CN107803207A - A kind of carbon-based double metallic composite material, preparation and its application - Google Patents
A kind of carbon-based double metallic composite material, preparation and its application Download PDFInfo
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- CN107803207A CN107803207A CN201710973860.7A CN201710973860A CN107803207A CN 107803207 A CN107803207 A CN 107803207A CN 201710973860 A CN201710973860 A CN 201710973860A CN 107803207 A CN107803207 A CN 107803207A
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- carbon
- transition metal
- composite material
- bimetallic
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- 239000002131 composite material Substances 0.000 title claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000001301 oxygen Substances 0.000 claims abstract description 66
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 66
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 59
- 150000003624 transition metals Chemical class 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000013110 organic ligand Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000013459 approach Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 43
- 239000003054 catalyst Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 150000001868 cobalt Chemical class 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- -1 phosphides Chemical class 0.000 description 11
- 150000002505 iron Chemical class 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000002525 ultrasonication Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- JTLDVOIZHSDIMJ-UHFFFAOYSA-N 4-[(2-phosphonoethylamino)methyl]benzoic acid Chemical compound P(=O)(O)(O)CCNCC1=CC=C(C(=O)O)C=C1 JTLDVOIZHSDIMJ-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YWLJSJUVCGYFAZ-UHFFFAOYSA-N [C].[P].[Co] Chemical compound [C].[P].[Co] YWLJSJUVCGYFAZ-UHFFFAOYSA-N 0.000 description 1
- JLFVIEQMRKMAIT-UHFFFAOYSA-N ac1l9mnz Chemical compound O.O.O JLFVIEQMRKMAIT-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 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 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种碳基双金属复合材料，包括炭基壳体，所述的炭基壳体的内表面复合有过渡金属A的硫化物，外表面复合有过渡金属B的氧化物；所述的过渡金属A和B选自不同金属。本发明还公开了所述的碳基双金属复合材料的制备方法，将包含过渡金属A的盐、过渡金属B的盐、有机配体、醇的混合液在60～180℃下进行水热反应，得双金属MOF；将获得的双金属MOF与升华硫混合后再在保护性气氛内、300～800℃下焙烧，得到所述的碳基双金属复合材料。此外，本发明还包括将所述的复合材料作为OER电催化剂的应用。本发明提供了一种全新结构的电催化剂；该材料具有优异的OER催化性能。在电流密度10mA/cm2下，氧气析出电位可接近0.55V；在过电位为320mV下，TOF可高达34.7s‑1。The invention discloses a carbon-based bimetallic composite material, comprising a carbon-based shell, the inner surface of the carbon-based shell is compounded with a transition metal A sulfide, and the outer surface is compounded with a transition metal B oxide; The transition metals A and B are selected from different metals. The invention also discloses a preparation method of the carbon-based bimetallic composite material, wherein the mixed liquid containing transition metal A salt, transition metal B salt, organic ligand and alcohol is hydrothermally reacted at 60-180°C , to obtain a bimetallic MOF; the obtained bimetallic MOF is mixed with sublimed sulfur and then calcined in a protective atmosphere at 300-800° C. to obtain the carbon-based bimetallic composite material. In addition, the present invention also includes the application of the composite material as an OER electrocatalyst. The invention provides an electrocatalyst with a new structure; the material has excellent OER catalytic performance. At a current density of 10mA/cm 2 , the oxygen evolution potential can approach 0.55V; at an overpotential of 320mV, the TOF can reach as high as 34.7s ‑1 .
Description
技术领域technical field
本发明涉及一种新型碳基双金属复合双壳中空结构电催化剂，属于能源和催化材料领域。The invention relates to a novel carbon-based bimetal composite double-shell hollow structure electrocatalyst, which belongs to the field of energy and catalytic materials.
背景技术Background technique
近年来，能源危机和环境污染问题日益突出，可再生能源和清洁能源的发展迫在眉睫。电化学分解水因其环保，产品纯度高，无温室气体排放而引起了广泛关注。有效的电解水催化剂对于阳极氧气析出反应(OER)和阴极析氢反应(HER)都需要低的超电势，但是电催化剂的效率被缓慢的OER动力学和高过电位限制，因此提高OER的电催化剂效率是水分解的关键。通常认为RuO2和IrO2被认为是最好的OER电催化剂，不幸的是，它们的大规模商业应用被高成本、耐用性差和供应稀缺所阻碍。因此设计一种制备方法简便、低成本、低的过电位和高稳定性的催化剂，成为目前研究团队的研究热点。In recent years, the energy crisis and environmental pollution problems have become increasingly prominent, and the development of renewable energy and clean energy is imminent. Electrochemical water splitting has attracted extensive attention due to its environmental friendliness, high product purity, and no greenhouse gas emissions. Efficient water electrolysis catalysts require low overpotentials for both anodic oxygen evolution reaction (OER) and cathodic hydrogen evolution reaction (HER), but the efficiency of electrocatalysts is limited by slow OER kinetics and high overpotentials, thus electrocatalysts that enhance OER Efficiency is the key to water splitting. RuO2 and IrO2 are generally regarded as the best OER electrocatalysts, unfortunately, their large - scale commercial application is hindered by high cost, poor durability, and scarce supply. Therefore, designing a catalyst with simple preparation method, low cost, low overpotential and high stability has become a research hotspot of the current research team.
