Tetravalent boron-containing proton-exchange solid supports and methods of making and using tetravalent boron-containing proton-exchange solid supports

Abstract

To provide a boron-containing proton-exchange solid support, a method for making the same, and a membrane electrode assembly.SOLUTION: A boron-containing proton-exchange solid support includes an oxygen atom and a tetravalent boron-based acid group including a boron atom covalently bonded to the oxygen atom.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] (Related Applications) This application is a continuation of U.S. Provisional Patent Application No. 63 / 109,943, filed November 5, 2020. , and international patent application PCT / US2021 / 0297 filed on April 28, 2021 This application claims priority from US Pat. No. 6,290,495, filed on Oct. 1, 2005, the contents of which are incorporated herein by reference in their entirety. It can be enjoyed. [Background technology]

[0002] Proton exchange membranes (PEMs) are impermeable to gases such as hydrogen (H2) and oxygen (O2). But proton (H + ) is a semipermeable membrane designed to transport. PEMs can be used in hydrogen fuel cells and water electrolysis systems under ambient conditions. It may consist of mechanically and chemically resistant particles and / or a porous framework that For example, Nafion-based proton exchange membranes are made of polytetrafluoroethylene (PTFE) with sulfonic acid groups. It contains a porous framework of fluoroethylene (PTFE). The phosphate groups function as proton transport agents in the membrane. Summary of the Invention [Problem to be solved by the invention]

[0003] The following is a simplified version of one or more aspects of the methods and systems described herein. This summary provides a basic understanding of such aspects. It is not intended to be an extensive overview of all aspects, but rather to identify key or important elements of all aspects. It is not intended to be exhaustive or to delineate the scope of any or all embodiments. Its sole purpose is to serve as a prelude to the more detailed description that follows. To present some concepts of one or more aspects of the methods and systems described herein in a simplified form. is.

[0004] In some illustrative examples, the boron-containing proton exchange solid support contains an oxygen atom. and a tetravalent boron compound containing a boron atom covalently bonded to said oxygen atom. and a base-based acidic group.

[0005] In some illustrative examples, the boron-containing proton exchange solid support has the general formula (Ia ), (Ib), (Ic) or (Id), [ka] In the formula, [SS] represents a solid support; X 1 is a substituent having the formula (IIa), (IIb), (IIc) or (IId): [ka] represents X 2 is a group having the formula (IIIa) or (IIIb): [ka] represents Y 1 and Y 2 are the same or different, and each is a tetravalent boron-based compound having the formula (IV): represents an acidic group of [ka] In the formula (IV), the boron (B) atom is X 1 or X 2 covalently bonded to the oxygen (O) atom of and Z 1 , Z 2 and Z3 are the same or different and are each an alkyl group, an alkoxy group, an alkyl group, an alkyl represents an alkyloxycarbonyl group, an aryl group, an aryloxy group, or a fluoro group; R is C1~C 30 represents an alkyl linker chain, and R is the same as each atom of the linker chain; or may be different, and may be hydrogen, hydroxyl group, fluoro group, chloro group, dialkylamino group, silyl group, Ano group, carboxylic acid group, carboxylic acid amide group, carboxylic acid ester group, alkyl group, alkoxy group It optionally has one or more pendant moieties which may include an oxy group or an aryl group.

[0006] In some illustrative examples, the method for preparing a boron-containing proton exchange solid support comprises: The proton exchange method involves modifying a solid support with tetravalent boron-based acidic groups.

[0007] In some illustrative examples, the membrane electrode assembly includes a cathode, an anode, and a a proton exchange membrane disposed between the anode and the proton exchange membrane; a proton exchange solid support containing an oxygen atom and a boron atom covalently bonded to said oxygen atom; and a tetravalent boron-based acidic group. [Brief explanation of the drawings]

[0008] The accompanying drawings illustrate various embodiments and are a part of the specification. The embodiments are merely examples and are not intended to limit the scope of the present disclosure. The same or similar reference numbers indicate the same or similar elements. [Figure 1] Figure 1A shows an exemplary structure of a solid support embodied as a framework of a porous structure, while Figure 1B shows another exemplary structure of a solid support embodied as a solid support particle. [Figure 2]2A and 2B show exemplary reaction schemes for synthesizing boron-containing proton-exchange solid supports that provide tetravalent boron-based acidic groups linked to sulfur (S) atoms by oxygen (O) atoms. [Figure 3] 3A and 3B show exemplary reaction schemes for synthesizing boron-containing proton-exchange solid supports that provide tetravalent boron-based acidic groups linked to carbon (C) atoms by oxygen (O) atoms. [Figure 4] 4A and 4B show exemplary reaction schemes for synthesizing boron-containing proton-exchange solid supports that provide tetravalent boron-based acidic groups linked to phosphorus (P) atoms by oxygen (O) atoms. [Figure 5] 5A and 5B show exemplary reaction schemes for synthesizing boron-containing proton-exchange solid supports that provide two tetravalent boron-based acidic groups linked to a phosphorus (P) atom by a single oxygen (O) atom. [Figure 6] 6A and 6B show another exemplary reaction scheme for synthesizing a boron-containing proton-exchange solid support, which provides a tetravalent boron-based acidic group linked to a phosphorus (P) atom by an oxygen (O) atom. [Figure 7] 7A and 7B show another exemplary reaction scheme for synthesizing a boron-containing proton-exchange solid support, which provides two tetravalent boron-based acidic groups linked to a phosphorus (P) atom by a single oxygen (O) atom. [Figure 8] 8A and 8B show exemplary reaction schemes for synthesizing boron-containing proton-exchange solid supports that provide tetravalent boron-based acidic groups linked to oxygen (O) atoms. [Figure 9] FIG. 9 shows an exemplary proton exchange membrane comprising a porous framework containing boron-based acidic groups attached to the pore surfaces of the porous framework. [Figure 10]FIG. 10 shows an exemplary proton exchange membrane water electrolysis system incorporating a boron-containing porous membrane. [Figure 11] FIG. 11 shows an exemplary proton exchange membrane fuel cell incorporating a boron-containing porous membrane. DETAILED DESCRIPTION OF THE INVENTION

[0009] As used herein, a tetravalent boron-containing proton exchange solid support, a tetravalent boron-containing proton -EXCHANGE SOLID SUPPORT-COMPRISING DEVICE AND METHOD FOR PREPARATION OF TETRAVALENT BORON-CONTAINING PROTON-EXCHANGE SOLID SUPPORT - Patent application In some instances, a tetravalent boron-containing proton exchange solid support is described, as well as methods of using the same. is a proton exchange solid support containing an oxygen atom and a boron atom covalently bonded to said oxygen atom. and a tetravalent boron-based acidic group comprising: The ion-exchange solid support has a sulfur atom, a carbon atom, or a phosphorus atom covalently bonded to the oxygen atom. The proton exchange solid support is an amorphous or crystalline inorganic material. , and / or may be formed of synthetic or natural polymers, and may be, for example, porous. It may be in the form of a polymer network, microparticles, or nanoparticles.

[0010] The tetravalent boron-based proton exchange solid supports described herein are strong proton exchangers. It is a superacid with exchange properties. Electrically neutral boron not only has three valence electrons, It forms a tetravalent ion with a formal negative charge by covalently bonding with four other atoms. Therefore, the tetravalent boron-based acidic groups are ionic in nature. and can function as proton transport agents. The ion-exchange solid support is a PEM for water electrolysis and / or fuel cell applications operating under acidic conditions. For example, in the boron-containing PEMs described herein, the cation The (proton) exchange occurs with a proton ionically linked to a tetravalent, negatively charged boron atom. The presence of oxygen-boron bonds improves the hydrophilicity of boron-containing PEMs. The boron-containing PEMs described herein have high High mechanical strength, high proton conductivity, low electronic conductivity, chemical stability under high pH gradient, It is durable and inexpensive to manufacture. In some instances, the Boron-containing PEM does not contain toxic materials. Tetravalent boron-containing proton exchange in PEM The implementation and use of solid supports is described in more detail below.

