CN115490871B - PolyMOF nano-sheet, preparation method, membrane prepared from PolyMOF nano-sheet and application of PolyMOF nano-sheet - Google Patents
PolyMOF nano-sheet, preparation method, membrane prepared from PolyMOF nano-sheet and application of PolyMOF nano-sheet Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 48
- 239000012528 membrane Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 10
- -1 preparation method Substances 0.000 title description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 18
- 239000000446 fuel Substances 0.000 claims abstract description 17
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 8
- 108010020346 Polyglutamic Acid Proteins 0.000 claims abstract description 5
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 5
- 229920002643 polyglutamic acid Polymers 0.000 claims abstract description 5
- 239000013384 organic framework Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 19
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 14
- 239000002064 nanoplatelet Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
Abstract
The invention belongs to the technical field of nanomaterials and fuel cell diaphragms, and particularly relates to a PolyMOF nanosheet, a preparation method thereof and application thereof in a fuel cell proton exchange membrane. The organic framework in the nano-sheet is a CuTCPP metal organic framework, and the polymer chain is one of polyacrylic acid and polyglutamic acid. The rich carboxylic acid groups in the nano-sheets endow the polymoff-based layered proton exchange membrane with super-strong proton conductivity, and meanwhile, the polymer chains with excellent moisture absorption capability construct continuous proton transfer channels along the vertical direction, so that the polymoff-based layered proton exchange membrane has high proton conductivity in a wide humidity range.
Description
Technical Field
The invention belongs to the technical field of nanomaterials and fuel cell diaphragms, and particularly relates to a PolyMOF nanosheet, a preparation method thereof and application thereof in a fuel cell proton exchange membrane.
Background
With the increasing demand of energy consumption in the global area, the traditional fossil fuels such as petroleum, coal, natural gas and the like are taken as no longer availableRaw resources, potentially in danger of energy shortage. Fuel cells are considered the first efficient and clean power generation technology in the 21 st century. Proton exchange membranes are known as "hearts" of fuel cells as key materials for fuel cells. The proton exchange membranes currently commercialized are represented by the Nafion series perfluorosulfonic acid membranes produced by Chemours, usa, and have excellent proton conductivity (-0.1S cm) at high humidity -1 ). However, the water loss under the conditions of high temperature and low humidity can lead to shrinkage and even collapse of the transmission channel, so that the conduction performance is reduced by orders of magnitude. Therefore, development of a proton exchange membrane having excellent conductivity and stable mechanical properties at high temperature and low humidity is critical to obtain a high-performance fuel cell.
The metal organic framework has higher crystallinity and ordered pore structure, can be used as a stable and regular proton exchange channel, and is considered as a promising proton exchange membrane material. However, due to the lack of sufficient proton carriers, the intrinsic conductivity of most MOFs is generally low and their structural instability in the humid environment of the fuel cell operation process also limits their further application.
Disclosure of Invention
The invention aims to provide a polymer-assisted self-inhibition synthetic PolyMOF nano-sheet, wherein a layered membrane prepared from the PolyMOF nano-sheet has excellent conductivity and water stability compared with the traditional MOF, and has stronger proton conductivity at high temperature and low humidity compared with a commercial Nafion membrane.
In order to solve the technical problems, the invention adopts the following technical scheme:
an organic framework in the PolyMOF nano-sheet is a CuTCPP metal organic framework, and a polymer chain is an oligomer rich in carboxylic acid groups, preferably one of polyacrylic acid and polyglutamic acid.
The nano sheet is in a two-dimensional sheet structure, the thickness is 4-5nm, and the transverse dimension is 3-5 mu m. The invention further provides a preparation method of the PolyMOF nanosheets, which comprises the following steps:
s1: dissolving copper nitrate trihydrate, an oligomer rich in carboxylic acid groups and pyrazine in a mixed solution of N, N-dimethylformamide and ethanol, and stirring for 20-40min to ensure that copper nitrate and the oligomer rich in the carboxylic acid groups are preassembled, and the copper nitrate is nucleated on side chains of the oligomer rich in the carboxylic acid groups;
s2: dissolving tetra (4-carboxyphenyl) porphyrin in a mixed solution of N, N-dimethylformamide and ethanol, and slowly dripping the solution into the solution in the step S1;
s3: and (3) carrying out hydrothermal reaction on the solution obtained in the step (S2) to obtain the PolyMOF nanosheets.