金属有机骨架(MOFs)是一种新兴的纳米多孔材料，由于其比表面积高，孔隙通道均匀可调，易功能化和可调节，以及良好的化学和热稳定性，在催化、储能、太阳能收集等领域具有巨大的应用潜力。近年来，过渡金属MOFs(如Fe，Co和Ni等)衍生的金属氧化物，磷化物，硫化物，硒化物，氮化物等由于其优异的催化性能已经吸引了大多数研究团队的高度关注。Metal-organic frameworks (MOFs) are emerging nanoporous materials. Due to their high specific surface area, uniform and adjustable pore channels, easy functionalization and adjustment, and good chemical and thermal stability, they are widely used in catalysis, energy storage, and solar energy. Fields such as collection have huge application potential. In recent years, metal oxides, phosphides, sulfides, selenides, nitrides, etc. derived from transition metal MOFs (such as Fe, Co, and Ni, etc.) have attracted the attention of most research groups due to their excellent catalytic performance.
Zhou等以4-[(膦酰基乙基氨基)-甲基]苯甲酸为配体材料，通过水热法制备Co-MOF前驱体，再通过高温煅烧合成了具有层状结构的钴磷碳化合物(Co-PC)，该催化剂具有低超电势、高极限电流密度等优点，在金属空气电池领域有良好的应用前景(ACSCatalysis，2017，7：6000-6007)。中国专利CN104056630A公布一种将碳源和钴盐按一定比例混合，通过高温煅烧得到碳包覆钴单质，该催化剂具有粒子直径均匀、导电性好、高电催化性能等优点，在金属空气电池、电催化水制氧等领域有良好的应用前景。中国专利CN104659357A公布一种将以镍、铁盐溶液与导电载体、粘合剂通过简单的物理混合-滚压得到金属盐/碳膜，然后通过低温热处理、原位沉淀和压合金属集流体得到负载型镍铁复合氢氧化物析氧电极，该催化剂具有高比表面且尺寸可调控、高活性位点等优点，展现了良好的工业前景和经济价值。中国专利CN105176528A公布一种将六水合硝酸钻、尿素和氟化铵为原料，通过溶剂热反应在碳纤维纸上生长碱式碳酸钻纳米线，然后加入硫粉为原料，通过低温硫化反应制备碳纤维纸负载硫化钻纳米线复合结构，最后利用电化学沉积法在碳纤维纸负载硫化钻纳米线复合结构表面电镀一层氢氧化钻纳米片，得到钻基多级纳米复合结构电解水制氧电催化剂，该催化剂具有低析氧过电位、高的电催化性能等优点，相对贵金属，有较低的成本，有良好的工业应用前景。中国专利CN105176528A公布一种将醋酸镍和氯化铁与柠檬酸、硫脉为原料，按一定的摩尔百分比均匀混合后，通过高温锻烧制得Ni0.9Fe0.1@CNx，该催化剂具有形貌呈纳米管状、多孔、比表面积大等优点，促进析氧电极材料用于电解水的规模化生产。Zhou et al. used 4-[(phosphonoethylamino)-methyl]benzoic acid as ligand material to prepare Co-MOF precursor by hydrothermal method, and then synthesized cobalt phosphorus carbon compound with layered structure by high temperature calcination. (Co-PC), the catalyst has the advantages of low overpotential and high limiting current density, and has good application prospects in the field of metal-air batteries (ACSCatalysis, 2017, 7: 6000-6007). Chinese patent CN104056630A discloses a method of mixing carbon source and cobalt salt in a certain proportion, and obtaining carbon-coated cobalt simple substance through high-temperature calcination. The catalyst has the advantages of uniform particle diameter, good conductivity, and high electrocatalytic performance. It is used in metal-air batteries, Electrocatalytic water oxygen production and other fields have good application prospects. Chinese patent CN104659357A discloses a metal salt/carbon film obtained by simple physical mixing-rolling of nickel and iron salt solution with conductive carrier and adhesive, and then obtained by low-temperature heat treatment, in-situ precipitation and pressing metal current collector Supported nickel-iron composite hydroxide oxygen evolution electrode, the catalyst has the advantages of high specific surface area, adjustable size and high active sites, showing good industrial prospects and economic value. Chinese patent CN105176528A discloses a method of using cobalt nitrate hexahydrate, urea and ammonium fluoride as raw materials to grow basic cobalt carbonate nanowires on carbon fiber paper through solvothermal reaction, and then adding sulfur powder as raw materials to prepare carbon fiber paper through low-temperature vulcanization reaction Carry cobalt sulfide nanowire composite structure, and finally use the electrochemical deposition method to electroplate a layer of cobalt hydroxide nanosheets on the surface of the carbon fiber paper-supported cobalt sulfide nanowire composite structure to obtain a cobalt-based multilevel nanocomposite structure. The catalyst has the advantages of low oxygen evolution overpotential, high electrocatalytic performance, etc. Compared with noble metals, it has lower cost and has good industrial application prospects. Chinese patent CN105176528A discloses a kind of nickel acetate, ferric chloride, citric acid, and thiaurea as raw materials, uniformly mixed according to a certain molar percentage, and then fired at high temperature to obtain Ni 0.9 Fe 0.1 @CN x , the catalyst has a morphology It has the advantages of being nano-tubular, porous, and large specific surface area, which promotes the large-scale production of oxygen evolution electrode materials for electrolysis of water.
