808, contains a metal node containing the same Zr6O4(OH)4 metal oxocluster, but its metal oxocluster is connected to coordination sites on the metal node via carboxylate functional groups, which are tricarboxylic acid-derived, by up to approximately 6 benzene-1,3,5-tricarboxylate (i.e., BTC) organic linkers, thereby forming a 6-linked spn topology.

[0026]

[0029] The MOF compositions disclosed herein include a plurality of metal nodes, each having at least two coordination sites, a plurality of organic linkers, wherein the metal nodes are connected by organic linkers bonded at one or more coordination sites on the metal nodes to form a metal-organic structure; the structure further includes a plurality of organic ligands, each having a coordination group bonded to the coordination sites of the metal nodes, each organic ligand further having at least one functional group; and the MOF composition further includes a metal salt that interacts with the structure.

[0027]

[0030] The metal nodes of the MOF include metal atoms M, which may be selected from the group including, but are not limited to, Zr, V, Al, Fe, Cr, Co, Ti, Hf, Cu, Zn, Ni, In, Ce, and mixtures thereof. Preferably, the plurality of metal nodes include a metal oxocluster comprising at least two metal atoms M selected from Zr, V, Al, Fe, Cr, Co, Ti, Hf, Cu, Zn, Ni, In, Ce, and mixtures thereof. Preferred subsets of the above metals may include, but are not limited to, Zr, Hf, Al, Fe, Cu, and Zn, as well as mixtures thereof. In one embodiment, the metal nodes may include any of zirconium, hafnium, and mixtures thereof. In one embodiment, at least some of the metal nodes may include zirconium.

[0028]

[0031] A metal oxocluster may contain two or more metal atoms bridged by oxygen atoms. A metal oxocluster may contain a bibridged oxygen atom represented as MOM, or typically a single oxygen atom represented as M-OH as a hydroxyl group. A metal oxocluster may have more or fewer hydroxyl groups through the desorption or addition of water to the metal oxocluster. For example, the previously mentioned Zr6O4(OH)4 metal oxocluster can desorb water to form a Zr6O5(OH)2 metal oxocluster. Coordination sites on the metal oxocluster may include hydroxyl groups, oxo groups, or metal moieties, or combinations thereof. In one embodiment, the coordination sites on the metal oxocluster may include hydroxyl groups.

[0029]

[0032] An organic linker is an organic molecule containing at least two groups, which can be bonded to a metal node, such as a carboxylate functional group. The carboxylate functional group can bond to a metal node at the coordination site to form a metal-organic structure. The organic linker containing at least two carboxylate functional groups may be selected from dicarboxylic acids, tricarboxylic acids, or tetracarboxylic acids.

[0030]

[0033] Organic linkers include, for example, oxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic acid, 4-oxopyrane-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, and 2-methyl benzoate. Noline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimidodicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, Pluriol E 200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-dicarboxylic acid, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-binaphthyidicarboxylic acid acid), 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran-250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenyllinedane 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, hydroxybenzophenone dicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E 400-dicarboxylic acid, Pluriol E 600-Dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diamino(diphenylether)diimidodicarboxylic acid, 4,4'-diaminodiphenylmethanediimidodicarboxylic acid, 4,4'-diamino(diphenylsulfone)diimidodicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2',3' -Diphenyl-p-terphenyl-4,4''-dicarboxylic acid, (diphenyl ether)-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, 2,5-dihydroxy-1,4-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4'-Dihydroxy-diphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorubin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1- The dicarboxylic acid may be methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazole dicarboxylic acid, 2-nitro-benzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbonane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, or camphor dicarboxylic acid.

[0031]

[0034] The organic linker may be a tricarboxylic acid such as 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,3-,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, or aurintricarboxylic acid.

[0032]

[0035] Organic linkers include tetracarboxylic acids such as 1,1-dioxideperiro[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylenetetracarboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid or perylene-1,12-sulfone-3,4,9,10-tetracarboxylic acid, butanetetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid or meso-1,2,3,4-butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3, These may be cyclopentanetetracarboxylic acids such as 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, or cyclopentane-1,2,3,4-tetracarboxylic acid.

[0033]

[0036] The MOF compositions disclosed herein preferably comprise a plurality of organic linkers selected from the group consisting of 1,3,5-benzenetricarboxylic acid, 1,4-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, functionalized derivatives thereof, and combinations thereof. The functionalized derivatives of the linkers may, but are not limited to, include one or more substituents, including -OH, -NH2, -OCH3, -CH3, -NH(CH3), -N(CH3)2, -CN, and halides. In one embodiment, the functionalized derivative is an amino derivative of the organic linker. For example, an amino functionalized derivative of 1,4-benzenedicarboxylic acid is 2-amino-1,4-benzenedicarboxylic acid (BDC-NH2).

[0034]

[0037] The metal-organic structural composition of the present invention further comprises a plurality of organic ligands, each of which comprises a coordinating group and at least one functional group. Preferably, the organic ligands may contain at least two functional groups. The organic ligands are organic molecules comprising a coordinating group selected from one or more of carboxylates, phosphonates, phosphonites, sulfonates, and sulfinates. The organic ligands bind to a coordination site on the metal node via the coordinating group, thereby providing a ligand-modified MOF, also referred to as a modified MOF. Examples of organic ligands that bind to a non-restrictive coordination site via the coordinating group are shown in Figures 1 and 2. In Figure 1, the synthesized MOF-808 is modified with tartaric acid, which is bound to the Zr-OH group on the metal node via a carboxylate group on the tartaric acid. In Figure 2, the synthesized MOF-808 is modified with gallic acid, which is bonded to the Zr-OH group on the metal node via a carboxylate group on the gallic acid. Typically, each coordinating group on the organic ligand can be bonded to one coordination site on the MOF. Organic ligands can be present in amounts ranging from at least about 0.1 molar equivalents per metal node to a maximum of about 11 molar equivalents per metal node. Organic ligands can be present in amounts ranging from at least approximately 0.25 molar equivalents per metal node to a maximum of approximately 8 molar equivalents per metal node, or from at least approximately 0.5 molar equivalents per metal node to a maximum of approximately 6 molar equivalents per metal node, or from at least approximately 0.75 molar equivalents per metal node to a maximum of approximately 5 molar equivalents per metal node, or from at least approximately 1.0 molar equivalent per metal node to a maximum of approximately 5 molar equivalents of organic ligands per metal node, or in combination thereof.

[0035]

[0038] The organic ligand further comprises at least one functional group. The functional group may be selected from one or more of hydroxyl, amine, amino, carboxylate, sulfonate, and phosphonate or a combination thereof. If two or more functional groups are present on the organic ligand, at least two of the functional groups on the organic ligand may be in vicinal positions. The organic ligand may be aromatic. The organic ligand may be aliphatic. The desired organic ligand may vary depending on the properties of the desired adsorbent. For clarity, tartaric acid is aliphatic and contains a carboxylate coordinating group, two hydroxyl functional groups, and another carboxylate functional group. The hydroxyl group is in a vicinal position on the aliphatic backbone. For clarity, gallic acid is aromatic and contains one carboxylate coordinating group and three hydroxyl functional groups in vicinal positions relative to each other on a phenyl ring.