Further, copper nitrate trihydrate: carboxylic acid groups in the oligomers rich in carboxylic acid groups: pyrazine: the mass ratio of tetra (4-carboxyphenyl) porphyrin was 7.5:1:5:2.5; in the solutions of steps S1 and S2, the molar ratio of N, N-dimethylformamide to ethanol is 3:1, a step of; in step S1, the concentration of copper nitrate trihydrate in the mixed solution is 1-1.6mmol/L.
The temperature of the hydrothermal reaction is 80 ℃ and the reaction time is 3-5h.
The invention can also be used for preparing the proton exchange membrane of the fuel cell by utilizing the nano-sheets, namely, the PolyMOF nano-sheets are firstly prepared into dispersion liquid and then formed into a membrane.
The concentration of the dispersion may be selected to be 0.1 to 5g/L, preferably 0.1g/L.
The proton exchange membrane of the fuel cell has good application in the fuel cell.
The PolyMOF nanosheets are prepared in one step by adopting a polymer-assisted self-inhibition synthesis strategy. The PolyMOF nanosheets are one of CuTCPP@PAA nanosheets and CuTCPP@PGA nanosheets, are of a two-dimensional lamellar structure, are regular in structure and uniform in size, have the characteristics of large specific surface area and strong water stability, and show excellent conductivity and mechanical properties when applied to fuel cell membranes.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) The invention provides a polymer assisted self-inhibition synthesis strategy for preparing a PolyMOF nanosheet, wherein a low molecular weight polymer chain rich in carboxyl is firstly selected in the reaction process, and the polymer chain participates in the MOF crystal growth process in situ through pre-assembly with metal ions, so that the growth of the crystal in the Z-axis direction is inhibited to prepare the PolyMOF nanosheet by one step, the reaction step is simplified, the preparation efficiency is improved, the solution generated in the preparation process is pollution-free, and the atomic utilization rate in the whole preparation process is high;
2) The PolyMOF nanomaterial prepared by the invention has a two-dimensional lamellar structure, and the nanoplatelets have the characteristics of regular structure, uniform size, large specific surface and strong water stability;
3) The crosslinking of polymer chains between layers of the prepared PolyMOF-based layered proton exchange membrane obviously improves the mechanical strength and the water stability of the membrane;
4) The rich carboxylic acid groups in the nano-sheets endow the polymoff-based layered proton exchange membrane with super-strong proton conductivity, and meanwhile, the polymer chains with excellent moisture absorption capability construct continuous proton transfer channels along the vertical direction, so that the polymoff-based layered proton exchange membrane has high proton conductivity in a wide humidity range.
Drawings
FIG. 1 is a scanning electron microscope image of PolyMOF nanoplatelets obtained in example 1;
FIG. 2 is N before and after water treatment of PolyMOF nanoplatelets obtained in example 1 2 Adsorption curve;
FIG. 3 is a sectional scanning electron microscope image and a corresponding physical image of the PolyMOF-based layered proton exchange membrane obtained in example 1;
FIG. 4 shows the strain curves and mechanical properties of the PolyMOF-based layered proton exchange membrane obtained in example 1;
FIG. 5 is a glancing-in X-ray diffraction pattern of a PolyMOF-based layered proton exchange membrane obtained in example 1 before and after water treatment;
FIG. 6 is a graph of humidity versus proton conductivity for a PolyMOF-based layered proton exchange membrane obtained in example 1.
Detailed Description
The following specific embodiments are used to illustrate the technical solution of the present invention, but the scope of the present invention is not limited thereto:
example 1
1) Preparation of PolyMOF nanosheets:
s1: 0.15mmol of copper nitrate trihydrate (36 mg), 0.1mmol of pyrazine (8 mg) and 0.02mmol of polyacrylic acid (40 mg) were dissolved in 120mL of a mixed solution of N, N-Dimethylformamide (DMF) and ethanol (V: V=3:1), and placed in a 200mL reaction vessel and stirred thoroughly;
s2: 0.05mmol of TCPP (40 mg) is dissolved in 40mL of a mixture of DMF and ethanol (V: V=3:1). Dropwise adding the solution of TCPP into the solution of S1 under stirring;
s3: and (3) heating the solution obtained in the step (S2) to 80 ℃ in a reaction kettle, performing thermal reaction for 3 hours, centrifuging and collecting for 10 minutes at 8000r/min, and washing with ethanol for 3 times to obtain the CuTCPP@PAA nano-sheet.