上述方法制备的电催化剂大多没有应用于电解水的阳极氧气析出反应，且部分催化剂的制备方法较为复杂，制备工艺条件不容易控制，因此发展成本低、不含贵金属、具有高电催化活性和稳定性的多壳中空碳球作为OER电催化剂，对于推动电解水制氧的商业化进程具有重大意义。Most of the electrocatalysts prepared by the above method are not used in the anode oxygen evolution reaction of electrolyzed water, and the preparation method of some catalysts is relatively complicated, and the preparation process conditions are not easy to control, so the development cost is low, does not contain precious metals, and has high electrocatalytic activity and stability. The unique multi-shell hollow carbon spheres as OER electrocatalysts are of great significance for promoting the commercialization of water electrolysis for oxygen production.
发明内容Contents of the invention
为解决现有技术存在的技术问题，本发明提供了一种具有全新结构的碳基双金属复合材料；该材料作为OER电催化剂，具有良好的催化性能。In order to solve the technical problems in the prior art, the invention provides a carbon-based bimetallic composite material with a new structure; the material has good catalytic performance as an OER electrocatalyst.
本发明第二目的在于，提供了一种所述的碳基双金属复合材料的制备方法。The second object of the present invention is to provide a method for preparing the carbon-based bimetal composite.
本发明第三目的在于，提供了所述的碳基双金属复合材料的应用。The third object of the present invention is to provide the application of the carbon-based bimetallic composite material.
一种碳基双金属复合材料，包括炭基壳体，所述的炭基壳体的内表面复合有过渡金属A的硫化物，外表面复合有过渡金属B的氧化物；所述的过渡金属A和B选自不同金属。A carbon-based bimetallic composite material, comprising a carbon-based shell, the inner surface of the carbon-based shell is compounded with a transition metal A sulfide, and the outer surface is compounded with a transition metal B oxide; the transition metal A and B are selected from different metals.
作为优选，所述的过渡金属A选自Co、Zn中的至少一种；进一步优选为Co。过渡金属A优选为Co时，制备的中空结构更均一，催化析氧性能更优。Preferably, the transition metal A is selected from at least one of Co and Zn; more preferably Co. When the transition metal A is preferably Co, the prepared hollow structure is more uniform, and the catalytic oxygen evolution performance is better.
作为优选，所述的过渡金属B选自Fe、Ni、Cu、Zn、Mn中的至少一种；进一步优选为Fe。过渡金属B优选为Fe时，催化析氧性能更优。Preferably, the transition metal B is selected from at least one of Fe, Ni, Cu, Zn and Mn; more preferably Fe. When the transition metal B is preferably Fe, the catalytic oxygen evolution performance is better.
作为优选，所述的炭基壳体中掺杂有杂元素，所述的杂原子为N、S中的至少一种。Preferably, the carbon-based shell is doped with heteroelements, and the heteroatoms are at least one of N and S.
作为优选，所述的炭基壳体的靠近内表面端渗入过渡金属A的硫化物；靠近外表面端渗入过渡金属B的氧化物。也即是，过渡金属A的硫化物部分渗入至炭基壳体内部；所述的过渡金属B的氧化物也部分渗入至炭基壳体内部。As a preference, the sulfide of the transition metal A is infiltrated into the end near the inner surface of the carbon-based shell; the oxide of the transition metal B is infiltrated near the end of the outer surface. That is, the sulfide of the transition metal A partly penetrates into the interior of the carbon-based shell; the oxide of the transition metal B also partly penetrates into the interior of the carbon-based shell.
作为优选，所述的碳基双金属复合材料呈球形或者类球形形貌。例如，所述的复合材料为球体；或者椭球体等形貌物料。研究表面，该优选形貌以及结构的材料，OER催化性能更优。Preferably, the carbon-based bimetallic composite material has a spherical or spherical shape. For example, the composite material is a sphere; or a shape material such as an ellipsoid. Research on the surface, the preferred morphology and structure of the material, the OER catalytic performance is better.