[0011] The tetravalent boron-containing proton exchange solid supports described herein can be used to treat bacteria, viruses, and They may also be used to filter and / or neutralize pathogens such as fungal spores and bacteria. The boron-containing proton exchange porous membranes are used in face masks, surgical masks, and air filters. air purifiers for air conditioners and enclosed spaces (e.g., homes, offices, hospitals, factories, vehicles, airplanes, etc.) It can be implemented in a cleaner.

[0012] The compositions, devices, and methods described herein may provide one or more of the benefits and / or This may provide a variety of additional and / or alternative benefits that may be identified herein. Various embodiments will now be described in more detail with reference to the figures. The following embodiments are merely illustrative and not limiting, as various modifications may be made within the scope of the present invention. You will understand that.

[0013] An exemplary tetravalent boron-containing proton exchange solid support comprises a sulfur atom covalently bonded to an oxygen atom. a proton exchange solid support containing a carbon atom, a phosphorus atom, or a hydroxyl group, and a covalent bond to the oxygen atom; The acidic groups each contain one or more tetravalent boron-based acidic groups each containing a boron atom. The tetravalent boron-containing proton exchange solid support has the general formula (Ia) or (Ib): [ka] and In the formula, [SS] represents a solid support, and X represents an oxygen (O) atom or one or more oxygen (O) atoms. Substituents containing a sulfur (S), carbon (C), or phosphorus (P) atom covalently bonded to an atom and Y 1 and Y 2 are boron atoms (B) covalently bonded to the oxygen atoms of the substituents X. represents a tetravalent boron-based acidic group containing atoms. As explained in more detail below, The group X can be a hydroxyl group, an acidic group (e.g., a phenolic or carboxylic acid group), a sulfonic acid group, (e.g., oxo acids such as sulfo groups, phosphonic acid groups, or phosphoric acid groups), or alcohols Optionally, the hydroxyl group may be derived from a substituent of a precursor containing tetravalent boron, such as The proton exchange solid support includes a linker chain connecting the substituent X to the solid support [SS]. For example, the tetravalent boron-containing proton exchange solid support may be represented by the general formula (Ic): Or (Id): [ka] and In the formula, R is C1 to C 30 R represents an alkyl linker chain, which may be the same or different. each independently represents a hydrogen atom, a hydroxyl group, a fluoro group, a chloro group, a dialkylamino group, carboxylic acid group, carboxylic acid amide group, ester group, alkyl group, alkoxy group and optionally one or more pendant moieties which may be selected from the group consisting of an aryl group, an alkoxy group, and an aryl group. Has.

[0014] The solid support [SS], the substituent X, and the optional linker chain R are combined to form a precursor Therefore, in combination, the proton exchange solid support is referred to herein as the proton exchange solid support. For example, as described in more detail below, tetravalent boron-based acids Gender Y 1 and / or Y 2 Proton-exchanged solid support ([SS]-X or [S S]-RX) is a commercially available ionomer (e.g., sulfonic acid-functionalized PTFE). Alternatively, the substituent X (e.g., a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphate group) may be by dissociation of precursors (e.g., phenolic, alcoholic, or hydroxyl groups) The body may function as a proton transport agent.

[0015] The solid support [SS] may be any suitable material, such as inorganic and / or organic materials, or materials Suitable inorganic materials include amorphous inorganic materials, materials (e.g., glass, fused silica, or ceramics), and / or crystalline inorganic materials (e.g., Suitable organic materials include, for example, quartz, single crystal silicon, or alumina. , for example, synthetic and / or natural polymers (e.g., lignin, cellulose, chitin, etc.) , ionomers, etc. In some examples, the substituent X may be a solid support [S S] or includes a side chain of a solid support [SS].

[0016] The solid support [SS] and / or the proton exchange solid support of formula (Ia)-(Id) (e.g. [SS]-X or [SS]-RX) is a porous framework or solid support. The framework of the porous structure may have any suitable shape and structure, such as particles. , a porous polymer network. FIG. 1A shows the framework of the porous structure. 102. As shown, the pores 106 are adjacent to the pores 100. The pore surfaces 104 are provided with tetravalent boron-based acidic groups 108 (e.g., Y 1 or Y 2 ) functionalized FIG. 1A shows a single tetravalent boron-based acidic group 10 attached to the pore surface 104. Although only 8 are shown, the porous framework 102 may have any other number and concentration of particles. The pore surfaces 104 may have tetravalent boron-based acidic groups 108 attached thereto.

[0017] Solid support particles include, for example, microparticles, nanoparticles, and / or resin beads. FIG. 1B shows a proton exchange solid support (e.g., [SS ]-X or [SS]-RX) are incorporated as solid support particles 110. The structure 100B shows the boron-based acidic groups 112 on the surface of the solid support particles 110. 114. In some examples (not shown), a plurality of solid support particles 1 10 are connected together and to the pore surfaces (e.g., surface 114) in the framework of the porous structure. A porous framework (e.g., porous porous structure) having attached boron-based acidic groups 112. The framework 102 of the quality structure may be formed.

[0018] The solid support particles 110 may be made of any suitable material, such as inorganic particles (e.g., quartz silica). particles, ceramic particles, etc.) or natural or synthetic organic molecules (e.g. polymers), The porous framework 102 may be formed from any of the materials described above. The carrier particles 110 may have any suitable shape and may range in size from tens of nanometers (nm) to hundreds of microns. The porous structure formed by the solid support particles 110 may have a range of sizes. The porosity of the framework is controlled and controlled by the size and / or shape of the solid support particles 110. The solid support particles 110 have mechanical strength, durability in a high pH gradient environment, and / or may be selected for their affinity for water (e.g., the solid support particles may be PE Depending on the balance of water affinity required for M100, hydrophilic or hydrophobic properties may be selected. .

[0019] Referring again to formulas (Ia) to (Id), the substituent X is an oxygen (O) atom or one Sulfur (S), carbon (C), or phosphorus (P) atoms covalently bonded to the above oxygen (O) atoms In some examples, the substituent X is a pendant linked to a solid support [SS]. pendant hydroxyl groups, pendant acidic groups (sulfonic acid groups, sulfate group, carboxylic acid group, carbonate group, phosphonic acid group, phosphoric acid group, or phenol group, or of a precursor substituent containing a hydroxyl group, such as an alcohol, linked to a solid support [SS] In some instances, the substituent X is covalently bonded to the oxygen atom and It contains a sulfur atom, a carbon atom, or a phosphorus atom covalently bonded to a further oxygen atom. Examples of groups X include, but are not limited to, (derived from pendant hydroxyl groups) ) oxygen atom (O), carboxylic acid ester (C(=O)O), carbonate ester (OC(=O) O), sulfonate ester (S(=O)2O), sulfate ester (OS(=O)2O), sulfonyl group (P(=O)(OH)O or P(=O)O2), and phosphate group (OP( =O)O2), an aryloxy group (OAr) (e.g., a phenoxy group), or an alkoxy group (OR). Further examples of substituent X are described below with reference to Figures 2A to 8B. This is shown in the exemplary reaction scheme described below.

[0020] Tetravalent boron-containing acidic group Y 1 and Y 2 may be the same or different, and in the general formula (IV), Represented, [ka] In the formula, the boron (B) atom is bonded to the oxygen (O) of the substituent X, which is derived from the hydroxyl group of the precursor. For example, the substituent X is covalently bonded to a sulfur (S) atom (not shown in Formula IV). When the acid group of a precursor containing a carbon (C) atom or a phosphorus (P) atom is a derivative of the boron The B atom is in a state where it ... It is covalently bonded to the oxygen (O) atom that is bonded to the substituent Z. 1 , Z 2 , and Z 3 The same one or different, each of which is an alkyl group, an alkoxy group, an alkyloxycarbonyl group, It represents an aryl group, an aryloxy group, a hydroxyl group, or a fluoro group. In the formula, the group Y 1 and / or Y 2 is an enzyme represented by formula (Va), (Vb), or (Vc) It may be stealth, [ka] In the formula, R', R'', and R''' may be the same or different, and may be, for example, an alkyl group. , an alkoxy group, an alkyloxycarbonyl group, an aryl group, or an aryloxy group. In another further example, Y 1 and / or Y 2 is boron trifluoride (i.e., Z 1 , Z 2 , and Z 3 Each is derived from a fluoro group (F). Y 1 and Y 2 Other examples of As shown and described in the exemplary reaction schemes described below with reference to Figures 2A through 8B .