[0036]

[0039] In one embodiment, the organic ligand may be selected from one or more of the following: tyron (4,5-dihydroxy-1,3-benzenedisulfonic acid disodium), gallic acid, 5-sulfosalicylic acid, tartaric acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, citric acid, 3-amino-4-hydroxybenzenesulfonic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-aminoterephthalic acid, 2,3-dihydroterephthalic acid, 2,5-dihydroterephthalic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, and pyrimidine-4,6-dicarboxylic acid. In one embodiment, the organic ligand may be selected from one or more of tyron(4,5-dihydroxy-1,3-benzenedisulfonic acid disodium), gallic acid, 5-sulfosalicylic acid, tartaric acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, citric acid, and 3-amino-4-hydroxybenzenesulfonic acid.

[0037]

[0040] Another aspect of the MOF compositions disclosed herein is a metal (M') salt that interacts with the structure. The M' metal includes, but is not limited to, Li, Na, K, Mg, Ca, Sr, Ba, Ti, Sc, Y, Ti, Zr, Hf, V, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Zn, Cd, Al, Ga, In, Sn, Pb, and mixtures thereof. The M' metal exists as a metal salt and is impregnated on the surface of the MOF, into the pores of the MOF, or both. Thereafter, the metal salt is said to interact with the MOF structure to form the disclosed MOF composition. Without being constrained by theory, it is considered that the metal salt can bond to a functional group or a base of an organic ligand. In some embodiments, the metal salt can bond to a functional group at the vicinal position on a single organic ligand.

[0038]

[0041] The metal salt may be a Lewis acid. The metal salt may be selected from halides, sulfates, carbonates, acetates, carboxylates, sulfons, nitrates, or mixtures thereof. The metal salt may be selected from the group of metal acetates, metal nitrates, metal halides, or combinations thereof. The metal salt may be a metal halide or a combination of metal halides. The metal salts are Li(C2H3O2), Li(NO3), LiCl, Na(C2H3O2), Na(NO3), NaCl, K(C2H3O2), K(NO3), KCl, Mg(C2H3O2)2, Mg(NO3)2, MgCl2, Ca(C2H3O2)2, Ca(NO3)2, CaCl2, Ba(C2H3O2)2, Ba(NO3)2, BaCl2, Ti(O)(NO3)2, Ti(O)(Cl)2,Ti The metal salt may be selected from one or more of the following: Cl4, ScCl3, YCl3, Zr(O)(NO3)2, Zr(O)(Cl)2, ZrCl4, HfCl4, VOCl3, VCl3, FeCl3, CoCl2, Co(C2H3O2)2, NiCl2, Ni(C2H3O2)2, CuCl2, Cu(C2H3O2)2, FeCl3, AgCl, ZnCl2, AlCl3, GaCl3, and InCl3. The metal salt may be selected from one or more of the following: NiCl2, ZnCl2, CuCl2, and FeCl3.

[0039]

[0042] The M metal and the M' metal may be the same or different. It is preferable that the M' metal is different from the M metal. The amount of metal salt impregnated onto the MOF can vary greatly, but is typically about 1 wt% to about 70 wt.%, or about 5 wt.% to about 65 wt.%, or about 10 wt.% to about 60 wt.%, or about 15 wt.% to about 55 wt.%, or about 20 wt.% to about 50 wt.%, or about 25 wt.% to about 45 wt.% as metal.

[0040]

[0043] Another aspect of the present invention is a method for preparing an MOF composition, comprising the steps of: synthesizing a first metal-organic structure comprising a plurality of metal nodes, each having at least two coordination sites, wherein the metal nodes are connected by a plurality of organic linkers bonded at one or more coordination sites on the metal nodes to form the first metal-organic structure; contacting the first MOF with a first solution comprising an organic ligand and a ligand-incorporation solvent to form a ligand-modified MOF; and contacting the ligand-modified MOF with a second solution comprising a metal salt and a salt-impregnation solvent to form an MOF composition. The MOF composition is then separated from the solution and activated as necessary.

[0041]

[0044] The initial steps of the synthesis involve preparing the first MOF by known synthetic techniques in the literature, including but not limited to solvothermal methods. Typically, a solution of the desired metal node and organolinker is prepared. Metal M can be introduced as a metal salt. The salt may be a nitrate, halide, sulfate, carbonate, or the like. Specific examples of salts that can be used include, but are not limited to, zirconium oxynitrate, zirconium oxychloride, zirconium sulfate, hafnium oxynitrate, hafnium oxychloride, vanadium chloride, copper sulfide, iron chloride, zinc nitrate, or zinc carbonate.

[0042]

[0045] The linker used may be an organic linker, which is an organic molecule containing at least two groups that can bond to a metal node, such as a carboxylate functional group. The linker may be added in a molar ratio such that the desired molar ratio is reached in the initial MOF.

[0043]

[0046] Once the reaction mixture is formed, i.e., all reactants are solubilized, the reaction mixture is reacted at a temperature and time to form the desired first MOF. The reaction temperature may vary from about 50°C to about 200°C, or from about 75°C to about 125°C. The reaction mixture is reacted at the desired temperature for a time selected from about 1 hour to about 78 hours, or about 8 hours to about 48 hours, or about 12 hours to about 24 hours. Once the first MOF is formed, it can be isolated by means of filtration, centrifugation, or other means. The wet first MOF can be dried, if necessary, at room temperature, or at a temperature of about 40°C to about 250°C, or about 75°C to about 150°C. The time for drying the wet first MOF may vary substantially, but is typically about 2 hours to about 14 days, or about 8 hours to about 7 days, or about 2 days to about 7 days.

[0044]

[0047] The first isolated MOF can then be contacted with a first solution containing an organic ligand and a ligand-integrated solvent. The organic ligand can be dissolved in ligand-integrated solvents, including but not limited to alcohols, amides, organic acids, sulfoxides, sulfones, water, acetone, ethers, and mixtures thereof. Specific examples of suitable ligand-integrated solvents include, but are not limited to, MeOH, H2O, DMF, acetic acid, trifluoroacetic acid, formic acid, dimethylacetamide, sulfolane, propylene glycol, ethylene glycol, DMSO, HCl, and any combination thereof. Ligand-integrated solvents may have high dielectric constants. The relative permittivity of ligand-integrated solvents may be greater than about 15. The molar ratio of the organic ligand to the first MOF can also be adjusted to reach a specific molar ratio of the ligand to the MOF. The first solution can be contacted with the MOF for a period of about 1 minute to about 24 hours at a temperature of about room temperature to about 100°C or about room temperature to about 65°C. The product is a ligand-modified MOF, also referred to herein as a ligand-integrated MOF or “modified” MOF.

[0045]

[0048] In another embodiment of the one-pot preparation, the initial MOF may be functionalized with an organic ligand without being subjected to the initial sorting and drying steps.

