CN112058268A - Preparation method of zeolite imidazolyl metal organic framework nanosheet for oxygen reduction reaction - Google Patents
Preparation method of zeolite imidazolyl metal organic framework nanosheet for oxygen reduction reaction Download PDFInfo
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- 239000001301 oxygen Substances 0.000 title claims abstract description 61
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000006722 reduction reaction Methods 0.000 title claims abstract description 60
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 33
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 27
- 239000010457 zeolite Substances 0.000 title claims abstract description 27
- 239000002135 nanosheet Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 230000003197 catalytic effect Effects 0.000 claims abstract description 31
- 230000009467 reduction Effects 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 174
- 239000000243 solution Substances 0.000 claims description 139
- 239000000463 material Substances 0.000 claims description 113
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 104
- 239000002904 solvent Substances 0.000 claims description 74
- 239000011259 mixed solution Substances 0.000 claims description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000008367 deionised water Substances 0.000 claims description 50
- 229910021641 deionized water Inorganic materials 0.000 claims description 50
- 229920000557 Nafion® Polymers 0.000 claims description 46
- 239000007864 aqueous solution Substances 0.000 claims description 46
- 238000001291 vacuum drying Methods 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 44
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 39
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 37
- 238000001354 calcination Methods 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 27
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical class O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 23
- 238000004502 linear sweep voltammetry Methods 0.000 claims description 23
- 238000012360 testing method Methods 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000012046 mixed solvent Substances 0.000 claims description 10
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 150000002460 imidazoles Chemical class 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- LDZYRENCLPUXAX-UHFFFAOYSA-N 2-methyl-1h-benzimidazole Chemical compound C1=CC=C2NC(C)=NC2=C1 LDZYRENCLPUXAX-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 239000013152 imidazole-based metal-organic framework Substances 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- -1 imidazole compound Chemical class 0.000 claims description 3
- OQZDJLFNMXRJHZ-UHFFFAOYSA-N 1-benzyl-2-ethylimidazole Chemical compound CCC1=NC=CN1CC1=CC=CC=C1 OQZDJLFNMXRJHZ-UHFFFAOYSA-N 0.000 claims description 2
- QKVROWZQJVDFSO-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethanamine Chemical compound CC1=NC=CN1CCN QKVROWZQJVDFSO-UHFFFAOYSA-N 0.000 claims description 2
- NJQHZENQKNIRSY-UHFFFAOYSA-N 5-ethyl-1h-imidazole Chemical compound CCC1=CNC=N1 NJQHZENQKNIRSY-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 45
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 40
- 239000012300 argon atmosphere Substances 0.000 description 25
- 238000005516 engineering process Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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Abstract
The invention discloses a preparation method of a zeolite imidazolyl metal organic framework nanosheet for oxygen reduction reaction. Is mainly suitable for preparing Fe and other non-noble metal-based electrocatalytic oxygen reduction catalysts as precursors. The invention mainly aims to solve the problems that the microporous structure on the surface of the existing zeolite imidazolyl metal-organic framework is not beneficial to the transfer of electrons and ions in the electrocatalytic reaction process, and the number of active sites is small. The zeolite imidazolyl metal-organic framework nanosheet is prepared through simple experimental operation, has a larger specific surface area and a larger active site density, and is easier for ion and electron transmission. The method has the advantages of wide application range, low cost, simple operation and environmental friendliness, does not need special equipment in the whole operation process, and is easy for industrial production. The catalyst obtained by the method has the advantages of good stability, many active sites, high catalytic performance and the like. The invention provides a preparation method of an oxygen reduction reaction catalyst with great industrial prospect.
Description
Technical Field
The invention specifically relates to modification of a porous coordination polymer, a zeolite imidazole ester framework material and a metal organic framework nano material, and belongs to the fields of preparation technology of nano materials and application of electrocatalytic energy materials.