[0021] The tetravalent boron-containing proton exchange solid support can be synthesized by any suitable method. In some examples, tetravalent phosphatase inhibitors may be used, as shown and described herein with reference to Figures 2A-8B. The boron-containing proton-exchange solid support is prepared by converting the proton-exchange solid support into boron trifluoride (BF 3) or by coupling with a boron-based ester (e.g., a tetravalent boron-based ester) The following reaction schemes are merely illustrative and not limiting. There is no.

[0022] Figure 2A shows a tetravalent boron-based acid linked to a sulfur (S) atom by an oxygen (O) atom. An exemplary reaction sequence for synthesizing a boron-containing proton exchange solid support providing functional groups is shown below. As shown, the proton exchange solid support 202 is a trifluoromethyl-2-(2-methyl-2-propanol)-2-one. The solid support is modified with boron fluoride 204 to produce a boron-containing proton-exchange solid support 206. Boron fluoride-204 is synthesized by diethyl ether and / or tetrahydrofuran complex synthesis. Boron trifluoride is a Lewis acid and has three boron-fluorine bonds. However, fluorine is the most electronegative element in the periodic table, making it a stronger acid than boric acid and boronic acid. be.

[0023] The proton exchange solid support 202 comprises a solid support 208, a linker chain 210, and a sulfo group. The linker chain 210 includes a phosphate group 212. However, the linker chain 210 is optional and may be omitted in other examples. The solid support 208 may be any solid support described herein (e.g., a solid support of the formula (Ia)-(Id) may be incorporated into any solid support, such as the solid support [SS] Alternatively, a porous framework (e.g., porous framework 102) or can be incorporated in any shape, such as as a solid support particle (e.g., solid support particle 110). In some examples, the proton exchange solid support 202 may be a polyfluorosulfone. sulfonated PTFE-based polymers, perfluorosulfonic acid polymers, or sulfonated PTFE-based polymers Proton exchange solid supports include sulfonic acid functionalized polymers such as fluoropolymers-copolymers. Examples of the carrier 202 include, but are not limited to, ethanesulfonyl fluoride, 2 -[1-[difluoro-[(trifluoroethenyl)oxy]methyl]-1,2,2,2 -tetrafluoroethoxy]-1,1,2,2-tetrafluoro, tetrafluoroethoxy ethylene and tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7- Octene sulfonic acid copolymers are commercially available sulfonic acid functionalized polymers. Examples include, but are not limited to, Nafion-H, Nafion HP, Nafion 117 , Nafion 115, Nafion 212, Nafion 211, Nafion NE1035 Nafion is sold by DuPont in various forms and grades, including Nafion XL. Aquivion (registered trademark), (Aquivion (registered trademark) E98-05, Aquivion (registered trademark) Available in various forms and greys, including Aquivion® PW98 and Aquivion® PW87S. Aquivion® (available from Solvay in the United States), WL Gore & Associates) GoreSelect®, (Asahi Shokubai Flemion (trademark), sold by its subsidiary, Ionomr Innovation Pemion+ (trademark) sold by Company S, and any combinations and derivatives thereof , grade or form.

[0024] The linker chain 210 may be any suitable linker chain capable of linking the sulfonic acid group 212 to the solid support 208. The linker chain 210 can be any of the linker chains described herein (e.g., Any suitable linker chain may be incorporated, such as a linker chain of formula (Ia)-(Id). In some examples, linker chain 210 includes carbon, oxygen, and / or nitrogen. As shown in FIG. 2A, the linker chain 210 is an alkyl chain of length m, where m ranges from 1 to 30. a alkyl chain having one or more side groups A, each of which independently represents a hydrogen (H) , hydroxyl group (OH), fluoro group (F), chloro group (Cl), dialkylamino group (NR2, where R can represent hydrogen or an organic linking group such as a methyl group (CH3), cyano (CN) group, carboxylic acid (COOH) group, carboxylic acid amide group, ester group, alkyl group , an alkoxy group, or an aryl group.

[0025] In some examples, the boron trifluoride 204 and sulfonic acid group 212 may be any other Although they can be combined in any suitable ratio, they are combined in an approximately 1:1 stoichiometric ratio. The boron-containing proton exchange solid support 206 contains a sulfur atom covalently bonded to an oxygen atom. a proton exchange solid support 214, and a tetravalent boron atom covalently bonded to said oxygen atom; The boron-containing proton exchange solid support 206 contains a strong acidic group 216. As mentioned above, the electrically neutral boron is a superacid with excellent proton exchange properties. As shown in B, it not only has three valence electrons but also has the ability to form covalent bonds with four other atoms. Therefore, a tetravalent ion with a negative formal charge can be formed. The boron-based acidic groups 216 are ionic in nature and function as proton transport agents. obtain.

[0026] Figure 2B shows a tetravalent boron-based acidic group linked to a sulfur (S) atom by an oxygen (O) atom. Other exemplary reaction schemes for synthesizing boron-containing proton exchange solid supports provide: Reaction scheme 200B shows the reaction of a proton-exchange solid support 202 with Instead of bonding with boron trifluoride 204, it bonds with a boron-based ester 218. Similar to Reaction Scheme 200A, except that Reaction Scheme 200B is The ester 218 of the base is a boric acid ester or a boronic acid ester. ter) (also called boronate ester) Boric acid esters may be, for example, boric acid (B(OH)3) or related boron oxides. This can be generated by reacting boronate with alcohol (ROH) in the presence of heat. Stells are prepared, for example, by reacting boronic acids or related boron oxides with alcohols (ROH) in the presence of heat. Therefore, the boron-based ester 2 in FIG. In 18, the groups X, Y, and Z are each independently an alkoxy group (RO), an aryl group (R-O ... an alkyl group (R), an aryl group (Ar), or a fluoro group (F) with the proviso that at least two of X, Y and Z are oxygen atoms bonded to a boron atom. The boron-based ester comprises a hydroxy group, and the hydroxy group ... forms a boron-based ester. Examples include, but are not limited to, trimethyl borate, triethyl borate, boric acid, Tributyl borate, n-octyl borate, tridecyl borate, tritetradecyl borate, boric acid Triisopropyl borate, tris(hexafluoroisopropyl) borate, trimethoxycyclohexyl Iotriboroxane, triphenyl borate, tri-o-tolyl borate, tris(tri)borate methylsilyl), tetraacetyl diborate, tris(2,2,2-trifluoroethylene) borate ethyl), bis-pinacol diboronate, pinacol boronate, allyl pinacolboronate boroxane, diisopropoxymethylboroxane, and diisopropoxymethylboroxane.

[0027] In some examples, the boron-based ester 218 and the sulfonic acid group 212 may be any The stoichiometric ratio is approximately 1:1, although the stoichiometric ratio may be any other suitable ratio. The resulting boron-containing proton-exchanged solid support 220 contains a sulfur atom covalently bonded to an oxygen atom. a proton exchange solid support 214 containing a boron atom covalently bonded to said oxygen atom; The boron-containing proton exchange solid support 20 comprises a tetravalent boron-based acidic group 222. 6, the boron-containing proton exchange solid support 220 has strong proton exchange properties. It is a superacid and is ionic in nature.

[0028] Figure 3A shows a tetravalent boron-based acidic molecule linked to a carbon (C) atom by an oxygen (O) atom. Provided is an exemplary reaction scheme 3 for synthesizing a boron-containing proton-exchange solid support. As shown, the proton-exchange solid support 302 is boron trifluoride. The solid support is modified with boron trifluoride 304 to produce a boron-containing proton-exchange solid support 306. Ion can be used in the synthesis of diethyl ether and / or tetrahydrofuran complexes .