2) Layered films were prepared using polymorf nanoplatelets: re-dispersing the obtained CuTCPP@PAA nano sheet in 100mL of ethanol to obtain a dispersion liquid of the CuTCPP@PAA two-dimensional nano sheet; 250mL of CuTCPP@PAA nano sheet dispersion liquid is added into a suction filtration device, suction filtration is carried out under the suction filtration pressure of 0.2bar, so that the CuTCPP@PAA nano sheets are slowly self-stacked on a base film, a CuTCPP@PAA layered film is obtained, and then the CuTCPP@PAA layered film is placed into a vacuum drying oven and dried for 12 hours at the temperature of 60 ℃.
As can be seen from fig. 2, the obtained cutcpp@paa layered film has a regular layered morphology with a thickness of 20 μm. The ultra-thin thickness and regular inter-layer channels provide a more efficient, regular, ordered transfer path for efficient proton transfer.
The vertical proton conductivity (Proton conductivity, sigma, S cm) of the material was measured using a ParStat MC1000 electrochemical workstation from Pranceton using a two electrode AC impedance method -1 ). The oscillating voltage is 10mV, and the scanning frequency range is 1M-10Hz. The temperature and humidity of the test were controlled by a MTS-740 membrane test apparatus manufactured by Scribnerrassicates Inc. The stabilization time was 1h for each temperature and humidity test.
Proton conductivity (σ) is calculated from the following formula:
wherein, the liquid crystal display device comprises a liquid crystal display device,l is the thickness (cm) of the film, R is the impedance (Ω) of the film, A is the area of contact between the film and the electrode (cm) 2 )。
The results show that the conductivity of the CuTCPP@PAA film reaches 98mS cm at 80 ℃ and 100% RH -1 The conductivity at 80 ℃ and 60% RH reaches 48.2mS cm -1 Higher than the existing commercial membrane Nafion 212 level.
Example 2
1) Preparation of PolyMOF nanosheets:
s1: 0.15mmol of copper nitrate trihydrate (36 mg), 0.1mmol of pyrazine (8 mg) and 0.007mmol of polyglutamic acid (70 mg) were dissolved in 120mL of a mixed solution of N, N-dimethylformamide and ethanol (V: V=3:1), and placed in a 200mL reaction vessel and stirred to be thoroughly mixed;
s2: 0.05mmol of TCPP (40 mg) is dissolved in 40mL of a mixture of DMF and ethanol (V: V=3:1). Dropwise adding the solution of TCPP into the solution of S1 under stirring;
s3: and (3) heating the solution in the step (S2) to 80 ℃ in a reaction kettle, performing thermal reaction for 3 hours, centrifuging and collecting for 10 minutes at 8000r/min, and washing with ethanol for 3 times to obtain the CuTCPP@PGA nanosheets.
2) Layered films were prepared using polymorf nanoplatelets: re-dispersing the obtained CuTCPP@PGA nano sheet in 100mL of ethanol to obtain a dispersion liquid of the CuTCPP@PGA two-dimensional nano sheet; adding 250mL of CuTCPP@PGA nanosheet dispersion liquid into a suction filtration device, performing suction filtration under the suction filtration pressure of 0.2bar, enabling the CuTCPP@PGA nanosheets to slowly self-stack on a base film to obtain a CuTCPP@PGA layered film, and then placing the layered film into a vacuum drying oven to be dried at 60 ℃ for 12 hours.
Vertical proton conductivity testing was performed using the same apparatus and method as in example 1. The results show that the conductivity of the CuTCPP@PGA film reaches 112mS cm at 80 ℃ and 100% RH -1 The conductivity at 80 ℃ and 60% RH reaches 55.6mS cm -1 The conductivity at 80℃and 20% RH reaches 25.6mS cm -1 Much higher than the commercial Nafion 212 level.
The tensile strength and Young's modulus of the PolyMOF nano-sheet-based layered film synthesized in the examples and the traditional layered film are shown in Table 1, and the films prepared from the nano-sheets synthesized in the examples have higher mechanical properties.
TABLE 1 tensile Strength and Young's modulus of different layered films
Graphene oxide and boron nitride in Table 1 are obtained with reference to Coleman J N, lotya M, neill A O, et al Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials [ J ], science,2011,331,568-571.