[0049] Ligand-integrated MOFs can be dried or activated as needed. A wet ligand-integrated MOF can be dried at room temperature, or at temperatures of approximately 40°C to 250°C, approximately 75°C to 150°C, or approximately 100°C to 125°C. The drying time for a wet ligand-integrated MOF can vary substantially, but when carried out, is typically approximately 2 hours to 14 days, or approximately 8 hours to 7 days, or approximately 2 days to 7 days. If necessary, a dried MOF can be activated by passing hot N2 gas through the entire MOF, or by applying a vacuum with or without heating.

[0046]

[0050] The ligand-modified MOF can then be brought into contact with a second solution containing a metal salt and a salt impregnation solvent. The salt impregnation solvent has a high dielectric constant. The relative permittivity of the salt impregnation solvent may be greater than about 15. The salt impregnation solvent may include, but is not limited to, alcohols, amides, water, acetone, ethers, and mixtures thereof. In one embodiment, the salt impregnation solvent may be selected from H2O, aliphatic alcohols, acetone, DMF, and mixtures thereof. The molar ratio of the metal salt to the ligand-modified MOF can also be adjusted to achieve a specific molar ratio of salt to MOF. Contact of the ligand-modified MOF with the second solution is carried out by impregnation technique, thereby impregnating the MOF with the metal salt.

[0047]

[0051] In the first method of salt impregnation, the ligand-modified MOF is first activated, and then a volume of a second solution equal to the total pore volume of the MOF being used is added. This is usually referred to as incipient wetness impregnation. The second solution can be brought into contact with the MOF for about 1 minute to about 24 hours at a temperature of about room temperature to about 65°C. The impregnated MOF composition can then be activated. In one exemplary process of this first method, 5 g of activated MOF powder is placed in a 40 mL vial, and then a 2-6 M solution of a metal salt (ZnCl2, FeCl3, CuCl2, NiCl2, etc.) (e.g., MeOH, H2O, acetone, etc.) is slowly added, mixing until the solid is not dry after addition. Generally, a 4 M solution in methanol is suitable for impregnation. The volume of the added solution is generally the mass volume of the pores, which can be obtained by isotherm. The resulting solid can be dried overnight at 150°C in a vacuum oven or similar device.

[0048]

[0052] In the second salt-impregnation method, contact of the MOF with the second solution may include contact of the ligand-modified MOF with the second solution in either an activated or deactivated form, and the second solution may be recirculated or immersed without recirculation. The contact may vary substantially in duration, but is typically carried out for about 1 hour to about 5 days, or about 3 hours to about 2 days, or about 8 hours to about 24 hours. The salt-impregnated ligand-modified MOF can then be separated from the second solution by filtration, centrifugation, or otherwise. The salt-impregnated ligand-modified MOF can be dried or activated using the above conditions. In one exemplary process of this second method, 5 g of deactivated MOF powder is added to a 40 mL vial, and then a 2-6 M solution of a metal salt (ZnCl2, FeCl3, CuCl2, NiCl2, etc.) (e.g., MeOH, H2O, acetone, etc.) is added until the solid is completely submerged and overnight equilibrium is reached. Generally, a 4M solution in methanol is suitable for impregnation. The volume to be added is generally 1:5 (mass of MOF to volume of solution). The slurry can be filtered, and the resulting solid can be dried overnight in a vacuum oven at 150°C.

[0049]

[0053] Methods for producing MOF compositions may further include the formation of a product, with or without a binder. Materials containing MOF compositions may be formed into various shapes, as discussed below, although certain processes involve the preparation of granules. Usable binders include both organic and inorganic binders. Examples of inorganic binders include, but are not limited to, clays such as kaolin, attapulgite, and boehmite, alumina, silica, metal oxides, and mixtures thereof. Specific examples of organic binders include, but are not limited to, polymers such as polyvinylpyrrolidone (PVP), starch, gelatin, carbon, cellulose, cellulose derivatives, sucrose, polyethylene glycol, and mixtures thereof.

[0050]

[0054] Granulation can be performed before, during, or after salt impregnation. In one embodiment, a dry powder of an MOF composition containing coordinated ligands and metal salts is mixed with a binder, and the combination is thoroughly mixed. In another embodiment, the ligand-modified MOF and binder are first thoroughly mixed, and then a second solution containing the desired metal (M') salt is mixed with the MOF / binder mixture to provide a material containing MOF impregnated with the binder. In any embodiment of the method, the MOF-binder mixture may be mixed for about 1 to 5 minutes until granules of the desired size are obtained. It is understood that a wide range of sizes is always obtained, and therefore the granules need to be sizing, i.e., sieved, to isolate granules of the desired size or size range. The size range of the granules will depend on the specific use of the final composition containing the MOF and will depend on various parameters such as pressure drop, packing material density, and others. Granules are desired that may have an average diameter of approximately 1680 microns (12 mesh) to approximately 250 microns (60 mesh), or approximately 1190 microns (16 mesh) to approximately 841 microns (20 mesh), or approximately 841 microns (20 mesh) to approximately 400 microns (40 mesh), or approximately 595 microns (30 mesh) to approximately 297 microns (50 mesh). The average diameter refers to the average diameter assuming an approximate spherical shape. This does not mean that the granules are actually spherical, but that the granules will pass through a sieve of a given diameter. Once granules of the desired size are obtained, the MOF composition is activated by drying the granules under vacuum at a temperature of approximately 50°C to approximately 250°C or approximately 100°C to approximately 250°C for the time required to reach a pressure of approximately 13.3 Pa (0.1 Torre). The composition can also be activated by heating it under a flow of hot gas, such as hot nitrogen.

[0051]

[0055] The MOF compositions disclosed herein can be characterized by the following properties: One property is that the static ammonia capacity measured at 1333 Pa (10 Torre) and 25°C may be at least 4 mmol / g, or at least 6 mmol / g, or at least 8 mmol / g, or at least 10 mmol / g, or at least 12 mmol / g, or at least 15 mmol / g, or at least 20 mmol / g, or at least 25 mmol / g. Another property of the MOF composition is that the Brunauer-Emmett Teller (BET) surface area, measured by N2 adsorption, may be at least 200, or at least 400, or at least 700, or at least 1200, or at least 2000 m². 2 / g is also acceptable.

[0052]

[0056] A material comprising the MOF composition disclosed herein can be used to capture a target chemical substance in a fluid flow, wherein a solid adsorbent composition comprising the MOF composition disclosed herein is brought into contact with a fluid flow containing the target chemical substance, and at least a portion of the target chemical substance is adsorbed by the solid adsorbent. The fluid flow may be an airflow, wherein a solid adsorbent composition comprising the MOF composition is brought into contact with an airflow containing the target chemical substance, and at least a portion of the target chemical substance is adsorbed by the solid adsorbent.