[0029] The proton exchange solid support 302 comprises a solid support 308, a linker chain 310, and a carbohydrate chain. The linker chain 310 includes a carboxylic acid group 312. However, the linker chain 310 is optional and may be omitted in other examples. Solid support 308 may be any solid support described herein, such as , or any suitable solid support (e.g., solid support [SS] of formula (Ia)-(Id)). Alternatively, a porous framework (e.g., a porous framework 102) or as solid support particles (e.g., solid support particles 110). In some instances, the proton exchange solid support 302 may be a polyamide. Includes carboxylic acid functionalized polymers such as acrylic acid polymers.

[0030] The linker chain 310 may be any suitable linker chain capable of linking the carboxylic acid group 312 to the solid support 308. The linker chain 310 can be any of the linker chains described herein (e.g., For example, the linker chain R of formula (Ia)-(Id) may be incorporated with any suitable linker chain. Linker strand 310 may be the same as or similar to linker strand 210.

[0031] In some examples, the boron trifluoride 304 and the carboxylic acid group 312 may be substituted with any other Although they can be combined in any suitable ratio, they are combined in an approximately 1:1 stoichiometric ratio. The boron-containing proton exchange solid support 306 contains a carbon atom covalently bonded to an oxygen atom. a proton exchange solid support 314, and a tetravalent boron atom covalently bonded to said oxygen atom; The boron-containing proton exchange solid support 306 contains a strong acidic group 316 of It is a superacid with good proton exchange properties and is ionic in nature.

[0032] Figure 3B shows a tetravalent boron-based acidic group linked to a carbon (C) atom by an oxygen (O) atom. Other exemplary reaction schemes for synthesizing boron-containing proton exchange solid supports provide: Reaction scheme 300B shows the reaction of a proton-exchange solid support 302 with , boron trifluoride 304 instead of boron-based ester 318. Similar to Reaction Scheme 300A except that Reaction Scheme 300B is a boron-based ester. The ester 318 may be the same as or similar to the boron-based ester 218.

[0033] In some examples, the boron-based ester 318 and the carboxylic acid group 312 may be any The stoichiometric ratio is approximately 1:1, although the stoichiometric ratio may be any other suitable ratio. The resulting boron-containing proton-exchanged solid support 320 contains a carbon atom covalently bonded to an oxygen atom. a proton exchange solid support 314 containing a boron atom covalently bonded to said oxygen atom; The boron-containing proton exchange solid support 30 comprises a tetravalent boron-based acidic group 322. 6, the boron-containing proton exchange solid support 320 has strong proton exchange properties. It is a superacid and is ionic in nature.

[0034] Figure 4A shows a tetravalent boron-based acidic group linked to a phosphorus (P) atom by an oxygen (O) atom. An exemplary reaction scheme for synthesizing a boron-containing proton-exchange solid support provides: 400A. As shown, the proton exchange solid support 402 is The solid support is modified with boron 404 to produce a boron-containing proton-exchange solid support 406. Boron can be used in the synthesis of diethyl ether and / or tetrahydrofuran complexes. do.

[0035] The proton exchange solid support 402 comprises a solid support 408, a linker chain 410, and a phospho The linker chain 410 includes a phosphate group 412. However, the linker chain 410 is optional and may be omitted in other examples. Solid support 408 may be any solid support described herein, such as , or any suitable solid support (e.g., solid support [SS] of formula (Ia)-(Id)). Alternatively, a porous framework (e.g., a porous framework 102) or as solid support particles (e.g., solid support particles 110). In some instances, the proton exchange solid support 402 may be a polyvinyl alcohol. These include phosphonic acid functionalized polymers such as poly(vinyl phosphonic acid) (PVPA) polymers.

[0036] The linker chain 410 may be any suitable linker chain capable of linking the phosphonic acid group 412 to the solid support 408. The linker chain 410 can be any of the linker chains described herein (e.g., For example, the linker chain R of formula (Ia)-(Id) may be incorporated with any suitable linker chain. Linker strand 410 may be the same as or similar to linker strand 210.

[0037] In some examples, the boron trifluoride 404 and the phosphonic acid group 412 may be any other Although they can be combined in any suitable ratio, they are combined in an approximately 1:1 stoichiometric ratio. The boron-containing proton exchange solid support 406 contains a phosphorus atom covalently bonded to an oxygen atom. a proton exchange solid support 414, and a tetravalent boron atom covalently bonded to said oxygen atom; The boron-containing proton exchange solid support 406 contains a strong acidic group 416. It is a superacid with good proton exchange properties and is ionic in nature.

[0038] Figure 4B shows a tetravalent boron-based acidic group linked to a phosphorus (P) atom by an oxygen (O) atom. Other exemplary reaction schemes for synthesizing boron-containing proton exchange solid supports provide: Reaction scheme 400B shows the reaction of a proton-exchange solid support 402 , boron trifluoride 404 instead of boron-based ester 418. Similar to reaction scheme 400A, except that boron-based esters are used. The ester 418 may be the same as or similar to the boron-based ester 218.

[0039] In some examples, the boron-based ester 418 and the phosphonic acid group 412 are The stoichiometric ratio is approximately 1:1, although the stoichiometric ratio may be any other suitable ratio. The resulting boron-containing proton-exchange solid support 420 contains a phosphorus atom covalently bonded to an oxygen atom. a proton-exchange solid support 414 containing a boron atom covalently bonded to said oxygen atom; The boron-containing proton exchange solid support 40 comprises a tetravalent boron-based acidic group 422. 6, the boron-containing proton exchange solid support 420 has strong proton exchange properties. It is a superacid and is ionic in nature.

[0040] Figure 5A shows two amines, each linked to the same phosphorus (P) atom by a different oxygen (O) atom. To synthesize boron-containing proton exchange solid supports, which provide tetravalent boron-based acidic groups, 5 shows an exemplary reaction scheme 500A for the proton exchange reaction of a hydroxyl group with a hydroxyl group. The solid support 502 is modified with boron trifluoride 504 to form a boron-containing proton exchange solid support. Boron trifluoride is reacted with diethyl ether and / or tetrahydrofuran to produce the compound 506. It can be used in the synthesis of fluorine complexes.

[0041] The proton exchange solid support 502 comprises a solid support 508, a linker chain 510, and a phospho The linker chain 510 includes a carboxylic acid group 512. However, the linker chain 510 is optional and may be omitted in other examples. Solid support 508 may be any solid support described herein, such as , or any suitable solid support (e.g., solid support [SS] of formula (Ia)-(Id)). Alternatively, a porous framework (e.g., a porous framework 102) or as solid support particles (e.g., solid support particles 110). In some examples, the proton exchange solid support 502 may be incorporated in the form of: Includes phosphonic acid functionalized polymers such as PVPA polymers.

[0042] The linker chain 510 may be any suitable linker chain capable of linking the phosphonic acid group 512 to the solid support 508. The linker chain 510 can be any of the linker chains described herein (e.g., For example, the linker chain R of formula (Ia)-(Id) may be incorporated with any suitable linker chain. Linker strand 510 may be the same as or similar to linker strand 210.

[0043] In some examples, the boron trifluoride 504 and the phosphonic acid group 512 may be any other Although they can be combined in any suitable ratio, they are combined in a stoichiometric ratio of approximately 2 to 1 (2:1). The boron-containing proton exchange solid support 506 is a proton exchange solid support containing phosphorus atoms. 514, as well as different oxygen atoms of the proton exchange solid support 506 (e.g., phosphonic acid Two tetravalent boron groups each containing a boron atom covalently bonded to a different oxygen atom in group 512 Contains iodine-based acidic groups 516-1 and 516-2. Boron-containing proton exchange solid support Body 506 is a superacid with strong proton exchange properties and is ionic in nature.

[0044] FIG. 5B shows two different oxygen (O) atoms linked to the same phosphorus (P) atom. A boron-containing proton exchange solid support was synthesized, providing two tetravalent boron-based acidic groups. 5 shows another exemplary reaction scheme 500B for producing , the proton-exchanged solid support 502 contains a boron-based fluoride instead of boron trifluoride 504. Reaction Scheme 500A is reaction scheme 500B, except that reaction scheme 500A is reaction scheme 500B, which combines with sterol 518. Boron-based Ester 518 is the same as Boron-based Ester 218. Or it may be similar.