作为优选，所述的复合材料，包括球形或类球形的炭基壳体；所述的炭基壳体的内表面复合有硫化钴层，外表面复合有氧化铁。Preferably, the composite material includes a spherical or quasi-spherical carbon-based shell; the inner surface of the carbon-based shell is compounded with a cobalt sulfide layer, and the outer surface is compounded with iron oxide.
所述的复合材料中，所述的过渡金属A的硫化物的含量为5～25％；所述的过渡金属B的氧化物的含量为1～15％；炭基壳体的含量为60～94％。In the composite material, the content of the sulfide of the transition metal A is 5-25%; the content of the oxide of the transition metal B is 1-15%; the content of the carbon-based shell is 60-25%. 94%.
本发明还公开了所述的碳基双金属复合材料的制备方法，将包含过渡金属A的盐、过渡金属B的盐、有机配体、醇的混合液在60～180℃下进行水热反应，得双金属MOF；将获得的双金属MOF与升华硫混合后再在保护性气氛内、300～800℃下焙烧，得到所述的碳基双金属复合材料。The invention also discloses a preparation method of the carbon-based bimetallic composite material, wherein the mixed liquid containing transition metal A salt, transition metal B salt, organic ligand and alcohol is hydrothermally reacted at 60-180°C , to obtain a bimetallic MOF; the obtained bimetallic MOF is mixed with sublimed sulfur and then calcined in a protective atmosphere at 300-800° C. to obtain the carbon-based bimetallic composite material.
本发明制备方法，所述所述的两种过渡金属，在醇溶剂氛围下、所述的温度下进行水热反应，可制得具有特殊中空形貌的双金属MOF；再独创性地将该形貌的双金属MOF与升华硫混合，在所述的温度下进行焙烧；可制得所述的独特形貌的复合材料；该材料整体为碳壳结构，且外表面复合有过渡金属氧化物，内表面复合有过渡金属硫化物；该形貌的材料被证实具有优异的OER催化性能。In the preparation method of the present invention, the two transition metals mentioned above are hydrothermally reacted under the atmosphere of an alcohol solvent at the above mentioned temperature to obtain a bimetallic MOF with a special hollow shape; The bimetallic MOF with the shape is mixed with sublimed sulfur and fired at the above temperature; the composite material with the unique shape can be obtained; the material has a carbon shell structure as a whole, and the outer surface is compounded with transition metal oxides , the inner surface is compounded with transition metal sulfides; the material with this morphology has been confirmed to have excellent OER catalytic performance.
本发明的制备方法的关键在于，采用双过渡金属、水热条件(例如水热温度、水热的醇溶剂氛围)；以及将得到的MOF和硫一并在所述的温度下焙烧。The key to the preparation method of the present invention is to use double transition metals, hydrothermal conditions (such as hydrothermal temperature, hydrothermal alcohol solvent atmosphere); and to roast the obtained MOF and sulfur at the temperature.
作为优选，所述的醇为C1～4的单元醇或多元醇。所述的醇优选为无水溶剂。例如为甲醇、乙醇、丙醇等。Preferably, the alcohol is a C1-4 monoalcohol or polyalcohol. The alcohol is preferably an anhydrous solvent. Examples include methanol, ethanol, propanol, and the like.
进一步优选，所述的醇为甲醇。Further preferably, the alcohol is methanol.
本发明中，所述的有机配体为二甲基咪唑、对苯二甲酸、吡啶中的至少一种。In the present invention, the organic ligand is at least one of dimethylimidazole, terephthalic acid and pyridine.
更进一步优选，所述的有机配体为二甲基咪唑。研究表明，采用该配体，配合所述的水热反应条件，可最终制得具有球形、中空形貌的复合材料，该结构的材料的OER催化性能更优异。More preferably, the organic ligand is dimethylimidazole. Studies have shown that by using this ligand and cooperating with the hydrothermal reaction conditions, a composite material with a spherical and hollow shape can be finally prepared, and the OER catalytic performance of the material with this structure is better.
作为优选，过渡金属A的盐可以为Co2+、Zn2+的水溶性盐，例如为氯化盐、硝酸盐、硫酸盐等。Preferably, the salt of transition metal A may be a water-soluble salt of Co 2+ or Zn 2+ , such as chloride salt, nitrate salt, sulfate salt and the like.
作为优选，过渡金属B的盐为Fe3+、Ni2+、Cu2+、Zn2+、Mn2+的水溶性盐，例如为氯化盐、硝酸盐、硫酸盐等。Preferably, the transition metal B salt is a water-soluble salt of Fe 3+ , Ni 2+ , Cu 2+ , Zn 2+ , Mn 2+ , such as chloride, nitrate, sulfate, etc.