[0053]

[0057] Examples of airflows that may need to be purified include, but are not limited to, airflows, industrial airflows, off-gas airflows, or contaminated airflows. In one embodiment, the airflow is an airflow. The MOF compositions disclosed herein can be prepared with selected metal nodes, organolinkers, organic ligands, and metal salts to be adapted for the removal of specific acidic and / or basic target chemicals from airflows. The target chemicals removed by the MOF compositions of this disclosure may include toxic industrial chemicals or chemical weapons (CWAs) or combinations thereof. Target chemicals that can be removed by MOF compositions include, but are not limited to, ammonia, bromine, boron tribromide, bromine chloride, boron trichloride, bromine trifluoride, bromine pentafluoride, carbonyl fluoride, chlorine, chlorine pentafluoride, chlorine trifluoride, sulfonic acid chloride, dichlorosilane, ethylphosphonitric acid dichloride, fluorine, hydrogen bromide, hydrogen chloride, hydrogen cyanide, hydrogen fluoride, hydrogen iodide, nitric acid, nitrogen dioxide, dinitrogen tetroxide, nitrogen trioxide, phosgene, phosphorus trichloride, silicon tetrafluoride, sulfuric acid, sulfuryl chloride, titanium tetrachloride, tungsten hexafluoride, and mixtures thereof. In some embodiments, the MOF compositions disclosed herein can remove both basic and acidic target chemicals, such as TIC in a gas stream.

[0054]

[0058] In one embodiment, the target chemical substance removed by adsorption may include ammonia. Ammonia in the airflow can be present at concentrations ranging from about 1 ppb to about 10%. The ammonia concentration in the airflow can range from about 1 ppb, or about 10 ppb, or about 100 ppb, or about 1 ppm, or about 10 ppm, or about 100 ppm, or more than about 1%, and can be about 10 wt%, or about 5 wt%, or about 1 wt%, or less than about 100 ppm.

[0055]

[0059] The amount of target chemicals (acidic or basic) that the MOF composition can remove may be at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at least 99% of the target chemicals. In one embodiment, the airflow is an airflow, the target chemicals are NO2 and / or ammonia, and the MOF composition removes at least 80% of the NO2 or at least 80% of the ammonia in the airflow. In another embodiment, a container having an inlet and outlet is filled with a material containing the MOF composition, through which an airflow passes, thereby substantially removing at least one basic target chemical, or at least one acidic target chemical, or at least one basic target chemical and one acidic target chemical from the flow. To achieve the desired removal rate, the airflow can flow through the MOF composition at a speed of approximately 0.1 L / min to approximately 500 L / min, or approximately 10 L / min to approximately 400 L / min, or approximately 30 L / min to approximately 200 L / min, or approximately 50 L / min to approximately 120 L / min.

[0056]

[0060] While materials containing MOF compositions can be used in powder form, it may be advantageous to form them into objects of various shapes, such as pellets, spheres, discs, monoliths, irregularly shaped particles, and extruded materials. Methods for forming these types of shapes are well known in the art. Specific methods for forming granular materials are described above. Materials containing MOF compositions can be formed into various shapes, either alone or by adding a binder. When selecting a binder, it is important to select one that does not adversely affect the surface area and adsorption capacity once the desired shape of the object is formed.

[0057]

[0061] The forming process typically involves preparing a thick paste-like material by mixing the MOF composition with a solvent or a binder containing a solvent. Once formed, the paste-like material can be extruded through a mold having holes of approximately 1–4 mm to form extruded objects of various lengths, e.g., 2–50 mm. The paste, or even the powder itself, can be compressed under high pressure to form pellets or pills. Other means of forming the shape include press forming, metal forming, pelletizing, granulation, extrusion, rolling, and spheroidizing.

[0058]

[0062] In yet another embodiment, MOF compositions can be deposited on articles such as monoliths, spherical supports, ceramic foams, glass fibers, woven fabrics, nonwoven fabrics, membranes, pellets, extrudes, irregularly shaped particles, and mixtures thereof, with or without a binder. If the desired article is a monolith, spherical support, ceramic foam, pellets, extrudes, or irregularly shaped particles, a slurry of the composition containing the MOF composition is prepared and deposited on the article by means such as dipping, spray drying, or otherwise, followed by drying and, if necessary, firing. MOF compositions can be deposited or dispersed on fabrics (woven and nonwoven) or polymers by techniques such as electrospinning, direct crystal growth, and layer-by-layer deposition.

[0059]

[0063] An article containing a material comprising an MOF composition, as described in the preceding paragraph, can be used to purify a stream of air or other gas containing a target chemical substance. The stream of air or other gas can flow through an article, such as a monolith, foam, membrane, or fabric, through which the MOF composition adsorbs at least a portion of at least one target chemical substance. Articles containing MOF compositions can also be placed in various types of rigid containers. For example, an extruded or pill-shaped object or sphere can be housed in a bed through which a stream of air or other gas flows. The bed can be placed in various types of housings, such as a filter canister with an inlet and an outlet. Fabrics (both woven and nonwoven) can also be formed into filters, such as pleated filters, which can also be housed in a rigid container, such as a cartridge, through which a stream to be treated flows. In one particular embodiment, the cartridge is part of a face mask. Pleated filters can also be supported in frames of various shapes and sizes, through which an airflow flows. The frame can be made from various types of materials, including but not limited to metal, wood, and plastic. Fiberglass can be formed into glass wool and housed in a rigid filter frame.

[0060]

[0064] Articles comprising materials containing the MOF compositions disclosed herein may further take the form of assemblies or apparatus comprising multiple layers or mixtures of non-layered particles through which airflow, e.g., air currents, flow. In certain embodiments, the first layer in contact with the airflow is a material containing the MOF composition, and the second layer contains activated carbon. Additional layers, e.g., a layer of hopkalite, may be added from time to time. For example, layers of two different MOF compositions may be used. Alternatively, two or more MOF compositions may be mixed to form one layer. These layers may be placed on a floor, which may be housed in a rigid structure such as a canister, e.g., or in a larger container, when a large airflow, e.g., airflow entering a commercial building, is being purified. As described above, the MOF compositions in the layers may be in the form of powders, and the materials containing the MOF compositions may be any of the shapes and forms described above.

[0061]

[0065] The activated carbon that can be used as the layer described above is a highly porous, high-surface-area adsorbent material, primarily having an amorphous structure. These are mainly composed of aromatically arranged carbon atoms linked by random crosslinking. The degree of order varies depending on the starting material and thermal history. Graphite plateslets in steam-activated coal are somewhat ordered, while more amorphous aromatic structures are found in chemically activated wood. Random bonding creates a highly porous structure with numerous cracks, gaps, and voids between the carbon layers. Activated carbon may be in the form of powder (PAC), granules (GAC), or extruded material (EAC). All three forms are available in a wide range of particle sizes.

[0062]

[0066] When a material containing an MOF composition and activated carbon is deposited on a fabric (woven or nonwoven), the fabric can be arranged as a layer for a face mask or other filtration device.