[0045] In some examples, the boron-based ester 518 and the phosphonic acid group 512 are The stoichiometry is approximately two to one (2:1), although any other suitable ratio may be used. The resulting boron-containing proton-exchange solid support 520 is a proton-exchange solid support containing phosphorus atoms. and different oxygen atoms of the solid support 514, as well as the proton exchange solid support 520 (e.g., Two sulfonic acid groups, each containing a boron atom covalently bonded to two different oxygen atoms. Contains tetravalent boron-based acidic groups 522-1 and 522-2. Boron-containing proton exchange The solid support 506 is a superacid with strong proton exchange properties and is ionic in nature. do.

[0046] Figure 6A shows a tetravalent boron-based acidic group linked to a phosphorus (P) atom by an oxygen (O) atom. Other exemplary reaction schemes for synthesizing boron-containing proton exchange solid supports provide: As shown, proton exchange solid support 602 is a trifluoride-containing solid support. The solid support is modified with boron chloride 604 to produce a boron-containing proton-exchange solid support 606. Boron fluoride is used in the synthesis of diethyl ether and / or tetrahydrofuran complexes. It is possible.

[0047] The proton exchange solid support 602 comprises a solid support 608, a linker chain 610, and a monophosphine The linker chain 610 includes a phosphate group 612. However, the linker chain 610 is optional, and in other examples The solid support 408 may be any solid support described herein ( For example, the solid support (SS) of formula (Ia)-(Id) can be prepared using any suitable solid support. or may be embedded in a porous framework (e.g., a porous frame) workpiece 102) or solid support particles (e.g., solid support particles 110). In some instances, the proton exchange solid support 60 2 is a phosphate-functionalized polybenzoimidazole (PBI) doped with phosphoric acid. Including Rimmer.

[0048] Linker chain 610 may be any suitable chain capable of linking phosphate group 612 to solid support 608. The linker chain 610 may be any of the linker chains described herein ( For example, any suitable linker chain may be incorporated, such as the linker chain R of formula (Ia)-(Id). Linker strand 610 may be the same as or similar to linker strand 210.

[0049] In some examples, the boron trifluoride 604 and phosphate group 612 may be substituted with any other Although they can be bound in any suitable ratio, they bind in an approximately 1:1 stoichiometric ratio. The boron-containing proton exchange solid support 606 contains a phosphorus atom covalently bonded to an oxygen atom. and a proton exchange solid support 614 containing a boron atom covalently bonded to said oxygen atom. The boron-containing proton exchange solid support 606 comprises a 2-valent boron-based acidic group 616. It is a superacid with strong proton exchange properties and is ionic in nature.

[0050] The resulting boron-containing proton-exchanged solid support 606 contains a phosphorus atom covalently bonded to an oxygen atom. a proton exchange solid support 614 containing a boron atom covalently bonded to said oxygen atom; The boron-containing proton exchange solid support 60 comprises a tetravalent boron-based acidic group 616. 6 is a superacid with strong proton exchange properties and is ionic in nature.

[0051] Figure 6B shows a tetravalent boron-based acidic group linked to a phosphorus (P) atom by an oxygen (O) atom. Other exemplary reaction schemes for synthesizing boron-containing proton exchange solid supports provide: Reaction scheme 600B shows the reaction of a proton-exchange solid support 602 , boron trifluoride 604 instead of boron-based ester 618. Similar to reaction scheme 600A, except that boron-based esters are used. The ester 618 may be the same as or similar to the boron-based ester 218.

[0052] In some examples, the boron-based ester 618 and the phosphate group 612 are optionally Although other suitable ratios may be used, the stoichiometry is approximately one to one (1:1). The boron-containing proton exchange solid support 620 has a phosphorus atom covalently bonded to an oxygen atom. a proton exchange solid support 614 comprising a boron atom covalently bonded to said oxygen atom; The boron-containing proton exchange solid support 606 includes tetravalent boron-based acidic groups 622. Thus, the boron-containing proton exchange solid support 620 is an ultra-high-molecular-weight material with strong proton exchange properties. It is an acid and is ionic in nature.

[0053] Figure 7A shows two cations, each linked to the same phosphorus (P) atom by a different oxygen (O) atom. Synthesize boron-containing proton exchange solid supports that provide tetravalent boron-based acidic groups. 7 shows an exemplary reaction scheme 700A for the phosphate functional group. The boron trifluoride-modified proton-exchange solid support 702 is modified with boron trifluoride 704 to form a boron-containing proton exchange solid support 702. To produce the ion-exchanged solid support 706, boron trifluoride is added in diethyl ether and / or It can be used in the synthesis of tetrahydrofuran complexes.

[0054] The proton exchange solid support 702 comprises a solid support 708, a linker chain 710, and a phosphate The linker chain 710 includes group 712. However, the linker chain 710 is optional and may be omitted in other examples. Solid support 708 may be any solid support described herein (e.g., a solid support of the formula (Ia)-(Id) may be incorporated into any suitable solid support, such as a solid support [SS]. Alternatively, a porous framework (e.g., a porous framework 10 2) or as solid support particles (e.g., solid support particles 110), in any suitable form. In some examples, the proton exchange solid support 702 may be incorporated with PB These include phosphate-functionalized polymers such as the I polymer.

[0055] Linker chain 710 may be any suitable site capable of linking phosphate group 712 to solid support 708. Linker strand 710 can be any linker strand described herein (e.g., or any suitable linker chain, such as the linker chain R of formula (Ia)-(Id). Linker strand 710 may be the same as or similar to linker strand 210.

[0056] In some examples, the boron trifluoride 704 and phosphate group 712 may be replaced with any other suitable Although the bonds can be formed in any ratio, they are generally formed in a stoichiometric ratio of approximately 2:1. The uran-containing proton exchange solid support 706 is a proton exchange solid support 71 containing phosphorus atoms. 4, and proton exchange with different oxygen atoms of the solid support 706 (e.g., phosphate groups) Two tetravalent boron atoms, each containing a boron atom covalently bonded to 712 different oxygen atoms. The boron-containing proton exchange solid support comprises boron-based acidic groups 716-1 and 716-2. 706 is a superacid with strong proton exchange properties and is ionic in nature.

[0057] Figure 7B shows two tetravalent boron benzyl groups linked to a phosphorus (P) atom by a single oxygen (O) atom. Another example is for synthesizing a boron-containing proton exchange solid support, which provides acidic groups for the base. Reaction scheme 700B shows an exemplary reaction scheme 700B. Reaction scheme 700B shows a proton-exchange solid Support 702 is bonded with boron-based ester 718 instead of boron trifluoride 704. This is similar to reaction scheme 700A, except that reaction scheme 700B is the reaction of boron. Boron-based ester 718 may be the same as or similar to boron-based ester 218. good.

[0058] In some examples, the boron-based ester 718 and the phosphate group 712 are The combination is preferably in a stoichiometric ratio of approximately two to one (2:1), although any other suitable ratio may be used. The resulting boron-containing proton exchange solid support 520 is a proton exchange solid support containing a phosphorus atom. solid support 714, as well as different oxygen atoms of the proton-exchange solid support 720 (e.g., Two phosphonic acid groups, each containing a boron atom covalently bonded to two different oxygen atoms (712) The tetravalent boron-based acidic groups 722-1 and 722-2 are boron-containing proton exchange groups. The exchange solid support 706 is a superacid with strong proton exchange properties and is ionic in nature. be.

[0059] FIG. 8A shows a boron-based acid group that provides a tetravalent boron-based acid group linked to an oxygen (O) atom. 8 shows another exemplary reaction scheme 800A for synthesizing a silicon-containing proton exchange solid support. As shown, the proton-exchanged solid support 802 is boron trifluoride 804. The boron trifluoride is modified to produce a boron-containing proton exchange solid support 806. It can be used in the synthesis of ethyl ether and / or tetrahydrofuran complexes.

[0060] The proton exchange solid support 802 comprises a solid support 808, a linker chain 810, and a hydrogel. The linker chain 810 includes an xyl group 812. However, the linker chain 810 is optional and may be omitted in other examples. Solid support 808 may be any solid support described herein, such as For example, the solid support [SS] of formula (Ia)-(Id) can be incorporated into any suitable solid support. or may be embedded in a porous framework (e.g., a porous framework 102) or solid support particles (e.g., solid support particles 110), In some examples, the proton exchange solid support 802 may be Natural polymers that provide hydroxyl groups, such as lignin, cellulose, or chitin, are also included. nothing.