作为优选，过渡金属A和B之间的摩尔比为5∶1～1∶2。Preferably, the molar ratio between transition metal A and B is 5:1˜1:2.
进一步优选，过渡金属A和B之间的摩尔比为3∶1～4∶1。More preferably, the molar ratio between transition metal A and B is 3:1-4:1.
有机配体物摩尔量与过渡金属A、B摩尔量之和大于或等于2。The sum of the molar weight of the organic ligand and the molar weight of the transition metals A and B is greater than or equal to 2.
作为优选，有机配体物摩尔量与过渡金属A、B摩尔量之和的比值为2～8倍；进一步优选为2～4。Preferably, the ratio of the molar weight of the organic ligand to the sum of the molar weights of the transition metals A and B is 2-8 times; more preferably 2-4.
优选地，将所述比例的过渡金属A的盐、过渡金属B的盐、有机配体分别用所述的醇超声分散和/或溶解；分别得到过渡金属A溶液、过渡金属B溶液和有机配体溶液；然后将过渡金属A溶液滴加至有机配体溶液中，超声分散后再滴加过渡金属B溶液；继续超声分散，随后再进行后续的水热反应。Preferably, the salt of transition metal A, the salt of transition metal B, and the organic ligand are dispersed and/or dissolved with the described alcohol ultrasonically; the transition metal A solution, the transition metal B solution, and the organic ligand are respectively obtained. body solution; then the transition metal A solution was added dropwise to the organic ligand solution, and after ultrasonic dispersion, the transition metal B solution was added dropwise; the ultrasonic dispersion was continued, and then the subsequent hydrothermal reaction was carried out.
各阶段超声的时间没有特别要求，以使溶液形成分散均匀的混悬液即可；优选的超声时间为0.1～0.5h。There is no special requirement on the time of ultrasonication at each stage, so that the solution can form a uniformly dispersed suspension; the preferred ultrasonic time is 0.1-0.5 h.
过渡金属A溶液的溶质的浓度没有特别要求，优选为1～30mg/mL。The concentration of the solute in the transition metal A solution is not particularly required, but is preferably 1 to 30 mg/mL.
过渡金属B溶液的溶质的浓度没有特别要求，优选为1～30mg/mL。The concentration of the solute in the transition metal B solution is not particularly required, but is preferably 1 to 30 mg/mL.
过渡金属A溶液和过渡金属B溶液的滴加速度为2～10mL/min。The dropping rate of transition metal A solution and transition metal B solution is 2-10 mL/min.
本发明中，优选的水热反应温度为80～160℃，优选在该温度下，产物形貌保持更完整均一。In the present invention, the preferred hydrothermal reaction temperature is 80-160°C, preferably at this temperature, the morphology of the product remains more complete and uniform.
进一步优选，水热反应温度为120～140℃。在该优选范围下，制得的双金属MOF的形貌更好，后续焙烧得到的复合材料的OER催化性能更优异。More preferably, the hydrothermal reaction temperature is 120-140°C. In this preferred range, the morphology of the prepared bimetallic MOF is better, and the OER catalytic performance of the composite material obtained by subsequent calcination is better.
水热反应在密闭容器中进行；在所述的水热反应条件下，优选的水热反应时间为1～12h。The hydrothermal reaction is carried out in a closed container; under the above hydrothermal reaction conditions, the preferred hydrothermal reaction time is 1-12h.
水热反应后进行固液分离，再经洗涤、干燥处理，得到双金属MOF。洗涤过程为：用水、乙醇交替清洗并离心数次直至上清液澄清为止，然后50～80℃真空干燥6～8小时，即获到了双金属MOF前驱体。After the hydrothermal reaction, the solid-liquid separation is carried out, and then the bimetallic MOF is obtained through washing and drying. The washing process is as follows: alternately washing with water and ethanol and centrifuging several times until the supernatant is clear, and then vacuum drying at 50-80°C for 6-8 hours to obtain the bimetallic MOF precursor.
将得到双金属MOF与升华硫混合后再进行焙烧处理，混合的方式可采用现有方法，例如球磨。The obtained bimetallic MOF is mixed with sublimed sulfur and then roasted. The mixing method can use existing methods, such as ball milling.
优选的双金属MOF与升华硫的质量比为1～4；进一步优选为1∶1。The preferred mass ratio of bimetallic MOF to sublimed sulfur is 1-4; more preferably 1:1.
焙烧过程在保护性气氛下进行；所述的保护性气氛为氮气或者惰性气体。The firing process is carried out under a protective atmosphere; the protective atmosphere is nitrogen or inert gas.
焙烧过程的升温速率为1℃/min～10℃/min；优选为2℃/min～8℃/min。The heating rate of the roasting process is 1°C/min-10°C/min; preferably 2°C/min-8°C/min.
优选的焙烧温度为300～800℃。在该优选的范围内，催化析氧性能得到进一步。The preferred firing temperature is 300-800°C. Within this preferred range, the catalytic oxygen evolution performance is further improved.