Background
At present, fossil energy is gradually exhausted, and the popularization of new energy technology is helpful for solving the problems of environmental pollution and greenhouse effect caused by the mass use of three fossil fuels (coal, petroleum and natural gas) from the source. In recent years, in order to solve the serious problem, a great deal of capital is invested in various countries around the world to research and develop sustainable new energy technologies, mainly including hydrogen-oxygen fuel cell technology, full-electrolytic water technology, metal-air battery technology and the like. The new energy technology relates to various types of electrochemical reactions, wherein an oxygen reduction reaction is a very critical reaction for realizing the new technology. In the past few years, although researchers have made some progress in the field of exploring and developing low-cost and high-activity electrocatalysts, noble metal catalysts such as Pt and Ir have been considered as the best catalysts among various electrocatalytic reactions. The scarcity and high cost of the total amount of precious metals limits their prospects for commercial applications. Therefore, the development of low-cost, high-activity and high-stability non-noble metal catalysts is urgent.
Through the development of the last 30 years, Metal Organic Frameworks (MOFs) materials are considered as ideal precursors for preparing carbon-based materials due to their large specific surface area and pore size and controllable and changeable metal central ions and organic ligands. The material has become a popular material for current research, and has a great application prospect in the fields of gas adsorption and separation, catalysis, sensing and the like. The zeolite imidazolyl metal-organic framework material has the characteristics of high pore volume, high hydrophobicity, high thermal stability, chemical stability and the like, so that a series of non-noble metal electrocatalytic oxygen reduction catalysts prepared by using the zeolite imidazolyl metal-organic framework material as a precursor show obvious catalytic advantages compared with catalysts prepared from other carbon-based precursors (carbon nano tubes, graphene, carbon black and the like). However, the microporous structure on the surface of the zeolite imidazolyl metal-organic framework material limits the doped metal ions from entering the zeolite imidazolyl metal-organic framework material, so that the number of active sites is reduced, and the transmission of ions and electrons is not facilitated in the electrocatalytic reaction process, so that the further improvement of the electrocatalytic performance is greatly limited.
Based on the research work, the invention provides a method for preparing an imidazolyl metal organic framework nanosheet through solvothermal-assisted heterogeneous nucleation. Compared with the dodecahedral structure imidazolyl metal-organic framework material prepared by the traditional method, the imidazolyl metal-organic framework nanosheet prepared by the method has many advantages. The catalyst has larger specific surface area and larger active site density, and is more beneficial to the transmission of ions and electrons in electrochemical reaction. The non-noble metal-based electro-catalytic oxidation reduction catalyst prepared by taking the imidazolyl metal organic framework nanosheet as a precursor is further improved on the basis of the original material catalytic performance.
Disclosure of Invention
The invention aims to provide a preparation method of a zeolite imidazolyl metal organic framework nanosheet for oxygen reduction reaction, so that the catalytic performance of the existing catalyst is improved, and the problems of few active sites, poor catalytic performance and the like of the existing catalyst are solved.
The purpose of the invention can be realized by the following technical scheme:
a method of preparing zeolite imidazolyl metal-organic framework nanosheets for use in oxygen reduction reactions, comprising the steps of:
(1) weighing a certain mass of imidazole compounds, and dissolving the imidazole compounds in a hydrophilic solvent (a single solvent or a mixed solvent), wherein the concentration of the imidazole compounds is 0.0001-10 g/mL.
(2) Weighing a certain mass of metal source compound, dissolving the metal source compound in a hydrophilic solvent (a single solvent or a mixed solvent), uniformly mixing the metal source compound with the imidazole compound solution obtained in the step (1), wherein the concentration of the metal source compound is 0.0001-10 g/mL, stirring for 1-48h to obtain an imidazole-based metal organic framework precursor, centrifuging, and dispersing in the hydrophilic solvent (the single solvent or the mixed solvent) again, wherein the concentration of the imidazole-based metal organic framework precursor is 0.0001-10 g/mL.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2).
The imidazole compounds described above include: 2-methylimidazole, 2-ethylimidazole, 4-methylimidazole, 4-ethylimidazole, 1-benzyl-2-ethylimidazole, 1-aminoethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-methylbenzimidazole. The metal source compound comprises: one or a mixed salt of two or more of ferric nitrate nonahydrate, ferrous nitrate, ferric chloride, ferrous oxalate, ferric sulfate, ferrous sulfate, nickel nitrate, nickel chloride, nickel oxalate, nickel sulfate, cobalt nitrate hexahydrate, cobalt chloride, cobalt oxalate, cobalt sulfate, cobalt acetate, zinc nitrate hexahydrate, zinc chloride, zinc sulfate, zinc oxalate, copper nitrate, copper chloride, cuprous chloride and copper sulfate. The hydrophilic solvent is one or more mixed solvents of deionized water, methanol, ethanol, ethylene glycol, glycerol, dimethylformamide, pyridine, piperidine and tetrahydrofuran.