[0067] A pleated sheet can be formed, comprising layers of a composition containing activated carbon and MOF. The pleated sheet can be formed in various ways, such as in a filter canister, or housed in a rigid container such as a frame made of various materials such as plastic, wood, metal, cardboard, or the like. [Examples]

[0063] Example 1 Synthesis of Zr (BTC)

[0068] Zr(BTC), also known as MOF-808, was prepared using a scaled-up version of a literature procedure (reference: Chem.Mater.2021, 33, 4, 1471-1476). Generally, the procedure involved adding BTC linker (21.7 g, 0.33 equivalents) to a 2 L flask using an overhead stirrer. Water (330 mL), followed by acetic acid (880 mL), was added to the flask. The solution was heated to approximately 100°C, ZrOCl2·8H2O (117 g, 1 equivalent) was added, and the mixture was reacted for 18 hours to provide the MOF. The MOF powder was isolated by filtration or centrifugation and washed with water and methanol. This material (Example 10) was used to produce Control 1 by proceeding to Example 2 or by granulation in Example 3.

[0064] Example 2 Incorporation of organic ligands

[0069] The MOF (60 g, 43 mmol) from Example 1, 10 molar equivalents of an organic ligand, and methanol (800 mL) were placed in a 1 L round-bottom flask using a stirring rod. The reaction was stirred overnight at 60°C. The reaction product was filtered and washed three times with methanol. The materials were used without further purification. The ligand-integrated MOFs shown in Table 1 were prepared using this method. The characteristics of the ligand equivalents were evaluated by NMR as described in Example 8.

[0065] Example 3 Granulation

[0070] 150 g of inactivated MOF (unmodified according to Example 1, or ligand-modified according to Example 2) was added to a pan mixer along with a colloidal silica solution (5 wt% SiO2, dry basis), and the mixture was thoroughly mixed. Water was added, and mixing was continued until granules were formed. The granules were sieved to separate granules of the desired size. The resulting solid was activated in a vacuum oven at 150°C until a dynamic pressure (less than 13.3 Pa (0.1 Torre)) was reached.

[0066]

[0071] Control 1 is Example 10 of this specification, which was granulated according to the procedure of Example 3, and Examples 3A to 3E are Examples 2A to 2E, which were granulated according to the procedure of Example 3.

[0067] [Table 1]

[0068] Example 4 Impregnation of granulated ligand-modified MOFs

[0072] For each of the activated granulated MOFs synthesized in Examples 3A to 3E above, 5 g of the granulated product was added to a 40 mL vial. A metal salt solution in methanol was added to the granulated product until the solid was completely submerged, and the mixture was kept in equilibrium overnight. The volume of added solution was generally in a 1:5 ratio of MOF mass to solution volume. The slurry was filtered, and the resulting solid was dried overnight in a vacuum oven at 150°C.

[0069]

[0073] Control 2: Control 1 was impregnated with a 2.5 M ZnCl2 solution.

[0074] Control 3: Control 1 was impregnated with a 4.0 M ZnCl2 solution.

[0075] Control 4: Control 1 was impregnated with a 4.125 M MgCl2 solution.

[0070]

[0076] Control 5: Control 1 was impregnated with a 5.0 M FeCl3 solution.

[0077] Control 6: Control 1 was impregnated with a 4.125 M CuCl2 solution.

[0071]

[0078] Control 7: Control 1 was impregnated with a 4.125 M NiCl2 solution.

[0079] Example 4A1: The MOF from Example 3A was impregnated with a 2.5 M ZnCl2 solution.

[0072]

[0080] Example 4A2: The MOF from Example 3A was impregnated with a 4.0 M CuCl2 solution.

[0081] Example 4A3: The MOF from Example 3A was impregnated with a 4.0 M FeCl3 solution.

[0073]

[0082] Example 4A4: The MOF from Example 3A was impregnated with a 4.0 M ZnCl2 solution.

[0083] Example 4A5: The MOF from Example 3A was impregnated with a 4.125 M MgCl2 solution.

[0074]

[0084] Example 4A6: The MOF from Example 3A was impregnated with a 5.0 M FeCl3 solution.

[0085] Example 4A7: The MOF from Example 3A was impregnated with a 4.125 M CuCl2 solution.

[0075]

[0086] Example 4A8: The MOF from Example 3A was impregnated with a 4.125 M NiCl2 solution.

[0087] Example 4B1: The MOF from Example 3B was impregnated with a 4.0 M ZnCl2 solution.

[0076]

[0088] Example 4B2: The MOF from Example 3B was impregnated with a 4.125 M MgCl2 solution.

[0089] Example 4B3: The MOF from Example 3B was impregnated with a 5.0 M FeCl3 solution.

[0077]

[0090] Example 4B4: The MOF from Example 3B was impregnated with a 4.125 M CuCl2 solution.

[0091] Example 4B5: The MOF from Example 3B was impregnated with a 4.125 M NiCl2 solution.

[0078]

[0092] Example 4C1: The MOF from Example 3C was impregnated with a 4.0 M ZnCl2 solution.

[0093] Example 4C2: The MOF from Example 3C was impregnated with a 4.125 M MgCl2 solution.

[0079]

[0094] Example 4C3: The MOF from Example 3C was impregnated with a 4.125 M CuCl2 solution.

[0095] Example 4C4: The MOF from Example 3C was impregnated with a 4.125 M NiCl2 solution.

[0080]

[0096] Example 4D1: The MOF from Example 3D was impregnated with a 4.0 M ZnCl2 solution.

[0097] Example 4D2: The MOF from Example 3D was impregnated with a 4.125 M MgCl2 solution.

[0081]

[0098] Example 4D3: The MOF from Example 3D was impregnated with a 5.0 M FeCl3 solution.

[0099] Example 4D4: The MOF from Example 3D was impregnated with a 4.125 M CuCl2 solution.

[0082] [000100] Example 4D5: The MOF from Example 3D was impregnated with a 4.125 M NiCl2 solution. [000101] Example 4E1: The MOF of Example 3E was impregnated with a 4.0 M CuCl2 solution.

[0083] [000102] Example 4E2: The MOF of Example 3E was impregnated with a 4.0 M FeCl3 solution. [000103] Example 4E3: The MOF of Example 3E was impregnated with a 4.0 M ZnCl2 solution.

[0084] [000104] Example 4E4: The MOF of Example 3E was impregnated with a 4.125 M MgCl2 solution. [000105] Example 4E5: The MOF of Example 3E was impregnated with a 5.0 M FeCl3 solution.

[0085] [000106] Example 4E6: The MOF of Example 3E was impregnated with a 4.125 M CuCl2 solution. [000107] Example 4E7: The MOF of Example 3E was impregnated with a 4.125 M NiCl2 solution.

[0086] Example 5 Synthesis of ligand-modified Zr(BDC-NH2) [000108] Step 1. Zr(BDC-NH2), also known as UiO-66-NH2, was prepared using the procedure described in the literature. Generally, the procedure involved filling a 2 L flask with BDC-NH2 using an overhead stirrer. DMF (440 mL), followed by formic acid (440 mL), was added to the flask. The solution was heated to a temperature of approximately 90°C, ZrOCl2 was added, and the solution was reacted for 18 hours to provide the MOF. The MOF powder was isolated and then washed with DMF and acetone.