更进一步优选，焙烧温度为500～600℃。More preferably, the calcination temperature is 500-600°C.
在所述的焙烧条件下，优选的焙烧时间为1～12h；进一步优选为3～6h。Under the above calcination conditions, the preferred calcination time is 1-12 hours; more preferably 3-6 hours.
焙烧后的产物采用所述的醇超声洗涤0.5～2小时，再用水、乙醇交替清洗并离心数次直至上清液澄清为止，然后50～80℃真空干燥6～8小时，得到所述的复合材料。The roasted product is ultrasonically washed with the alcohol for 0.5 to 2 hours, then alternately washed with water and ethanol and centrifuged several times until the supernatant is clear, and then vacuum dried at 50 to 80°C for 6 to 8 hours to obtain the composite Material.
本发明还公开了所述的碳基双金属复合材料的应用，作为催化剂，催化碱性电解水制氧反应。The invention also discloses the application of the carbon-based bimetal composite material as a catalyst to catalyze the oxygen production reaction of alkaline electrolyzed water.
本发明使用过渡金属盐、咪唑类化合物为原料，通过超声波辅助法联合高温热处理获得新型碳基双金属复合双壳中空结构电催化剂。该催化剂应用于电解水制氧，并且在碱性条件下表现出与商用RuO2相媲美的OER电催化活性。The invention uses transition metal salts and imidazole compounds as raw materials, and obtains a novel carbon-based bimetal composite double-shell hollow structure electrocatalyst through an ultrasonic-assisted method combined with high-temperature heat treatment. The catalyst was applied in the electrolysis of water for oxygen generation, and exhibited OER electrocatalytic activity comparable to that of commercial RuO2 under alkaline conditions.
本发明一种优选的制备方法，包括如下步骤：A preferred preparation method of the present invention comprises the steps of:
a.称取重量份为120过渡金属盐分散在重量份为30的醇溶液中，在超声器中超声0.2～0.5小时，使过渡金属盐完全分散在醇溶液中；a. Weighing 120 parts by weight of the transition metal salt and dispersing it in an alcohol solution of 30 parts by weight, sonicating in an ultrasonic machine for 0.2 to 0.5 hours, so that the transition metal salt is completely dispersed in the alcohol solution;
b.将重量份为400的咪唑类化合物加入到上述混合物中，继续超声0.2～0.5小时，使咪唑类化合物与过渡金属盐在溶液中混合均匀，继续加入重量份为40另一种过渡金属盐，然后继续超声0.2～0.5小时；b. Add 400 parts by weight of the imidazole compound into the above mixture, continue ultrasonication for 0.2 to 0.5 hours, mix the imidazole compound and the transition metal salt in the solution evenly, and continue to add another transition metal salt of 40 parts by weight , and then continue ultrasonication for 0.2 to 0.5 hours;
c.再转入高压反应釜80～160℃处理1～6小时，自然冷却后，用水、乙醇交替清洗并离心数次直至上清液澄清为止，然后50～80℃真空干燥6～8小时，即获到了双金属MOF前驱体；c. Transfer to a high-pressure reactor at 80-160°C for 1-6 hours. After natural cooling, alternately wash with water and ethanol and centrifuge several times until the supernatant is clear, then vacuum-dry at 50-80°C for 6-8 hours. That is, the bimetallic MOF precursor was obtained;
d.将重量份为100双金属MOF与重量份100升华硫研磨均匀，得到双金属MOF/硫复合物；d. Evenly grinding 100 parts by weight of bimetallic MOF and 100 parts by weight of sublimated sulfur to obtain a bimetallic MOF/sulfur composite;
e.将双金属MOF/硫复合物在氩气的氛围下，在管式炉中300～800℃温度下处理2小时，对上述样品进行醇类溶剂超声洗涤0.5～2小时，再用水、乙醇交替清洗并离心数次直至上清液澄清为止，然后50～80℃真空干燥6～8小时，得到新型碳基双金属复合双壳中空结构电催化剂。e. Treat the bimetallic MOF/sulfur complex in an argon atmosphere at a temperature of 300-800°C in a tube furnace for 2 hours, and ultrasonically wash the above-mentioned samples with an alcohol solvent for 0.5-2 hours, and then wash them with water and ethanol. Alternately washing and centrifuging for several times until the supernatant is clear, and then vacuum-drying at 50-80°C for 6-8 hours to obtain a novel carbon-based bimetal composite double-shell hollow structure electrocatalyst.