CuTCPP is obtained in reference to WangY, gaoH X, wuW J, nafion-threaded MOF laminar membrane with efficient and stable transfer channels towards highly enhancedproton conduction [ J ], nano Research,2022,15,3195-3203.
The MN-C@Nafion is obtained by references Tian M, pei F, yao M S, ultrathin MOF nanosheet assembled highly oriented microporous membrane as an interlayer for lithium-sulforbates [ J ], energy Storage Materials,2019,21,14-21.
Claims (10)
1. The PolyMOF nanosheets are characterized in that an organic framework in the nanosheets is a CuTCPP metal organic framework, and polymer chains are oligomers rich in carboxylic acid groups;
the PolyMOF nanosheets are obtained by the following method:
s1: dissolving copper nitrate trihydrate, an oligomer rich in carboxylic acid groups and pyrazine in a mixed solution of N, N-dimethylformamide and ethanol, and stirring for 20-40min to ensure that copper nitrate and the oligomer rich in the carboxylic acid groups are preassembled, and the copper nitrate is nucleated on side chains of the oligomer rich in the carboxylic acid groups;
s2: dissolving tetra (4-carboxyphenyl) porphyrin in a mixed solution of N, N-dimethylformamide and ethanol, and slowly dripping the solution into the solution in the step S1;
s3: and (3) carrying out hydrothermal reaction on the solution obtained in the step (S2) to obtain the PolyMOF nanosheets.
2. The polymorf nanoplatelets of claim 1, wherein the polymer chains in the nanoplatelets are one of polyacrylic acid, polyglutamic acid.
3. The polymofer nanoplatelets of claim 1, wherein the nanoplatelets have a two-dimensional platelet structure having a thickness of 4-5nm and a lateral dimension of 3-5 μm.
4. The method for preparing polymofa nanoplatelets according to claim 1, characterized by the following steps:
s1: dissolving copper nitrate trihydrate, an oligomer rich in carboxylic acid groups and pyrazine in a mixed solution of N, N-dimethylformamide and ethanol, and stirring for 20-40min to ensure that copper nitrate and the oligomer rich in the carboxylic acid groups are preassembled, and the copper nitrate is nucleated on side chains of the oligomer rich in the carboxylic acid groups;
s2: dissolving tetra (4-carboxyphenyl) porphyrin in a mixed solution of N, N-dimethylformamide and ethanol, and slowly dripping the solution into the solution in the step S1;
s3: and (3) carrying out hydrothermal reaction on the solution obtained in the step (S2) to obtain the PolyMOF nanosheets.
5. The method of preparing polymorf nanoplatelets as in claim 4, wherein copper nitrate trihydrate: carboxylic acid groups in the oligomers rich in carboxylic acid groups: pyrazine: the mass ratio of tetra (4-carboxyphenyl) porphyrin was 7.5:1:5:2.5; in the solutions of steps S1 and S2, the molar ratio of N, N-dimethylformamide to ethanol is 3:1, a step of; in step S1, the concentration of copper nitrate trihydrate in the mixed solution is 1-1.6mmol/L.
6. The method of preparing polymorf nanosheets of claim 5, wherein the oligomer rich in carboxylic acid groups is polyacrylic acid or polyglutamic acid.
7. The method of preparing polymofer nanoplatelets as in claim 4, wherein the hydrothermal reaction is carried out at a temperature of 80 ℃ for a reaction time of 3-5h.
8. A proton exchange membrane for a fuel cell, wherein the membrane is obtained by forming a polymorf nanosheet according to any one of claims 1-3 into a dispersion and then forming the membrane.
9. The fuel cell proton exchange membrane according to claim 8 wherein the concentration of the dispersion is 0.1 to 5 g/L.
10. Use of the fuel cell proton exchange membrane of claim 8 in a fuel cell.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017052474A1 (en) * | 2015-09-23 | 2017-03-30 | Nanyang Technological University | A metal-organic framework nanosheet |
| CN110258119A (en) * | 2019-05-17 | 2019-09-20 | 天津工业大学 | A kind of preparation method of metal organic framework nanofiber modified proton exchange film |
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| KR102050597B1 (en) * | 2018-01-02 | 2019-12-03 | 재단법인대구경북과학기술원 | METOHD OF in situ preparATION OF a metal-organic framework from a diffusion-control within an ionic polymer |
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