[0087] [000109] Step 2. The MOF obtained in Step 1 was stirred in 1N HCl (2L) at 60°C for 12 hours. The resulting solid was washed three times with water. This material (Example 50) was then used in Step 3, or granulated in Example 6 to produce Control 8.

[0088] [000110] Step 3. The HCl-treated MOF (50 g, 28.5 mmol), 10 molar equivalents of the organic ligand, and methanol (800 mL) were placed in a 1 L round-bottom flask using a stirring rod. The reaction was stirred overnight at 60°C. The reaction was filtered and washed three times with methanol. The characteristics of the ligand equivalent were evaluated by NMR as described in Example 8.

[0089] Example 6 Granulation [000111] 150 g of inactivated MOF (unmodified after step 2 in Example 5, or ligand-modified after step 3 in Example 5) was added to a pan mixer along with colloidal silica solution (5 wt% SiO2, dry basis), and the mixture was thoroughly mixed. Water was added, and mixing was continued until granules were formed. The granules were sieved to separate granules of the desired size.

[0090] [000112] Control 8 is Example 50 of this specification, which was granulated according to the procedure of Example 6, and Examples 6A to 6D are Examples 5A to 5D, which were granulated according to the procedure of Example 6.

[0091] [Table 2]

[0092] Example 7 metal salt impregnation [000113] For each of the activated granulated MOFs of Examples 6A to 6D synthesized above, 5 g of the granulated product was added to a 40 mL vial. A 1.25 to 1.5 M aqueous ZnCl2 solution was added to the granulated product until the solid was completely submerged, and the mixture was kept in equilibrium overnight. The volume added was generally in a 1:5 ratio of MOF mass to solution volume. The granules were filtered, and the resulting solid was dried overnight in a vacuum oven at 100°C until a dynamic pressure (less than 13.3 Pa (0.1 Torre)) was reached.

[0093] [000114] Control 9: Control 8 was impregnated with a 1.5 M ZnCl2 solution. [000115] Control 10: Control 8 was impregnated with a 1.5 M MgCl2 solution.

[0094] [000116] Control 11: Control 8 was impregnated with a 1.5 M FeCl3 solution. [000117] Control 12: Control 8 was impregnated with a 1.5 M CuCl2 solution.

[0095] [000118] Control 13: Control 8 was impregnated with a 1.5 M NiCl2 solution. [000119] Example 7A1: The MOF of Example 6A was impregnated with a 1.5 M ZnCl2 solution.

[0096] [000120] Example 7A2: The MOF of Example 6A was impregnated with a 1.5 M MgCl2 solution. [000121] Example 7A3: The MOF of Example 6A was impregnated with a 1.5 M FeCl3 solution.

[0097] [000122] Example 7A4: The MOF of Example 6A was impregnated with a 1.5 M CuCl2 solution. [000123] Example 7A5: The MOF of Example 6A was impregnated with a 1.5 M NiCl2 solution.

[0098] [000124] Example 7B1: The MOF of Example 6B was impregnated with a 1.5 M ZnCl2 solution. [000125] Example 7B2: The MOF from Example 6B was impregnated with a 1.5 M MgCl2 solution.

[0099] [000126] Example 7B3: The MOF from Example 6B was impregnated with a 1.5 M FeCl3 solution. [000127] Example 7B4: The MOF from Example 6B was impregnated with a 1.5 M CuCl2 solution.

[0100] [000128] Example 7B5: The MOF from Example 6B was impregnated with a 1.5 M NiCl2 solution. [000129] Example 7C1: The MOF of Example 6C was impregnated with a 1.5 M ZnCl2 solution.

[0101] [000130] Example 7D1: The MOF of Example 6D was impregnated with a 1.25 M ZnCl2 solution. [000131] Example 7D2: The MOF of Example 6D was impregnated with a 1.5 M MgCl2 solution.

[0102] [000132] Example 7D3: The MOF of Example 6D was impregnated with a 1.5 M FeCl3 solution. [000133] Example 7D4: The MOF of Example 6D was impregnated with a 1.5 M CuCl2 solution.

[0103] [000134] Example 7D5: The MOF of Example 6D was impregnated with a 1.5 M NiCl2 solution. Example 8 Characterization method and breakthrough test [000135] Nuclear magnetic resonance (NMR) samples were prepared using standard literature techniques. Ligand-modified MOFs were immersed in 1 M NaOH in D2O for 10 minutes. Ligands were measured using quantitative NMR against the linker. The ratio of ligands to nodes was determined using the ratio of the theoretical linker to zirconium in the corresponding MOF (6 Zr per node for Zr(BTC) and 12 per node for Zr(BDC-NH2)).

[0104] [000136] All ammonia adsorption and desorption measurements were performed at 25°C using a Micromeritics 3Flex Surface Characterization Analyzer (Micromeritics, Norcross, Ga.), dosing to absolute pressure and using a 3-second equilibrium interval.

[0105] [000137] In the following examples, all N2 gas adsorption / desorption measurements were performed at -196.15°C (77K) using a Micromeritics Tristar II 3020 system (Micromeritics, Norcross, Ga.) unless otherwise specified. Samples between 75 and 200 mg were used for each measurement. The specific surface area for N2 was calculated using the Brunauer-Emmett-Teller (BET) model with a P / P0 in the range of greater than 0.005 and less than 0.05. N2 intake was measured with a P / P0 of 0.9, where P / P0 is the pressure measured in comparison to atmospheric pressure.

[0106] Breakthrough test [000138] A fixed volume of the material from the above example (1.0 cm in a 40 mm tube) was packed into the breakthrough system. After nitrogen purging, a flow containing ammonia in the air was introduced and passed through the MOF at 12.4 cm / second. The breakthrough time was recorded when the outlet concentration was measured to be 5% of the original airflow. Sample details and results are specified in Table 3. Data are reported in concentration time (Ct), which is measured by the concentration of the gas before breakthrough (e.g., NH3) and the length of exposure (in minutes).

[0107] [000139] The above results show that a composition comprising a MOF comprising a plurality of metal nodes each having at least two coordination sites, a plurality of organic linkers, wherein the metal nodes are connected by organic linkers bonded at one or more coordination sites on the metal nodes to form a metal-organic structure, a plurality of organic ligands each having a coordinating group bonded to the coordination sites of the metal nodes, each organic ligand having at least one functional group, and a metal salt that interacts with the structure is very effective in removing target chemicals from the airflow.

[0108] [000140] Specifically, for Zr(BTC) modified with gallic acid, each of item numbers 9-16 in Table 3, which includes the impregnated metal salt, will be found to have a higher ammonia intake and a longer ammonia breakthrough time than item number 8 in Table 3, which is the unimpregnated version. Comparing item numbers 17-22 for Zr(BTC) modified with citric acid, item numbers 18-22, which include the impregnated metal salt, will have a higher ammonia intake and a longer ammonia breakthrough time than item number 17 in Table 3, which is the unimpregnated version. Comparing item numbers 23-27 for Zr(BTC) modified with 5-sulfosalicylic acid, item numbers 24-27, which include the impregnated metal salt, will have a higher ammonia intake and a longer ammonia breakthrough time than item number 23 in Table 3, which is the unimpregnated version.