本发明所述的制备方法，是以两种过渡金属盐的醇溶液与咪唑类化合物通过简单的超声辅助混合得到双金属有机骨架(MOF)，然后加入升华硫，通过低温热处理得到新型碳基双金属复合双壳中空结构的析氧电催化剂。通过调控在载体内预先吸附的金属盐的比例，控制了新型碳基双金属复合双壳中空结构催化剂的尺寸，提高了活性位点；其次，由于引入杂原子硫进行掺杂，在热处理过程中生成硫化物，进一步调控了电极的析氧活性；再者，中空结构有利于降低析氧反应过程中的体积膨胀和促进电荷转移。该电极材料制备方法具有工序简单、条件温和、原料利用率高的优点，展现了良好的电解水制氧的应用前景和经济价值。The preparation method of the present invention is to obtain a bimetallic organic framework (MOF) by simple ultrasonic-assisted mixing of an alcohol solution of two transition metal salts and an imidazole compound, and then add sublimated sulfur to obtain a new type of carbon-based bismuth by low-temperature heat treatment. Oxygen evolution electrocatalyst with metal composite double shell hollow structure. By adjusting the ratio of pre-adsorbed metal salts in the carrier, the size of the new carbon-based bimetallic composite double-shell hollow structure catalyst is controlled, and the active site is increased; secondly, due to the introduction of heteroatom sulfur for doping, during the heat treatment process The generation of sulfide further regulates the oxygen evolution activity of the electrode; moreover, the hollow structure is beneficial to reduce the volume expansion and promote charge transfer during the oxygen evolution reaction. The preparation method of the electrode material has the advantages of simple process, mild conditions and high utilization rate of raw materials, and shows good application prospects and economic value of oxygen production by electrolysis of water.
本发明所述的焙烧，也称为煅烧或者热处理。The roasting described in the present invention is also called calcining or heat treatment.
有益效果Beneficial effect
本发明提供了一种全新结构的电催化剂；该材料具有优异的OER催化性能。在电流密度10mA/cm2下，氧气析出电位可接近0.55V；在过电位为320mV下，TOF可高达34.7s-1。The invention provides an electrocatalyst with a new structure; the material has excellent OER catalytic performance. At a current density of 10mA/cm 2 , the oxygen evolution potential can approach 0.55V; at an overpotential of 320mV, the TOF can reach as high as 34.7s -1 .
本发明制备方法简单，制得的材料的性能稳定。The preparation method of the invention is simple, and the performance of the prepared material is stable.
附图说明Description of drawings
图1为a为对比例1制备的实心复合材料的SEM图；b为对比例1制备的实心复合材料的TEM图；c为实例1制备的中空Co/Fe双金属MOF的SEM图；e为其TEM图；d为实例1制备的碳基双金属复合双壳中空结构的SEM图，f为其TEM图；g为实例1制备的碳基双金属复合双壳中空结构的HAADF-STEM图；h为对应的的元素mapping图。(图1h可以看出，钴、硫主要集中在内壳，铁、氧重要集中在外壳，很好的说明成功制备了碳基双金属复合双壳中空结构)。Fig. 1 is the SEM figure that a is the solid composite material prepared by comparative example 1; b is the TEM figure of the solid composite material prepared by comparative example 1; c is the SEM figure of the hollow Co/Fe bimetallic MOF prepared by example 1; e is Its TEM figure; d is the SEM picture of the carbon-based bimetallic composite double-shell hollow structure prepared by Example 1, and f is its TEM figure; g is the HAADF-STEM figure of the carbon-based bimetallic composite double-shell hollow structure prepared by Example 1; h is the corresponding element mapping diagram. (It can be seen from Figure 1h that cobalt and sulfur are mainly concentrated in the inner shell, and iron and oxygen are mainly concentrated in the outer shell, which well shows that the carbon-based bimetallic composite double-shell hollow structure was successfully prepared).
图2为实例12使用对苯二甲酸制备的碳基双金属复合双壳中空结构的SEM图。Fig. 2 is the SEM image of the carbon-based bimetal composite double-shell hollow structure prepared by using terephthalic acid in Example 12.
图3为实例1制备的碳基双金属复合双壳中空结构的XRD图。3 is an XRD pattern of the carbon-based bimetallic composite double-shell hollow structure prepared in Example 1.
图4为实例1，2，3，4，RuO2制备催化剂的析氧电化学性能对比图。Fig. 4 is a comparative diagram of oxygen evolution electrochemical performance of catalysts prepared by RuO2 in Examples 1, 2, 3, and 4.
这些结果说明，碳基双金属复合双壳中空结构的形貌是粒径大约为500nm的中空球体，并且碳基双金属复合双壳中空结构催化剂有着与商用RuO2在碱性条件下相当的氧气析出性能。These results indicate that the morphology of the carbon-based bimetallic composite double-shell hollow structure is a hollow sphere with a particle size of about 500 nm, and that the carbon-based bimetallic composite double -shell hollow structure catalyst has an oxygen content comparable to that of commercial RuO2 under alkaline conditions. Precipitation performance.