[0061] The linker chain 810 may be any suitable chain capable of linking the hydroxyl group 812 to the solid support 808. The linker chain 810 may be any of the linker chains described herein ( For example, any suitable linker chain may be incorporated, such as the linker chain R of formula (Ia)-(Id). Linker strand 810 may be the same as or similar to linker strand 210.

[0062] In some examples, the boron trifluoride 804 and the hydroxyl group 812 are Although they can be bound in any suitable ratio, they bind in an approximately 1:1 stoichiometric ratio. The boron-containing proton exchange solid support 806 has an oxygen atom from a hydroxyl group 812. and a proton exchange solid support 814 comprising a boron atom covalently bonded to said oxygen atom. The boron-containing proton exchange solid support 806 includes a tetravalent boron-based acidic group 816. is a superacid with strong proton exchange properties and is ionic in nature.

[0063] FIG. 8B shows a boron-based acid group that provides a tetravalent boron-based acid group linked to an oxygen (O) atom. 8 shows another exemplary reaction scheme 800B for synthesizing a silicon-containing proton exchange solid support. Reaction scheme 800B shows that proton-exchange solid support 802 reacts with boron trifluoride. Reaction scheme 800B is coupling with boron-based ester 818 instead of 804. The reaction is similar to Reaction Scheme 800A, except that boron-based ester 818 is It may be the same as or similar to the iodine-based ester 218.

[0064] In some examples, the boron-based ester 818 and the hydroxyl group 812 are The combination may be in any other suitable ratio, but is preferably in an approximately one to one (1:1) stoichiometric ratio. The resulting boron-containing proton exchange solid support 820 is a proton exchange solid support containing oxygen atoms. a solid support 814, and a tetravalent boron-based compound including a boron atom covalently bonded to said oxygen atom. The boron-containing proton exchange solid support 806 contains an acidic group 822. The proton exchangeable solid support 820 is a superacid with strong proton exchange properties and is essentially It is highly ionic.

[0065] Reaction Schemes 200A-800B are based on commercially available polymers and ionomers, or (e.g. , sulfonic acid group, carboxylic acid group, phosphonic acid group, phosphate group, phenol group, alkoxy group PEMs with pendant hydroxyl groups (derived from pendant hydroxyl groups) In addition to functionalizing the materials with tetravalent boron-based acidic groups, we have also incorporated dopants, nanoparticles, and microcrystalline cellulose. It may also be used to modify components of PEMs such as particles and ionomers. Onomers generally include a class of polymeric materials with pendant acidic groups. Thus, a solid support (e.g., solid support 208 optionally having a linker chain 210) ) is a polymer and contains pendant acidic groups, the boron-based acidic groups in question (e.g., The resulting boron-containing proton exchange is due to, for example, boron-based acidic groups 216 or 222. such as a boron-containing proton-exchange solid support (e.g., boron-containing proton-exchange solid support 206 or 220). The proton-exchanged solid support of the precursor (e.g., proton-exchanged solid support 202) is It is an ionomer due to the presence of acidic groups (e.g., sulfonic acid groups 212). When the proton exchangeable solid support is an ionomer, the PEM is a boron-containing proton exchanger. Form a proton-exchanged solid support (e.g., boron-containing proton-exchanged solid support 206 or 220). Catalyst coated membranes can also be fabricated by depositing catalyst on both sides of the PEM. Ionomeric forms of boron-containing proton exchange solid supports as binders for supporting It can be made using

[0066] The boron-containing proton exchange solid supports described herein can be used in water electrolysis and / or fuel cell electrolysis. It may also be used in pond applications, an exemplary application of which is described herein with reference to Figures 9-11. .

[0067] In some instances, tetravalent boron-containing proton exchange solid supports are used in PEM. FIG. 9 shows an exemplary proton exchange membrane 900 (PEM 900). 900 is a porous structure framework 902, and and tetravalent ions are distributed throughout the porous structure and bound to the pore surfaces of the framework 902. containing boron-based acidic groups 904.

[0068] The porous framework 902 may be made of any of the materials described herein, such as inorganic and / or organic materials. It may be formed of any suitable solid support or combination of solid supports described. The inorganic material may be an amorphous inorganic material (e.g., glass, quartz glass, or ceramic). and / or crystalline inorganic materials (e.g., quartz, single crystal silicon, or alumina). Suitable organic materials include, for example, synthetic and / or natural polymers (e.g. cellulose).

[0069] The PEM 900 may have a thickness d ranging from a few microns to hundreds of microns. With the structure described in the document, PEM900 can withstand a pressure difference of up to 30 atmospheres and acid PEM900 may be permeable to water and protons. These may travel through PEM 900 as shown by arrow 906, but not through PEM 900. 00 is generally impermeable to gases such as hydrogen and oxygen.

[0070] FIG. 10 illustrates an exemplary proton exchange membrane water electrolysis system incorporating a boron-containing porous membrane. The PEM water electrolysis system 1000 is shown. 000 uses electricity to separate water into oxygen (O2) and hydrogen (H2) through an electrochemical reaction. The structure of the PEM water electrolysis system 1000, like any other suitable water electrolysis system, is as follows: These are merely exemplary and not limiting, as other suitable structures may incorporate the boron-containing porous membrane. It is not something that is done.

[0071] As shown in FIG. 10, the PEM water electrolysis system 1000 includes a membrane electrode assembly 1002 ( MEA 1002), porous transport layers 1004-1 and 1004-2, bipolar plate 1006 -1 and 1006-2, and a power supply source 1008. Also, the PEM water electrolysis system 1000 may include additional or alternative structures not shown in FIG. 10 as specific implementations may allow. It may also include a composition element.

[0072] The MEA 1002 is disposed between a first catalyst layer 1012-1 and a second catalyst layer 1012-2. The PEM 1010 contains a proton (H + ) and other cations While providing selective conductivity and preventing the permeation of gases such as hydrogen and oxygen, This electrically separates the first catalyst layer 1012-1 from the second catalyst layer 1012-2. The PEM 1010 can be any suitable PEM. For example, the PEM 1010 can be a porous Porous structures having boron-based acidic groups attached to the pore surfaces within the framework of the structure. The porous membrane may be a boron-containing membrane (eg, PEM900) that includes a framework of the structure.

[0073] The first catalyst layer 1012-1 and the second catalyst layer 1012-2 are made of platinum, ruthenium, and and / or a conductive electrode with an embedded electrochemical catalyst (not shown) such as cerium (IV) oxide. In some examples, the first catalyst layer 1012-1 and the second catalyst layer 101 2-2 is formed using an ionomer that binds catalyst nanoparticles. The ionomers used to form the first catalyst layer 1012-1 and the second catalyst layer 1012-2 are As described herein, it may include a tetravalent boron-containing proton exchange solid support. .

[0074] MEA 1002 is placed between porous transport layers 1004-1 and 1004-2. EA 1002 is similarly placed between bipolar plates 1006-1 and 1006-2, Flow channels 1014-1 and 1014-2 are formed between bipolar plate 1006 and porous transport layer 1004. Located between.

