CN116344879B - Nano composite film with metal-organic framework and preparation method thereof - Google Patents
Nano composite film with metal-organic framework and preparation method thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 90
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000002086 nanomaterial Substances 0.000 claims abstract description 54
- 239000004693 Polybenzimidazole Substances 0.000 claims abstract description 50
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000012528 membrane Substances 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 150000003839 salts Chemical class 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 24
- 239000012265 solid product Substances 0.000 claims description 21
- -1 transition metal salt Chemical class 0.000 claims description 19
- 229960000583 acetic acid Drugs 0.000 claims description 18
- 239000012362 glacial acetic acid Substances 0.000 claims description 18
- 239000013110 organic ligand Substances 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000944 Soxhlet extraction Methods 0.000 claims description 6
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 3
- XXXRZGXFFMAJKQ-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)benzoic acid Chemical compound OC(=O)C1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 XXXRZGXFFMAJKQ-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 9
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 9
- 239000000446 fuel Substances 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000005501 phase interface Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Electrochemistry (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a nano composite membrane with a metal-organic framework and a preparation method thereof, belonging to the field of fuel cells. The application prepares the nano composite membrane through the metal organic framework nano material grafted with the polybenzimidazole on the surface and the perfluorinated sulfonic acid polymer, the porous structure of the metal organic framework nano material can provide more water storage areas in the nano composite membrane, the polybenzimidazole is combined with a rigid chain structure, the polybenzimidazole is outwards and radially grafted on the surface of the metal organic framework nano material, the imidazole structural unit is aprotic, the sulfonic acid group of the perfluorinated sulfonic acid polymer can be adsorbed, the interaction between the metal organic framework nano phase and the perfluorinated sulfonic acid polymer phase is increased, the compatibility is improved, the mechanical property is improved, and the proton conductivity under low water content is improved.
Description
Technical Field
The invention relates to a fuel cell, in particular to a nano composite membrane with a metal-organic framework and a preparation method thereof.
Background
Fuel cells have become one of the research hotspots in the energy field as a renewable, efficient electrical energy conversion technology. In fuel cells, proton exchange membranes are one of the key components responsible for separating hydrogen and oxygen on both sides of the anode and cathode, respectively, and converting them into electrical energy by proton transfer. Proton exchange membranes play a very important role in fuel cells. Firstly, the proton exchange membrane can effectively separate hydrogen and oxygen, and avoid mixing of the hydrogen and the oxygen, thereby ensuring the high-efficiency conversion of the fuel cell. Secondly, the proton exchange membrane has excellent proton conductivity, and can efficiently transfer hydrogen ions to the cathode to generate required electric energy. In addition, the proton exchange membrane can prevent electron mixing between electrodes, thereby avoiding internal short circuit of the battery.
At present, a perfluorosulfonic acid membrane is mainly adopted as the proton exchange membrane, and has excellent proton conductivity and chemical stability. However, the proton conductivity of perfluorosulfonic acid membranes is strongly dependent on water content, limiting their use in high temperature (> 100 ℃) anhydrous or low humidity environments. In addition, although there is a method of producing a composite film by press molding a perfluorosulfonic acid resin and a perfluorocarboxylic acid resin in the prior art, there is a problem that the interlayer of the composite film is liable to foam and peel.
Disclosure of Invention
Based on the above, in order to solve the problem of low proton conductivity of the nanocomposite membrane under the conditions of high temperature and no water or low humidity in the prior art, the invention provides a nanocomposite membrane with a metal-organic framework and a preparation method thereof, and the specific technical scheme is as follows:
a nanocomposite membrane of a metal-organic framework, the nanocomposite membrane is composed of a metal-organic framework nanomaterial of which the surface is grafted with polybenzimidazole and a perfluorosulfonic acid polymer, the metal-organic framework nanomaterial comprises a metal salt and an organic ligand, the metal salt comprises a first metal salt and a second metal salt, and the first metal salt and the second metal salt are one or two of a transition metal salt and a lanthanide metal salt; the organic ligand is one or two of aromatic dicarboxylic acid and aromatic tricarboxylic acid compounds.