(4) Transferring the solution obtained in the step (3) into a reaction kettle, and reacting for a certain time (1-48h) at a certain temperature (40-200 ℃). The obtained material is centrifugally washed by deionized water and absolute ethyl alcohol in sequence, and then is put into a vacuum drying oven to be dried for a certain time (5-48 h).
(5) And (4) dispersing the material obtained in the step (4) in a hydrophilic solution of an Fe source compound, centrifugally separating, putting into a vacuum drying oven, and drying for a certain time (5-48 h). Calcining for 1-24h at 500-1200 ℃ under an inert atmosphere.
The Fe source compounds described above include: one or more than two Fe salts selected from ferric nitrate nonahydrate, ferrous nitrate, ferric chloride, ferrous oxalate, ferric sulfate and ferrous sulfate. The hydrophilic solvent is one or more mixed solvents of deionized water, methanol, ethanol, ethylene glycol, glycerol, dimethylformamide, pyridine, piperidine and tetrahydrofuran.
(6) And (3) using the material obtained in the step (5) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a 5% nafion aqueous solution, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a linear sweep voltammetry with a three electrode system with 0.1M KOH electrolyte.
Advantageous effects
1. The invention relates to a method for preparing an oxygen reduction catalyst precursor zeolite imidazolyl metal organic framework material nanosheet through solvent heat-assisted heterogeneous nucleation, so as to improve the oxygen reduction catalytic performance of a Fe-based catalyst, and the chemical structure of the material is not changed in the synthesis process.
2. The modification method provided by the invention is simple to operate, low in cost and mild in condition, is different from a dodecahedral structure of the zeolite imidazolyl metal organic framework prepared by a traditional synthesis method, and is used for preparing the zeolite imidazolyl metal organic framework nanosheet. The catalytic performance is further improved on the basis of the catalytic performance of the original catalyst.
3. The Fe-based catalyst taking the zeolite imidazolyl metal organic framework nanosheet as the carrier is a good catalyst for oxygen reduction reaction, and the half-wave potential of the oxygen reduction reaction is increased from 0.840V to 0.862V in 0.1M KOH solution under the scanning speed of 5 mV/s.
Drawings
FIG. 1 is an X-ray diffraction pattern of the zeolite imidazolyl metal-organic framework nanosheet prepared in example 1 after calcination at 900 ℃ for 3h under an argon atmosphere;
FIG. 2 is an X-ray diffraction pattern of the zeolite imidazolyl metal-organic framework nanosheet prepared in example 3 after calcination at 900 ℃ for 3h under an argon atmosphere;
figure 3 is a scanning electron microscope image of zeolite imidazolate metal organic framework nanosheets prepared in example 4;
figure 4 is a scanning electron microscope photograph of zeolite imidazolate metal organic framework nanosheets prepared in example 6;
FIG. 5 is a plot of the linear voltammetry scan performance in 0.1M KOH electrolyte for samples 1 and 2 prepared in example 7.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings to assist understanding of the present invention, but the present invention is not limited to the following embodiments.
Example 1
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.860V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
FIG. 1 is an X-ray diffraction pattern of the zeolite imidazolyl metal-organic framework nanosheet prepared in the present embodiment after calcination at 900 ℃ for 3h under an argon atmosphere. The figure shows that the obtained material has a good structural characteristic peak of graphite carbon obtained after the zeolite imidazolyl metal-organic framework nanosheet is calcined, and the crystallinity of the material is good.
Example 2
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of cobalt nitrate hexahydrate and zinc nitrate hexahydrate (mass ratio of 1:1) are weighed and dissolved in 18mL of methanol solvent, and the mixture and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.8580V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 3
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc chloride is weighed and dissolved in 18mL of methanol solvent, and the zinc chloride and the 2-ethylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.861V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
FIG. 2 is an X-ray diffraction pattern of the zeolite imidazolyl metal-organic framework nanosheet prepared in the present embodiment after calcination at 900 ℃ for 3h under an argon atmosphere. The figure shows that the obtained material has a good structural characteristic peak of graphite carbon obtained after the zeolite imidazolyl metal-organic framework nanosheet is calcined, and the crystallinity of the material is good.