[0075] In the MEA 1002, the first catalyst layer 1012-1 functions as an anode, and the second catalyst layer 1012-2 functions as an anode. The catalyst layer 1012-2 functions as a cathode. When the electrodes are powered by a power supply 1008, the acid is represented by the following electrochemical half reaction: An elementary evolution reaction (OER) occurs at anode 1012-1. 2H2O→O2+4H + +4e - Protons pass through the PEM 1010 from the anode 1012-1 to the cathode 1012-2 The electrons are then conducted from the anode 1012-1 to the cathode 1012-2 by a conduction path around the PEM 100. The PEM 1010 conducts electricity from the anode 1012-1 to the cathode 1012-2. Proton (H + ) and water, but not oxygen or hydrogen. At the cathode 1012-2, protons are released into the hydrogen atmosphere via the following electrochemical half-reaction: It combines with electrons in the bioreaction (HER). 4H + +4e - →2H2

[0076] OER and HER are two complementary electrochemical reactions that split water using electricity. This is represented by the overall water electrolysis reaction below: 2H2O → 2H2 + O2

[0077] FIG. 11 illustrates an exemplary proton exchange membrane fuel cell 1100 (P The PEM fuel cell 1100 is a PEM fuel cell that generates electricity as a result of an electrochemical reaction. In this example, the electrochemical reaction is hydrogen gas (H2) and oxygen gas (O2). Other suitable proton exchange membrane fuels include reacting oxygen (O2) with water to produce water and electricity. Similar to fuel cells, other suitable structures may incorporate boron-containing porous membranes, thus The structure of the M fuel cell 1100 is merely exemplary and not limiting.

[0078] As shown in FIG. 11, a PEM fuel cell 1100 includes a membrane electrode assembly 1102 (MEA 1102), porous transport layers 1104-1 and 1104-2, bipolar plates 1106-1 and The electric device 1108 is electrically connected to the MEA 1102 and has a P The PEM fuel cell 1100 is also powered by a PEM fuel cell 1100. 11. Additional or alternative components not shown in FIG. 11 may be included to provide .

[0079] The MEA 1102 is disposed between a first catalyst layer 1112-1 and a second catalyst layer 1112-2. The PEM 1110 is a proton (H + ) and other cations While providing selective conduction and preventing the permeation of gases such as hydrogen and oxygen, , electrically separating the first catalyst layer 1112-1 from the second catalyst layer 1112-2. EM 1100 may be provided by any suitable PEM. For example, PEM 1110 has boron-based acidic groups attached to the pore surfaces of the porous framework, This was carried out on a boron-containing porous membrane (e.g., PEM900) containing a porous framework. This may also be done.

[0080] The first catalyst layer 1112-1 and the second catalyst layer 1112-2 are embedded electrochemical catalysts. In some examples, the first catalyst layer 1112-1 is a conductive electrode having a first catalyst layer 1112-1 (not shown). and the second catalyst layer 1112-2 is formed using an ionomer that binds catalyst nanoparticles. In some examples, the first catalyst layer 1112-1 and the second catalyst layer 1104 The ionomer used to form -2 is a tetravalent boron-containing ionomer as described herein. Includes ionomers incorporating proton exchange solid supports.

[0081] MEA 1102 is placed between porous transport layers 1104-1 and 1104-2, resulting in The flow path 1114 is located between the bipolar plates 1106-1 and 1106-2. In the MEA 1102, the first catalyst layer 1112-1 is located between the cathode and the cathode. The first catalyst layer 1112-1 functions as the cathode, and the second catalyst layer 1112-2 functions as the anode. The anode 1112-1 and the anode 1112-2 are electrically connected to the device 1108. Electricity is generated by a PEM fuel cell 1100 that drives the

[0082] During operation of the PEM fuel cell 1100, hydrogen gas (H2) is The anode side of the PEM fuel cell 1100 is fed with oxygen gas (O2), which flows into the cathode side of the PEM fuel cell 1100. At the anode 1112-2, the hydrogen molecules undergo the following hydrogen oxidation reaction (HOR): Therefore, the catalyst generates protons (H + ) and electrons (e - ) 2H2→4H + +4e - Protons pass through the PEM 1100 and travel from the anode 1112-2 to the cathode 1112- 1, the electrons travel through the conduction path and device 1108 to the annulus around the PEM 1110. The electrons are conducted from the cathode 1112-2 to the cathode 1112-1. The protons and electrons combine with oxygen gas according to the oxygen reduction reaction (ORR): O2+4H + +4e - →2H2O Therefore, the overall electrochemical reaction in the PEM fuel cell 1100 is: 2H2+O2→2H2O is.

[0083] In the overall reaction, the PEM fuel cell 1100 produces water at the cathode 1112-1. Water flows through the PEM 1110 from the cathode 1112-1 to the anode 1112-2. and removed through outlets on the cathode and / or anode sides of the PEM fuel cell 1100. The overall reaction generates electrons at the anode that power the device 1108. .

[0084] (as a porous framework (e.g., PEM900) or as solid support particles) The tetravalent boron-containing proton exchange solid supports described herein (incorporated herein) are useful for the treatment of diseases. For example, the porous structure framework 902 may be , with pores small enough to prevent the transfer of pathogens such as bacteria, fungal spores, and viruses. The boron-based acidic groups 904 may also be used to inhibit the growth of bacteria, fungi, and SARS-CoV-2. For example, SARS-CoV-2 The basic protein sites of pathogens such as erythrocytes ionically bond with the acidic boron sites of the proton exchange membrane. The membrane may then be combined with the proton exchange membrane, thereby preventing the transfer of pathogens through the membrane. Proton exchange membranes are used in face masks, surgical masks, and in enclosed spaces (e.g., homes, Implemented in air filters and air purifiers for offices, hospitals, factories, vehicles, aircraft, etc. It is possible.

[0085] In the foregoing description, various exemplary embodiments have been described with reference to the accompanying figures. However, various modifications and variations thereto may be made without departing from the scope of the following claims. It will be apparent that further embodiments may be implemented, for example Certain features of one embodiment described herein may be combined with other embodiments described herein. These features may be combined or substituted for other features of the present invention. should be considered illustrative rather than limiting.

Claims

1. a proton exchange solid support containing oxygen atoms; a tetravalent boron-based acidic group comprising a boron atom covalently bonded to said oxygen atom; , a boron-containing proton exchange solid support.

2. The proton exchange solid support has a sulfur atom, a carbon atom or a hydroxyl group covalently bonded to the oxygen atom.

2. The boron-containing proton exchange solid support of claim 1, wherein further comprises a phosphorus atom.

3. The sulfur atom, the carbon atom, or the phosphorus atom is shared by a double bond with an additional oxygen atom. The boron-containing proton exchange solid support of claim 2, wherein the boron-containing proton exchange solid support is bonded.

4. 3. The boron-containing proton exchange solid support of claim 2, comprising: further comprising an additional tetravalent boron-based acidic group comprising an additional boron atom; The sulfur atom, the carbon atom, or the phosphorus atom is further covalently bonded to an additional oxygen atom. And, the additional boron atom is covalently bonded to the additional oxygen atom. Roton exchange solid support.

5. The proton exchange solid support is bonded to the sulfur atom, the carbon atom, or the phosphorus atom. further comprising a linker strand, The linker chain is C １ ~C ３０ containing an alkyl chain, The linker chain may be the same or different, with each atom of the linker chain being hydrogen, hydroxyl group, fluoro group, chloro group, dialkylamino group, cyano group, carboxylic acid group, carboxylic acid One or more alkyl groups, which may include an amide group, an ester group, an alkyl group, an alkoxy group, or an aryl group.

10. The boron-containing proton exchange solid support of claim 1, optionally having pendant moieties thereon. body.

6. 10. The boron-containing proton exchange solid support of claim 1, wherein the proton exchange solid support comprises an inorganic material. ion-exchange solid support.

7. 10. The boron-containing proton exchange solid support of claim 1, wherein the proton exchange solid support comprises an organic material. ion-exchange solid support.

8. 10. The method of claim 1, wherein the proton exchange solid support comprises a microparticle or a nanoparticle. Boron-containing proton exchange solid supports.

9. the proton exchange solid support comprises a porous polymer network; The tetravalent boron-based acidic groups are located on the pore surfaces of the porous polymer network.

2. The boron-containing proton exchange solid support of claim 1, wherein the boron-containing proton exchange solid support is placed on a substrate.

10. 10. The method of claim 1, wherein the proton exchange solid support comprises a sulfonic acid functionalized polymer. Boron-containing proton exchange solid supports.

11. 10. The method of claim 1, wherein the proton exchange solid support comprises a carboxylic acid-functionalized polymer. Boron-containing proton exchange solid supports.

12. 10. The method of claim 1, wherein the proton exchange solid support comprises a phosphonic acid-functionalized polymer. Boron-containing proton exchange solid supports.