In addition, the present application provides a method for preparing a nanocomposite film of a metal-organic framework, the method comprising the steps of:
s1, adding a first metal salt and an organic ligand into an organic solvent for dissolution, then adding glacial acetic acid and water, transferring the solution into an autoclave, reacting for 6-48 hours at 100-200 ℃, centrifugally separating, and taking a solid product to obtain a metal-organic framework nanomaterial;
s2, adding tetraminobiphenyl and a dicarboxylic acid compound into polyphosphoric acid, carrying out heat preservation reaction at 140-160 ℃ under the protection of inert gas, heating to 190-210 ℃ after the heat preservation reaction is completed, adding phosphorus pentoxide and triphenyl phosphite for continuous reaction, adding a precipitant, taking a precipitate, washing with alkali solution and water, carrying out Soxhlet extraction, and drying to obtain carboxyl-terminated polybenzimidazole;
s3, dispersing the metal-organic framework nano material in an organic solvent of a second metal salt by ultrasonic, adding glacial acetic acid and water, placing in an autoclave for reaction at 100-200 ℃ for 24 hours, and centrifugally separating to obtain a solid product;
s4, dispersing the solid product in an organic solvent, performing ultrasonic dispersion, adding the carboxyl-terminated polybenzimidazole, reacting for 12-48 hours at 100-200 ℃ in an autoclave, and performing centrifugal separation to obtain a metal organic framework nano material with the surface grafted with the polybenzimidazole;
s5, dissolving the metal organic framework nano material grafted with polybenzimidazole and the perfluorinated sulfonic acid polymer on the surface in an organic solvent, pouring the organic solvent into a mold frame, carrying out vacuum curing for 24-48 h at 80 ℃, and carrying out curing for 24-48 h at 130 ℃ to obtain the nano composite film with the metal organic framework.
Further, in step S1, the molar ratio of the first metal salt, the organic ligand, the glacial acetic acid, the water and the organic solvent is 1: (0.5-3): (30-60): (1-10): (150-300).
Further, the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
Further, in the step S2, the dicarboxylic acid compound is at least one of isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, 4' -dicarboxydiphenyl ether, 2-bis (4-carboxyphenyl) hexafluoropropane, and sebacic acid.
Further, in the step S2, the molar ratio of the tetraminobiphenyl to the dicarboxylic acid compound is 1 (1.001-1.5).
Further, in step S3, the molar ratio of the second metal salt, the glacial acetic acid, the water, and the organic solvent is 1: (30-60): (1-10): (150-300).
Further, in the step S3, the configuration concentration of the metal-organic framework nano material is 5 mg/mL-60 mg/mL.
Further, in the step S4, the configuration concentration of the solid product is 5 mg/mL-60 mg/mL, and the configuration concentration of the carboxyl-terminated polybenzimidazole is 5 mg/mL-60 mg/mL.
Further, in the step S5, the mass ratio of the metal organic framework nano material grafted with polybenzimidazole on the surface to the perfluorinated sulfonic acid polymer is (0.5-10): 100.
according to the scheme, the metal organic framework nano material with the polybenzimidazole grafted on the surface and the perfluorinated sulfonic acid polymer are used for preparing the nano composite membrane, the porous structure of the metal organic framework nano material can provide more water storage areas in the nano composite membrane, the polybenzimidazole is combined with a rigid chain structure and is grafted on the surface of the metal organic framework nano material in an outward radial mode, the imidazole structural unit is aprotic and can adsorb sulfonic acid groups of the perfluorinated sulfonic acid polymer, interaction between the metal organic framework nano material and the perfluorinated sulfonic acid polymer phase can be increased, compatibility and mechanical performance can be improved, the arrangement of the sulfonic acid groups at the phase interface of the metal organic framework nano material can be guided, and a water delivery channel (sulfonic acid group area) which takes the water storage area (metal organic framework phase) as the center and is outward radial is formed, so that proton conductivity under low water content is improved, bubbling and stripping are easy to occur between the composite membrane layers, and the nano composite membrane prepared by the method can be better applied in a high-temperature anhydrous or low-humidity environment.
Drawings
FIG. 1 is a schematic view of proton conductivity of the composite membrane and Nafion prepared in examples 1-3 and comparative examples 1-3;
FIG. 2 is a schematic illustration of the interface of a perfluorinated sulfonic acid polymer with a metal-organic framework material;
FIG. 3 is a schematic diagram of the interface between a perfluorinated sulfonic acid polymer and a polybenzimidazole modified metal organic framework material.