[0109] [Table 3-1]

[0110] [Table 3-2]

[0111] [Table 3-3]

[0112] [Table 3-4]

[0113]

[0001] Comparing items 28-33 for Zr(BTC) modified by Tyrone, items 29-33, which contain impregnated metal salts, have higher ammonia uptake and longer ammonia breakthrough times than item 28 in Table 3, which is the unimpregnated version.

[0114]

[0002] Comparing items 34-41 for Zr(BTC) modified with tartaric acid, each of items 35-41 containing impregnated metal salts has a higher ammonia uptake and a longer ammonia breakthrough time than item 34 in Table 3, which is the unimpregnated version. The same trend is observed for the MOF of Zr(BDC-NH2). Comparing items 48-53 for Zr(BDC-NH2) modified with citrate, items 49-53 containing impregnated metal salts have a higher ammonia uptake and a longer ammonia breakthrough time than item 48 in Table 3, which is the unimpregnated version. Comparing items 54-59 for Zr(BDC-NH2) modified with gallic acid, items 55-59 containing impregnated metal salts have a higher ammonia uptake and a longer ammonia breakthrough time than item 54 in Table 3, which is the unimpregnated version. Comparing items 61–66 for Zr(BDC-NH2) modified with 3-amino-4-hydroxybenzenesulfonic acid, items 62–66, which contain the impregnated metal salt, exhibit higher ammonia uptake and longer ammonia breakthrough times than item 61 in Table 3, which is the unimpregnated version. The data demonstrate an unexpectedly high synergistic effect on ammonia adsorption between the MOF, ligand, and metal salt, as measured by both ammonia uptake and breakthrough time.

[0115]

[0003] While the above refers to specific embodiments, it will be understood that the present invention is not limited thereto. Those skilled in the art will notice that various modifications may be made to the disclosed embodiments, and that such modifications are intended to be within the scope of the present invention.

[0116] Specific Embodiments

[0004] Specific embodiments are described below, but it should be understood that the following description is not intended to limit the scope of the prior description and the appended claims, but rather to be illustrative.

[0117]

[0005] A first embodiment of the present invention is a metal-organic structure (MOF) composition comprising a plurality of metal nodes, each having at least two coordination sites, a plurality of organic linkers, the metal nodes being connected by organic linkers bonded at one or more coordination sites on the metal nodes to form a metal-organic structure, a plurality of organic ligands each having a coordination group bonded to the coordination sites of the metal nodes, each organic ligand having at least one functional group, and a metal salt that interacts with the structure. Embodiments of the present invention are any or all of the embodiments described in the preceding paragraphs to the first embodiment of this paragraph, wherein the coordination groups of the organic ligands are selected from one or more of carboxylates, phosphonates, phosphonites, sulfonates, and sulfinates. Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein at least one functional group on the organic ligand is selected from one or more of hydroxyl, amine, amino, carboxylate, sulfonate, and phosphonate. Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein at least one functional group is in the vicinal position on the organic ligand. Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein the organic ligand is aromatic. Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein the organic ligand is aliphatic. Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein a metal salt interacts with at least one functional group on the organic ligand.Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein at least one functional group interacting with a metal salt is located in the vicinal position on the organic ligand. Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein a plurality of metal nodes comprise a metal oxocluster containing at least two metal atoms M selected from Zr, V, Al, Fe, Cr, Co, Ti, Hf, Cu, Zn, Ni, In, Ce, and mixtures thereof. Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein at least some of the metal nodes comprise zirconium. Embodiments of the present invention are one or all of the embodiments described in the preceding paragraph to the second embodiment of this paragraph, wherein the MOF has a static adsorption capacity for at least 4 mmol / g of ammonia, as measured at 1.33 kPa (10 Torr) at 25°C. Embodiments of the present invention are one or all of the embodiments described in the preceding paragraph to the second embodiment of this paragraph, wherein the metal salt is selected from the group consisting of metal acetates, metal nitrates, metal halides, or combinations thereof. Embodiments of the present invention are one or all of the embodiments described in the preceding paragraph to the second embodiment of this paragraph, wherein the metal salt is a metal halide or a combination of metal halides. Embodiments of the present invention are one or all of the embodiments described in the preceding paragraph to the second embodiment of this paragraph, wherein the metal salt is selected from one or more of NiCl2, ZnCl2, CuCl2, and FeCl3. Embodiments of the present invention are any or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein a plurality of organic linkers are selected from the group consisting of 1,3,5-benzenetricarboxylic acid, 1,4-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, functionalized derivatives thereof, and combinations thereof.

[0118]

[0006] A second embodiment of the present invention is a method for producing a composition containing an MOF, comprising the steps of: synthesizing a metal-organic structure comprising a plurality of metal nodes, each having at least two coordination sites, wherein the metal nodes are connected by a plurality of organic linkers bonded at one or more coordination sites on the metal nodes to form a metal-organic structure; contacting the MOF with a first solution comprising an organic ligand and a ligand-integrating solvent; contacting the ligand-modified MOF with a second solution comprising a metal salt and a salt-impregnation solvent; separating the composition containing the MOF from the solution; and activating the composition containing the MOF.

[0119]