Example 4
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of nickel chloride is weighed and dissolved in 18mL of methanol solvent, and the nickel chloride and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.857V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Fig. 3 is a scanning electron microscope image of the zeolite imidazolyl metal-organic framework nanosheet prepared in this example. The obtained material has good nanosheet morphology, uniform morphology and good dispersibility.
Example 5
(1) 2g of 2-ethylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-ethylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.858V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution. .
Example 6
(1) 2g of 4-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 4-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.857V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution. Fig. 4 is a scanning electron microscope image of the zeolite imidazolyl metal-organic framework nanosheets prepared in this example. The obtained material has good nanosheet morphology, uniform morphology and good dispersibility.
Example 7
Sample 1
(1) 2g of 2-methylbenzimidazole and 2-methylimidazole (mass ratio of 1:1) were weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the solution of the 2-methylbenzimidazole and the 2-methylimidazole (the mass ratio is 1:1) obtained in the step (1) is uniformly mixed and stirred for 24 hours.
(3) And (3) after the reaction in the step (2) is finished, centrifugally washing the mixture for three times by using deionized water and absolute ethyl alcohol, putting the mixture into a vacuum drying oven at the temperature of 80 ℃, and drying the mixture for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.840V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
(1) 2g of 2-methylbenzimidazole and 2-methylimidazole (mass ratio of 1:1) were weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-methylbenzimidazole and 2-methylimidazole (the mass ratio is 1:1) solution obtained in the step (1) are uniformly mixed, stirred for 24 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 180 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.862V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
FIG. 5 is a plot of the linear voltammetry scan performance in 0.1M KOH electrolyte for samples 1 and 2 prepared in example 7. It is shown that the oxygen reduction half-wave potential of the sample 1 synthesized by the conventional synthesis method is only 0.840V, while the oxygen reduction half-wave potential of the sample 2 prepared by the method of the present invention is increased to 0.862V, measured at a scanning speed of 5 mV/s.
Example 8
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of aqueous solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of aqueous solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of aqueous solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.861V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 9
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of dimethylformamide solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of dimethylformamide solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of dimethylformamide solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.857V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 10
(1) 2g of 2-methylimidazole was weighed out and dissolved in 18mL of a mixed solvent of methanol and water (volume ratio: 1).
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of mixed methanol-water solvent (volume ratio is 1:1), the mixed solution and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of mixed methanol-water solvent (volume ratio is 1: 1).
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.860V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 11
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 24 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.860V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 12
(1) 2g of 2-methylimidazole are weighed out and dissolved in 50mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 50mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 50mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.860V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 13
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 200 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.858V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 14
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 24 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.859V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 15
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 1100 ℃ for 3h under an argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.861V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 16
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 12h under an argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.860V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 17
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with ferric chloride concentration of 6mmoL/L, centrifugally separating, and then putting into a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.858V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 18
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (3) dispersing the material obtained in the step (3) in 10mL of isopropanol solution with the total concentration of ferric nitrate nonahydrate and ferric chloride (the molar ratio is 1:1) being 6mmoL/L, centrifugally separating, and then placing the mixture into a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.860V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 19
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (4) dispersing the material obtained in the step (3) in 10mL of glycol solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and placing in a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.858V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Example 20
(1) 2g of 2-methylimidazole are weighed out and dissolved in 18mL of methanol solvent.
(2) 0.8g of zinc nitrate hexahydrate is weighed and dissolved in 18mL of methanol solvent, and the zinc nitrate hexahydrate and the 2-methylimidazole solution obtained in the step (1) are uniformly mixed, stirred for 5 hours, centrifuged and dispersed in 18mL of methanol solvent again.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2), transferring the mixture into a reaction kettle, and reacting for 2 hours at 120 ℃. After the reaction is finished, the mixture is centrifugally washed for three times by deionized water and absolute ethyl alcohol, and is placed into a vacuum drying oven at the temperature of 80 ℃ for drying for 10 hours.