Detailed Description
The present invention will be described in further detail with reference to the following examples thereof in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The nano composite membrane of the metal-organic framework comprises a metal-organic framework nano material with polybenzimidazole grafted on the surface and a perfluorinated sulfonic acid polymer, wherein the metal-organic framework nano material comprises metal salts and organic ligands, the metal salts comprise first metal salts and second metal salts, and the first metal salts and the second metal salts are one or two of transition metal salts and lanthanide metal salts; the organic ligand is one or two of aromatic dicarboxylic acid and aromatic tricarboxylic acid compounds.
In addition, the present application provides a method for preparing a nanocomposite film of a metal-organic framework, the method comprising the steps of:
s1, adding a first metal salt and an organic ligand into an organic solvent for dissolution, then adding glacial acetic acid and water, transferring the solution into an autoclave, reacting for 6-48 hours at 100-200 ℃, centrifugally separating, and taking a solid product to obtain a metal-organic framework nanomaterial;
s2, adding tetraminobiphenyl and a dicarboxylic acid compound into polyphosphoric acid, carrying out heat preservation reaction at 140-160 ℃ under the protection of inert gas, heating to 190-210 ℃ after the heat preservation reaction is completed, adding phosphorus pentoxide and triphenyl phosphite for continuous reaction, adding a precipitant, taking a precipitate, washing with alkali solution and water, carrying out Soxhlet extraction, and drying to obtain carboxyl-terminated polybenzimidazole;
s3, dispersing the metal-organic framework nano material in an organic solvent of a second metal salt by ultrasonic, adding glacial acetic acid and water, placing in an autoclave for reaction at 100-200 ℃ for 24 hours, and centrifugally separating to obtain a solid product;
s4, dispersing the solid product in an organic solvent, performing ultrasonic dispersion, adding the carboxyl-terminated polybenzimidazole, reacting for 12-48 hours at 100-200 ℃ in an autoclave, and performing centrifugal separation to obtain a metal organic framework nano material with the surface grafted with the polybenzimidazole;
s5, dissolving the metal organic framework nano material grafted with polybenzimidazole and the perfluorinated sulfonic acid polymer on the surface in an organic solvent, pouring the organic solvent into a mold frame, carrying out vacuum curing for 24-48 h at 80 ℃, and carrying out curing for 24-48 h at 130 ℃ to obtain the nano composite film with the metal organic framework.
In one embodiment, in step S1, the molar ratio of the first metal salt, the organic ligand, the glacial acetic acid, the water, and the organic solvent is 1: (0.5-3): (30-60): (1-10): (150-300).
In one embodiment, the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.
In one embodiment, in step S2, the dicarboxylic acid compound is at least one of isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, 4' -dicarboxydiphenyl ether, 2-bis (4-carboxyphenyl) hexafluoropropane, and sebacic acid.
In one embodiment, in the step S2, the molar ratio of the tetraminobiphenyl to the dicarboxylic acid compound is 1 (1.001-1.5).
In one embodiment, in step S3, the molar ratio of the second metal salt, the glacial acetic acid, the water, and the organic solvent is 1: (30-60): (1-10): (150-300).
In one embodiment, in the step S3, the configuration concentration of the metal-organic framework nanomaterial is 5mg/mL to 60mg/mL.
In one embodiment, in the step S4, the configuration concentration of the solid product is 5 mg/mL-60 mg/mL, and the configuration concentration of the carboxyl-terminated polybenzimidazole is 5 mg/mL-60 mg/mL.
In one embodiment, in the step S5, the concentration of the perfluorinated sulfonic acid polymer is 50 mg/mL-150 mg/mL.
In one embodiment, in the step S5, the mass ratio of the metal-organic framework nanomaterial with polybenzimidazole grafted on the surface to the perfluorosulfonic acid polymer is (0.5-10): 100.
according to the scheme, the metal organic framework nano material with the polybenzimidazole grafted on the surface and the perfluorinated sulfonic acid polymer are used for preparing the nano composite membrane, the porous structure of the metal organic framework nano material can provide more water storage areas in the nano composite membrane, the polybenzimidazole is combined with a rigid chain structure and is grafted on the surface of the metal organic framework nano material in an outward radial mode, the imidazole structural unit is aprotic and can adsorb sulfonic acid groups of the perfluorinated sulfonic acid polymer, interaction between the metal organic framework nano material and the perfluorinated sulfonic acid polymer phase can be increased, compatibility and mechanical performance can be improved, the arrangement of the sulfonic acid groups at the phase interface of the metal organic framework nano material can be guided, and a water delivery channel (sulfonic acid group area) which takes the water storage area (metal organic framework phase) as the center and is outward radial is formed, so that proton conductivity under low water content is improved, bubbling and stripping are easy to occur between the composite membrane layers, and the nano composite membrane prepared by the method can be better applied in a high-temperature anhydrous or low-humidity environment.