[0007] A third embodiment of the present invention is a method for capturing a target chemical substance in an airflow, comprising the steps of preparing a solid adsorbent comprising a composition comprising an MOF, and bringing an airflow containing the target chemical substance into contact with the solid adsorbent, thereby adsorbing at least a portion of the target chemical substance by the solid adsorbent. An embodiment of the present invention is one or all of the preceding embodiments to the second embodiment of this paragraph, wherein the target chemical substance is ammonia. An embodiment of the present invention is one or all of the preceding embodiments to the second embodiment of this paragraph, wherein the ammonia in the airflow is present at a concentration of about 1 ppb to about 10%. An embodiment of the present invention is one or all of the preceding embodiments to the second embodiment of this paragraph, wherein the MOF is formed in a shape selected from the group consisting of pellets, granules, spheres, discs, monoliths, irregularly shaped particles, extruded products, and mixtures thereof. Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein the MOF is deposited on a solid support selected from monoliths, spherical supports, ceramic foams, glass fibers, woven fabrics, nonwoven fabrics, membranes, pellets, extruded materials, irregularly shaped particles, and mixtures thereof. Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein the solid support is a woven fabric or a nonwoven fabric. Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein the nonwoven fabric is part of a facial mask. Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein the organic ligand is present as at least 1 molar equivalent of ligand per two metal nodes.Embodiments of the present invention are one, any, or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein the organic ligand is tyron(4,5-dihydroxy-1,3-benzenedisulfonic acid disodium), gallic acid, 5-sulfosalicylic acid, tartaric acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, citric acid, and 3-amino-4-hydroxybenzenesulfonic acid, 3,4-dihydroxybenzoic acid, 3, Embodiments include one or more selected from 5-dihydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-aminoterephthalic acid, 2,3-dihydroterephthalic acid, 2,5-dihydroterephthalic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, and pyrimidine-4,6-dicarboxylic acid. Embodiments of the present invention include one or all of the preceding embodiments to the second embodiment of this paragraph, further comprising the step of forming a ligand-modified MOF with or without a binder. Embodiments of the present invention are any or all of the embodiments described in the preceding paragraph to the second embodiment of this paragraph, wherein the ligand-integrated solvent is selected from MeOH, H2O, DMF, acetic acid, trifluoroacetic acid, formic acid, dimethylacetamide, sulfolane, propylene glycol, ethylene glycol, DMSO, HCl, and combinations thereof. Embodiments of the present invention are any or all of the embodiments described in the preceding paragraph to the second embodiment of this paragraph, wherein the salt impregnation solvent is selected from H2O, aliphatic alcohols, acetone, DMF, and combinations thereof. Embodiments of the present invention are any or all of the embodiments described in the preceding paragraph to the second embodiment of this paragraph, wherein the gas stream further comprises nitrogen dioxide, sulfur dioxide, hydrogen sulfide, carbon monoxide, hydrogen cyanide, carbon dioxide, and / or chlorine.Embodiments of the present invention are one or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein the concentration of nitrogen dioxide, sulfur dioxide, hydrogen sulfide, carbon monoxide, hydrogen cyanide, carbon dioxide, and / or chlorine is about 1 ppb to about 10%. Embodiments of the present invention are one or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein the method captures more than 50% of the target chemical substance, including the airflow. Embodiments of the present invention are one or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein the method captures more than 60% of the target chemical substance, including the airflow. Embodiments of the present invention are one or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein the method captures more than 70% of the target chemical substance, including the airflow. Embodiments of the present invention are any or all of the embodiments described in the preceding paragraph to the second embodiment described in this paragraph, wherein the target chemical substance is selected from the group consisting of X, Y, Z and combinations thereof.

[0120]

[0008] A fourth embodiment of the present invention is an article comprising a composition containing the MOF described in the first embodiment of the present invention.

[0009] Without further detail, it is expected that those skilled in the art will be able to make full use of the present invention, readily grasp the essential features of the invention without departing from its spirit and scope, and make various changes and modifications to the present invention to adapt it to various uses and conditions. Accordingly, the preferred specific embodiments described herein are merely illustrative and are not intended to limit the remainder of this disclosure, but rather to cover various modifications and adjustments of equivalents that fall within the scope of the appended claims.

[0121]

[0010] In the above, unless otherwise specified, all temperatures are given in Celsius, and all parts and percentages are given in weight.

Claims

1. A metal-organic frame (MOF) composition, Multiple metal nodes, each having at least two coordination sites, A plurality of organic linkers, wherein the metal node is connected by the organic linkers bonded at one or more coordination sites on the metal node to form a metal-organic structure. A plurality of organic ligands, each containing a coordinating group bonded to the coordination site of a metal node, wherein each of the organic ligands has at least one functional group, and Metal salts that interact with the aforementioned structure A metal-organic frame (MOF) composition containing the above.

2. The MOF composition according to claim 1, wherein the coordinating group of the organic ligand is selected from one or more of carboxylates, phosphonates, phosphonites, sulfonates, and sulfinates.

3. The MOF composition according to claim 1, wherein the at least one functional group on the organic ligand is selected from one or more of hydroxyl, amine, amino, carboxylate, sulfonate, and phosphonate.

4. The MOF composition according to claim 1, wherein the organic ligand has at least two functional groups, and the functional groups are in the vicinal position on the organic ligand.

5. The MOF composition according to claim 1, wherein the organic ligand is aromatic.

6. The MOF composition according to claim 1, wherein the organic ligand is aliphatic.

7. The MOF composition according to claim 1, wherein the metal salt interacts with the at least one functional group on the organic ligand.

8. The MOF composition according to claim 4, wherein the metal salt interacts with the at least two functional groups on the organic ligand.

9. The MOF composition according to claim 1, wherein the plurality of metal nodes comprises a metal oxocluster containing at least two metal atoms M selected from Zr, V, Al, Fe, Cr, Co, Ti, Hf, Cu, Zn, Ni, In, Ce, and any two or more mixtures thereof.

10. The MOF composition according to claim 9, wherein at least some of the metal nodes include zirconium.

11. The MOF composition according to claim 1, having a static adsorption capacity for at least 4 mmol / g of ammonia, as measured at 1.33 kPa (10 Torr) at 25°C.

12. The MOF composition according to claim 1, wherein the metal salt is selected from the group consisting of a metal acetate, a metal nitrate, a metal halide, or any two or more combinations thereof.

13. The MOF composition according to claim 1, wherein the metal salt is a metal halide or a combination of metal halides.

14. The aforementioned metal salt is NiCl ２ ZnCl ２ CuCl ２ and FeCl ３ The MOF composition according to claim 1, selected from one or more of the following.

15. The MOF composition according to claim 1, wherein the plurality of organic linkers are selected from the group consisting of 1,3,5-benzenetricarboxylic acid, 1,4-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, functionalized derivatives thereof, and any two or more combinations thereof.

16. A method for producing a composition containing the MOF described in claim 1, A step of synthesizing a metal-organic structure comprising a plurality of metal nodes, each having at least two coordination sites, wherein the metal nodes are connected by a plurality of organic linkers bonded at one or more coordination sites on the metal nodes to form the first metal-organic structure. The first MOF is brought into contact with a first solution containing an organic ligand and a ligand-integrating solvent to form a ligand-modified MOF. The steps include contacting the ligand-modified MOF with a second solution containing a metal salt and a salt impregnation solvent, The steps of separating the composition containing the MOF from the solution, step of activating the composition containing the MOF Methods that include...

17. A method for capturing target chemical substances in an airflow, A step of preparing a solid adsorbent containing the MOF composition described in claim 1, and Step of bringing an airflow containing the target chemical substance into contact with the solid adsorbent. A method comprising a solid adsorbent wherein at least a portion of the target chemical substance is adsorbed by the solid adsorbent.

18. The method according to claim 17, wherein the target chemical substance is ammonia.

19. The method according to claim 17, wherein the ammonia in the airflow is present at a concentration of about 1 ppb to about 10%.

20. The method according to claim 17, wherein the solid adsorbent is formed in a shape selected from the group consisting of pellets, granules, spheres, discs, monoliths, irregularly shaped particles, extruded products, and mixtures thereof.

21. The method according to claim 17, wherein the solid adsorbent is deposited on a solid support selected from a monolith, a spherical support, a ceramic foam, glass fiber, a woven fabric, a nonwoven fabric, a membrane, a pellet, an extruded product, irregularly shaped particles, and a mixture thereof.

22. The method according to claim 21, wherein the solid support is a woven fabric or a nonwoven fabric.

23. The method according to claim 22, wherein the nonwoven fabric is part of a facial mask.

24. An article comprising the MOF composition described in claim 1.

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