(4) And (3) dispersing the material obtained in the step (3) in 10mL of isopropanol and ethylene glycol (volume ratio is 1:1) solution with ferric nitrate nonahydrate concentration of 6mmoL/L, centrifugally separating, and putting the solution into a vacuum drying oven for drying for 10 hours. Calcining at 900 ℃ for 3h under the argon atmosphere.
(5) And (3) using the material obtained in the step (4) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a nafion aqueous solution with the concentration of 5%, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a three-electrode system with linear sweep voltammetry. The half-wave potential of the oxygen reduction reaction reached 0.861V, measured at a sweep rate of 5mV/s in a 0.1M KOH solution.
Claims (6)
1. A preparation method of a zeolite imidazolyl metal-organic framework nanosheet for oxygen reduction reaction comprises the following steps:
(1) weighing a certain mass of imidazole compounds, and dissolving the imidazole compounds in a hydrophilic solvent (a single solvent or a mixed solvent), wherein the concentration of the imidazole compounds is 0.0001-10 g/mL.
(2) Weighing a certain mass of metal source compound, dissolving the metal source compound in a hydrophilic solvent (a single solution or a mixed solution), uniformly mixing the metal source compound with the imidazole compound solution obtained in the step (1), wherein the concentration of the metal source compound is 0.0001-10 g/mL, stirring for 1-48h to obtain an imidazole-based metal organic framework precursor, centrifuging, and dispersing in the hydrophilic solvent (the single solvent or the mixed solvent) again, wherein the concentration of the imidazole-based metal organic framework precursor is 0.0001-10 g/mL.
(3) And (3) uniformly mixing the solution obtained in the step (1) and the solution obtained in the step (2).
(4) Transferring the solution obtained in the step (3) into a reaction kettle, and reacting for a certain time (1-48h) at a certain temperature (40-200 ℃). The obtained material is centrifugally washed by deionized water and absolute ethyl alcohol in sequence, and then is put into a vacuum drying oven to be dried for a certain time (5-48 h).
(5) And (4) dispersing the material obtained in the step (4) in a hydrophilic solution of an Fe source compound, centrifugally separating, putting into a vacuum drying oven, and drying for a certain time (5-48 h). Calcining for 1-24h at 500-1200 ℃ under an inert atmosphere.
(6) And (3) using the material obtained in the step (5) as an oxygen reduction catalytic material, and dispersing the material in a mixed solution (the proportion of ethanol to deionized water is 1:1) and a 5% nafion aqueous solution, wherein the proportion of the mixed solution to the nafion aqueous solution in the mixed solution is (90-95): (10-5). And coating the prepared solution on the surface of a glassy carbon electrode, and airing at room temperature. The test was performed using a linear sweep voltammetry with a three electrode system with 0.1M KOH electrolyte.
2. The method of claim 1, wherein: the imidazole compounds comprise 2-methylimidazole, 2-ethylimidazole, 4-methylimidazole, 4-ethylimidazole, 1-benzyl-2-ethylimidazole, 1-aminoethyl-2-methylimidazole, 2-ethyl-4-methylimidazole and 2-methylbenzimidazole.
3. The method of claim 1, wherein: the metal source compound comprises one or more mixed salts of ferric nitrate nonahydrate, ferrous nitrate, ferric chloride, ferrous oxalate, ferric sulfate, ferrous sulfate, nickel nitrate, nickel chloride, nickel oxalate, nickel sulfate, cobalt nitrate hexahydrate, cobalt chloride, cobalt oxalate, cobalt sulfate, cobalt acetate, zinc nitrate hexahydrate, zinc chloride, zinc sulfate, zinc oxalate, copper nitrate, copper chloride, cuprous chloride and copper sulfate.
4. The method of claim 1, wherein: the hydrophilic solvent is one or more mixed solvents of deionized water, methanol, ethanol, glycol, glycerol, dimethylformamide, pyridine, piperidine and tetrahydrofuran.
5. The method of claim 1, wherein: the Fe source compound comprises one or more mixed salts of ferric nitrate nonahydrate, ferrous nitrate, ferric chloride, ferrous oxalate, ferric sulfate and ferrous sulfate.
6. The method of claim 1, wherein: the hydrophilic solvent is one or more mixed solvents of deionized water, methanol, ethanol, glycol, glycerol, dimethylformamide, pyridine, piperidine and tetrahydrofuran.
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