Embodiments of the present invention will be described in detail below with reference to specific examples.
Example 1:
a method for preparing a nano composite film with a metal-organic framework, which comprises the following steps:
(1) Adding 1g of zirconium chloride and 1g of 2-amino terephthalic acid into 80mL of N, N-dimethylacetamide for dissolution, continuously adding 10mL of glacial acetic acid and 1mL of water, transferring the solution into an autoclave, reacting for 9h at 140 ℃, centrifugally separating, and taking a solid product to obtain a metal-organic framework nanomaterial;
(2) Adding 2g of tetraminobiphenyl and 1.72g of dicarboxylic acid compound into 110g of polyphosphoric acid, carrying out heat preservation reaction at 150 ℃ under the protection of inert gas, heating to 210 ℃ after the heat preservation reaction is completed, adding 3g of phosphorus pentoxide and 0.1g of triphenyl phosphite for continuous reaction, adding the obtained product into water to obtain a precipitate, washing the obtained precipitate with alkaline solution and water in sequence, carrying out Soxhlet extraction, and drying to obtain carboxyl-terminated polybenzimidazole;
(3) 1g of carboxyl-terminated polybenzimidazole is ultrasonically dispersed in 80mL of N, N-dimethylacetamide solution containing 1g of zirconium chloride, 10mL of glacial acetic acid and 1mL of water are added, and the mixture is placed in an autoclave for reaction at 140 ℃ for 24 hours, and centrifugal separation is carried out, so that a solid product is obtained;
(4) Dispersing 1g of solid product in 100mL of N, N-dimethylacetamide, performing ultrasonic dispersion, adding 1g of carboxyl-terminated polybenzimidazole, reacting for 24 hours at 140 ℃ in an autoclave, and performing centrifugal separation to obtain a metal organic framework nanomaterial with the surface grafted with polybenzimidazole;
(5) 0.05g of metal organic framework nano material with polybenzimidazole grafted on the surface and 1g of perfluorinated sulfonic acid polymer are dissolved in 10mL of N, N-dimethylacetamide, poured into a mold frame, vacuum cured for 48 hours at 80 ℃, and cured for 48 hours at 130 ℃ to obtain the nano composite membrane with the metal organic framework.
Example 2:
a method for preparing a nano composite film with a metal-organic framework, which comprises the following steps:
(1) Adding 0.5g of zirconium chloride, 0.7g of nickel nitrate hexahydrate, 0.5g of 2-amino terephthalic acid and 0.6g of terephthalic acid into 80mL of N, N-dimethylformamide for dissolution, continuously adding 10mL of glacial acetic acid and 1mL of water, transferring the solution into an autoclave, reacting for 12 hours at 200 ℃, centrifuging, and taking a solid product to obtain a metal-organic framework nanomaterial;
(2) Adding 2g of tetraminobiphenyl and 1.86g of dicarboxylic acid compound into 110g of polyphosphoric acid, carrying out heat preservation reaction at 150 ℃ under the protection of inert gas, heating to 200 ℃ after the heat preservation reaction is completed, adding 3g of phosphorus pentoxide and 0.1g of triphenyl phosphite for continuous reaction, adding the obtained product into water to obtain a precipitate, washing the obtained precipitate with alkaline solution and water in sequence, carrying out Soxhlet extraction, and drying to obtain carboxyl-terminated polybenzimidazole;
(3) 1g of carboxyl-terminated polybenzimidazole is dispersed in 80mLN, N-dimethylformamide solution containing 1g of zirconium chloride by ultrasonic, 10mL of glacial acetic acid and 1mL of water are added, and the mixture is placed in an autoclave for reaction at 140 ℃ for 24 hours, and centrifugal separation is carried out, so that a solid product is obtained;
(4) Dispersing 1g of solid product in 50mL of N, N-dimethylformamide, performing ultrasonic dispersion, adding 1g of carboxyl-terminated polybenzimidazole, reacting for 24 hours at 140 ℃ in an autoclave, and performing centrifugal separation to obtain a metal organic framework nanomaterial with the surface grafted with the polybenzimidazole;
(5) 0.01g of metal organic framework nano material with polybenzimidazole grafted on the surface and 1g of perfluorinated sulfonic acid polymer are dissolved in 15mL of N, N-dimethylformamide, poured into a mold frame, cured for 48h at 80 ℃ in vacuum, and then cured for 48h at 130 ℃ to obtain the nano composite membrane with the metal organic framework.