13. 13. The method of claim 12, wherein the phosphonic acid-functionalized polymer comprises a polyvinyl phosphonic acid polymer.

1. A boron-containing proton exchange solid support according to claim 1.

14. 10. The method of claim 1, wherein the proton exchange solid support comprises a phosphate-functionalized polymer. Boron-containing proton exchange solid support.

15. The phosphate-functionalized polymer is a phosphonic acid doped polybenzimidazole.

15. The boron-containing proton exchange solid support of claim 14, comprising a polymer.

16. The tetravalent boron-based acidic group has the general formula (IV): 【Chemical 1】 In the formula, B is a boron atom, and Z １ , Z ２ , and Z ３ are the same or different, and alkyl group, alkoxy group, alkyloxycarbonyl group, aryl group, aryloxy group, or a fluoro group.

17. 2. The method of claim 1, wherein the tetravalent boron-based acidic group comprises a derivative of a boron-based ester.

2. The boron-containing proton exchange solid support according to claim 1.

18. 2. The method of claim 1, wherein the tetravalent boron-based acidic group comprises a derivative of a boron trifluoride group. The boron-containing proton exchange solid support described above.

19. A boron-containing proton exchange solid having the general formula (Ia), (Ib), (Ic) or (Id) A body support, 【Chemistry 2】 wherein [SS] represents a solid support; X １ is a substituent having the formula (IIa), (IIb), (IIc) or (IId): 【Chemistry 3】 represents X ２ is a group having the formula (IIIa) or (IIIb): 【Chemistry 4】 represents Y １ and Y ２ are the same or different, and each is a tetravalent boron-based acid having the formula (V): represents a functional group, 【Chemistry 5】 In the formula (IV), the boron (B) atom is X １ or X ２ covalently bonded to the oxygen (O) atom of And Z １ , Z ２ and Z ３ are the same or different and are each an alkyl group, an alkoxy group, an alkyl group, an alkyl represents an alkyloxycarbonyl group, an aryl group, an aryloxy group, or a fluoro group; R is C １ ~C ３０ represents an alkyl linker chain, and R is the same as each atom of the linker chain; or may be different, and may be hydrogen, hydroxyl group, fluoro group, chloro group, dialkylamino group, silyl group, Ano group, carboxylic acid group, carboxylic acid amide group, carboxylic acid ester group, alkyl group, alkoxy group boron, optionally having one or more pendant moieties which may include oxy or aryl groups; Element-containing proton exchange solid support.

20. 20. The boron-containing proton exchange solid of claim 19, wherein the solid support comprises an inorganic material. support.

21. 20. The boron-containing proton exchange solid of claim 19, wherein the solid support comprises an organic material. support.

22. 20. The method of claim 19, wherein the solid support comprises an ionomer. Solid support.

23. 20. The boron-containing solid support of claim 19, wherein the solid support comprises a microparticle or a nanoparticle. Proton exchange solid support.

24. [SS]-X 1 , [SS]-X 2 , [SS]-RX 1 , and [SS]-RX 2 are porous polymer networks, respectively. Including Y １ and Y ２ are located on the pore surfaces of the porous polymer network.

20. A boron-containing proton exchange solid support according to 19.

25. 1. A method for making a boron-containing proton exchange solid support, comprising: a boron-based proton exchange solid support, comprising modifying the proton exchange solid support with tetravalent boron-based acidic groups; A method for preparing a proton exchange solid support containing an ion.

26. the proton exchange solid support comprises pendant hydroxyl groups; The modification is carried out by transferring a boron atom contained in the tetravalent boron-based acidic group to the pendant 26. The method of claim 25, comprising covalently bonding the hydroxyl group to an oxygen atom of the hydroxyl group.

27. The modification may be performed using boron trifluoride or a boron-based fluoride in a stoichiometric ratio of about two to one (2:1).

27. The method of claim 26, comprising attaching an ester to the pendant hydroxyl group. method.

28. 26. The method of claim 25, wherein the proton exchange solid support comprises an inorganic material.

29. 26. The method of claim 25, wherein the proton exchange solid support comprises an organic material.

30. 26. The method of claim 25, wherein the proton exchange solid support comprises an ionomer.

31. 26. The method of claim 25, wherein the proton exchange solid support comprises a microparticle or a nanoparticle. How to do it.

32. the proton exchange solid support comprises a porous polymer network; The tetravalent boron-based acidic groups are located on the pore surfaces of the porous polymer network.

26. The method of claim 25, wherein

33. The proton exchange solid support has a sulfur atom covalently bonded to the oxygen atom of the hydroxyl group. a pendant acidic group comprising a sulfur atom, a carbon atom, or a phosphorus atom, contains a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, a phenol group, or a phosphate group 26. The method of claim 25, comprising:

34. The tetravalent boron-based acidic group is a derivative of boron trifluoride or a boron-based ester. The method of claim 25 including a conductor.

35. modifying said proton exchange solid support with additional tetravalent boron-based acidic groups; 26. The method of claim 25, further comprising:

36. The proton exchange solid support has a hydroxyl group covalently bonded to the oxygen atom of the hydroxyl group. a hydroxyl group, and a further oxygen atom of the further hydroxyl group, The modification of the proton exchange solid support with the tetravalent boron-based acidic groups The boron atom contained in the uran-based acidic group is covalently bonded to the oxygen atom of the hydroxyl group. combining modifying the proton exchange solid support with the additional tetravalent boron-based acidic groups by The further boron atom contained in the further tetravalent boron-based acidic group is 36. The method of claim 35, comprising covalently bonding the additional oxygen atom of a hydroxyl group to the additional oxygen atom of the hydroxyl group. How to post.

37. A membrane electrode assembly, a cathode; an anode; a proton exchange membrane disposed between the cathode and the anode; The proton exchange membrane comprising a proton exchange solid support is an oxygen atom, a tetravalent boron-based acidic group comprising a boron atom covalently bonded to said oxygen atom; Mm, membrane electrode assembly.

38. 38. The membrane electrode assembly of claim 37, wherein the proton exchange solid support comprises an inorganic material.

39. 38. The membrane electrode assembly of claim 37, wherein the proton exchange solid support comprises an organic material.

40. 38. The membrane electrode junction of claim 37, wherein the proton exchange solid support comprises an ionomer. body.

41. 38. The method of claim 37, wherein the proton exchange solid support comprises a microparticle or a nanoparticle. Membrane electrode assembly.

42. the proton exchange solid support comprises a porous polymer network; The tetravalent boron-based acidic groups are located on the pore surfaces of the porous polymer network.

38. The membrane electrode assembly of claim 37,

43. 38. The method of claim 37, wherein the proton exchange solid support comprises a sulfonic acid functionalized polymer. Membrane electrode assembly.

44. 38. The method of claim 37, wherein the proton exchange solid support comprises a carboxylic acid-functionalized polymer. Membrane electrode assembly.

45. 38. The method of claim 37, wherein the proton exchange solid support comprises a phosphonic acid-functionalized polymer. Membrane electrode assembly.

46. 46. ​​The phosphonic acid functionalized polymer comprises a polyvinyl phosphonic acid polymer. The membrane electrode assembly according to claim 1.

47. 38. The method of claim 37, wherein the proton exchange solid support comprises a phosphate-functionalized polymer. The membrane electrode assembly shown in Fig.

48. The phosphate-functionalized polymer is a phosphoric acid-doped polybenzimidazole poly 48. The membrane electrode assembly of claim 47, comprising a mer.

49. At least one of the anode or the cathode has a catalyst and a bonding material for bonding the catalyst. Contains ionomers, 38. The membrane electrode assembly of claim 37, wherein the ionomer comprises boron-based acidic groups. 。

50. The tetravalent boron-based acidic group comprises the general formula (IV): 【Chemistry 6】 In the formula, B is a boron atom, and Z １ , Z ２ and Z ３ are the same or different, and each is an alkyl group. an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an aryl group, an aryloxy group, or 38. The membrane electrode assembly of claim 37, wherein represents a fluoro group.

51. The tetravalent boron-based acidic group is boron trifluoride or a boron-based ester group.

38. The membrane electrode assembly of claim 37, comprising a derivative.

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