Example 3:
a method for preparing a nano composite film with a metal-organic framework, which comprises the following steps:
(1) Adding 0.5g of zirconium chloride, 0.6g of copper nitrate trihydrate, 0.8g of 2-amino terephthalic acid and 0.3g of terephthalic acid into 60mL of N, N-dimethylformamide for dissolution, adding 10mL of glacial acetic acid and 1mL of water, transferring the solution into an autoclave, reacting at 180 ℃ for 24 hours, centrifuging, and taking a solid product to obtain a metal organic framework nano material;
(2) Dissolving 2g of tetraminobiphenyl and 2.1g of dicarboxylic acid compound in 110g of polyphosphoric acid, carrying out heat preservation reaction at 150 ℃ under the protection of inert gas, heating to 190-210 ℃ after heat preservation is finished, adding 3g of phosphorus pentoxide and 0.1g of triphenyl phosphite for continuous reaction, adding the obtained product into water to obtain a precipitate, washing the obtained precipitate with alkaline solution and water in sequence, carrying out Soxhlet extraction, and drying to obtain carboxyl-terminated polybenzimidazole;
(3) 1g of metal organic framework nano material is ultrasonically dispersed in 100mLN, N-dimethylacetamide solution containing 1.2g of copper nitrate trihydrate, 10mL of glacial acetic acid and 1mL of water are added, and the mixture is placed in an autoclave for reaction at 180 ℃ for 24 hours, and centrifugal separation is carried out, so that a solid product is obtained;
(4) Dispersing 1g of solid product in 20mL of N, N-dimethylacetamide, performing ultrasonic dispersion, adding 1g of carboxyl-terminated polybenzimidazole, reacting for 24 hours at 140 ℃ in an autoclave, and performing centrifugal separation to obtain a metal organic framework nanomaterial with the surface grafted with polybenzimidazole;
(5) 0.1g of metal organic framework nano material with polybenzimidazole grafted on the surface and 1g of perfluorinated sulfonic acid polymer are dissolved in 20mL of N, N-dimethylformamide, poured into a mold frame, cured for 48 hours at 80 ℃ in vacuum, and then cured for 48 hours at 130 ℃ to obtain the nano composite membrane with the metal organic framework.
Comparative example 1:
comparative example 1 is different from example 3 in that the metal-organic framework nanomaterial in comparative example 1 is not modified with polybenzimidazole, i.e., the surface of the metal-organic framework nanomaterial is not grafted with polybenzimidazole.
Comparative example 2:
comparative example 2 differs from example 3 in that in comparative example 3 only the carboxy-terminated polybenzimidazole and perfluorosulfonic acid polymer were dissolved in 20ml of n, n-dimethylformamide and poured into a mold frame, vacuum-cured at 80 ℃ for 48 hours, and then cured at 130 ℃ for 48 hours to obtain a nanocomposite film. Namely, the metal-organic framework nano material is not added in the comparative example 2.
Comparative example 3:
comparative example 3 differs from example 3 in that the metal-organic framework nanomaterial with polybenzimidazole grafted on the surface of comparative example 3 is replaced with a cage polysilsesquioxane to which polybenzimidazole hydrochloride is attached.
In addition, the nanocomposite films prepared in examples 1 to 3 and the composite films prepared in comparative examples 1 to 3 were subjected to the relevant performance test, and the results are shown in table 1 below.
Table 1:
from the data analysis of table 1, it is known that the nanocomposite film of the present application has excellent mechanical properties, the surface of the nano material with metal-organic framework added in comparative example 1 is not grafted with polybenzimidazole, the mechanical properties are worse than those of the nano material with metal-organic framework added in example 3, the mechanical properties are obviously reduced, and the synergistic effect between the components of the present application is demonstrated, so that not only can excellent proton conductivity be obtained, but also excellent mechanical properties can be given.
In addition, fig. 1 shows proton conductivities of Nafion membranes and perfluorosulfonic acid nanocomposite membranes based on metal-organic frameworks at different temperatures, with a membrane moisture content of 10wt%. FIG. 2 is a schematic illustration of the interface of a perfluorinated sulfonic acid polymer with a metal-organic framework material; FIG. 3 is a schematic diagram of the interface between a perfluorinated sulfonic acid polymer and a polybenzimidazole modified metal organic framework material. The coarse-grained kinetics simulation water bead distribution density chart (water content 5 wt%) and the arrangement of the sulfonic acid groups at the phase interface of the metal-organic framework nano-material can be seen in combination with fig. 2 and 3, so as to form a water delivery channel (sulfonic acid group region) which is radially outwards centered on the water storage region (metal-organic framework phase).
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. The nano composite membrane is characterized by comprising a metal organic framework nano material with a polybenzimidazole grafted on the surface and a perfluorinated sulfonic acid polymer, wherein the metal organic framework nano material comprises a metal salt and an organic ligand, the metal salt comprises a first metal salt and a second metal salt, and the first metal salt and the second metal salt are one or two of a transition metal salt and a lanthanide metal salt; the organic ligand is one or two of aromatic dicarboxylic acid and aromatic tricarboxylic acid compounds;
the preparation method of the nano composite film with the metal-organic framework comprises the following steps:
s1, adding a first metal salt and an organic ligand into an organic solvent for dissolution, then adding glacial acetic acid and water, transferring the solution into an autoclave, reacting for 6-48 hours at 100-200 ℃, centrifugally separating, and taking a solid product to obtain a metal-organic framework nanomaterial;
s2, adding tetraminobiphenyl and a dicarboxylic acid compound into polyphosphoric acid, carrying out heat preservation reaction at 140-160 ℃ under the protection of inert gas, heating to 190-210 ℃ after the heat preservation reaction is completed, adding phosphorus pentoxide and triphenyl phosphite for continuous reaction, adding a precipitant, taking a precipitate, washing with alkali solution and water, carrying out Soxhlet extraction, and drying to obtain carboxyl-terminated polybenzimidazole;
s3, dispersing the metal-organic framework nano material in an organic solvent of a second metal salt by ultrasonic, adding glacial acetic acid and water, placing in an autoclave for reaction at 100-200 ℃ for 24 hours, and centrifugally separating to obtain a solid product;
s4, dispersing the solid product in an organic solvent, performing ultrasonic dispersion, adding the carboxyl-terminated polybenzimidazole, reacting for 12-48 hours at 100-200 ℃ in an autoclave, and performing centrifugal separation to obtain a metal organic framework nano material with the surface grafted with the polybenzimidazole;
s5, dissolving the metal organic framework nano material grafted with polybenzimidazole and the perfluorinated sulfonic acid polymer on the surface in an organic solvent, pouring the organic solvent into a mold frame, carrying out vacuum curing for 24-48 h at 80 ℃, and carrying out curing for 24-48 h at 130 ℃ to obtain the nano composite film with the metal organic framework.
2. The metal-organic framework nanocomposite film according to claim 1, wherein in step S1, the molar ratio of the first metal salt, the organic ligand, the glacial acetic acid, the water and the organic solvent is 1: (0.5-3): (30-60): (1-10): (150-300).
3. The metal-organic framework nanocomposite film according to claim 2, wherein the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone.
4. The metal-organic framework nanocomposite film according to claim 2, wherein in step S2, the dicarboxylic acid compound is at least one of isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, 4' -dicarboxydiphenyl ether, 2-bis (4-carboxyphenyl) hexafluoropropane, and sebacic acid.
5. The metal-organic framework nanocomposite film according to claim 4, wherein in step S2, the molar ratio of the tetraminobiphenyl to the dicarboxylic acid compound is 1 (1.001 to 1.5).
6. The metal-organic framework nanocomposite film according to claim 2, wherein in step S3, the second metal salt, the glacial acetic acid, the water, the organic solvent are in a molar ratio of 1: (30-60): (1-10): (150-300).
7. The metal-organic framework nanocomposite film according to claim 2, wherein in step S3, the metal-organic framework nanomaterial is disposed at a concentration of 5mg/mL to 60mg/mL.
8. The metal-organic framework nanocomposite film according to claim 2, wherein in step S4, the solid product is disposed at a concentration of 5mg/mL to 60mg/mL, and the carboxyl-terminated polybenzimidazole is disposed at a concentration of 5mg/mL to 60mg/mL.
9. The metal-organic framework nanocomposite film according to claim 2, wherein in step S5, the mass ratio of the metal-organic framework nanomaterial to the perfluorosulfonic acid polymer, on which polybenzimidazole is grafted on the surface, is (0.5-10): 100.
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