具体实施方式Detailed ways
以下实施例旨在说明本发明而不是对本发明的限定。在实例中The following examples are intended to illustrate the invention rather than limit it. in the example
取电流密度为10mA/cm2作为统一的参考点，氧气析出电位直接从催化剂的LSV图读出，参比电极为Ag/AgCl电极。催化剂在过电位为320mV的TOF可根据以下方程计算得出：Taking the current density of 10mA/cm 2 as a unified reference point, the oxygen evolution potential can be read directly from the LSV diagram of the catalyst, and the reference electrode is Ag/AgCl electrode. The TOF of the catalyst at an overpotential of 320mV can be calculated according to the following equation:
TOF＝(J×A)/(4×F×n)TOF＝(J×A)/(4×F×n)
J代表给定的过电位，A代表电极面积，4代表每摩尔O2转移4摩尔电子，F代表法拉第常数，n代表电极上金属离子的摩尔量。J represents a given overpotential, A represents the electrode area, 4 represents the transfer of 4 moles of electrons per mole of O2 , F represents Faraday’s constant, and n represents the molar amount of metal ions on the electrode.
实施例1Example 1
取钴盐(硝酸钴)3mol、二甲基咪唑8mol、铁盐(三氯化铁)1mol，分别溶解在40mL甲醇中，超声10min形成均匀溶液，再钴盐的甲醇溶液以5mL/min的滴加速率加入二甲基咪唑的甲醇溶液中，继续超声10min，接着铁盐的甲醇溶液以5mL/min的滴加速率加入上述溶液中，继续超声30min，然后转入高压反应釜中，加热至120℃处理4h，冷却至室温，水、无水乙醇交替洗涤离心三次，60℃真空干燥10h，得到中空Co3/Fe1双金属MOF(SEM和TEM附图见图1的c和e)；取10g中空Co3/Fe1双金属MOF与10g升华硫研磨均匀，在氩气氛围下，以5℃/min升温速率至500℃(煅烧温度)热处理3小时，冷却至室温，溶于40mL甲醇中超声30min，10000rpm离心5min，60℃干燥10h；得所述的复合材料；该材料的SEM和TEM附图见图1的d和f。包含碳壳，且碳壳的内表面复合有硫化钴，外表面复合有氧化铁。复合材料的粒径为500nm，其中，硫化钴的含量为15％，四氧化三铁的含量为10％，碳含量为68％。Take 3 mol of cobalt salt (cobalt nitrate), 8 mol of dimethylimidazole, and 1 mol of iron salt (ferric chloride), and dissolve them in 40 mL of methanol respectively, and ultrasonicate for 10 min to form a uniform solution, and then add the methanol solution of cobalt salt at a rate of 5 mL/min. Add the methanol solution of dimethylimidazole at the acceleration rate, continue to sonicate for 10min, then add the methanol solution of iron salt to the above solution at a dropping rate of 5mL/min, continue to sonicate for 30min, then transfer to the autoclave and heat to 120 ℃ for 4 hours, cooled to room temperature, alternately washed with water and absolute ethanol and centrifuged three times, and vacuum-dried at 60 ℃ for 10 hours to obtain a hollow Co 3 /Fe 1 bimetallic MOF (see Figure 1 c and e for SEM and TEM drawings); 10g of hollow Co 3 /Fe 1 bimetallic MOF and 10g of sublimated sulfur were evenly ground, heat-treated in an argon atmosphere at a heating rate of 5°C/min to 500°C (calcination temperature) for 3 hours, cooled to room temperature, and dissolved in 40mL of methanol Sonicate for 30 minutes, centrifuge at 10,000 rpm for 5 minutes, and dry at 60° C. for 10 hours; the composite material is obtained; the SEM and TEM drawings of the material are shown in d and f of FIG. 1 . It includes a carbon shell, and the inner surface of the carbon shell is compounded with cobalt sulfide, and the outer surface is compounded with iron oxide. The particle size of the composite material is 500nm, wherein the content of cobalt sulfide is 15%, the content of ferric oxide is 10%, and the content of carbon is 68%.
氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.55V；在过电位为320mV下，TOF为34.7s-1。The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.55V; at an overpotential of 320mV, the TOF is 34.7s -1 .
实施例2：Example 2:
和实施例1相比，区别仅在于，金属钴盐与铁盐的摩尔比为4∶1；其他物料、参数取值均不变。得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.63V；在过电位为320mV下，TOF为11.3s-1。Compared with Example 1, the only difference is that the molar ratio of metal cobalt salt to iron salt is 4:1; other materials and parameters are all unchanged. A composite material with a structure and morphology similar to Example 1 was obtained. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.63V; at an overpotential of 320mV, the TOF is 11.3s -1 .
实施例3：Example 3:
和实施例1相比，区别仅在于，金属钴盐与铁盐的摩尔比为2∶1；其他物料、参数取值均不变。得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.67V；在过电位为320mV下，TOF为8.6s-1。Compared with Example 1, the only difference is that the molar ratio of metal cobalt salt to iron salt is 2:1; other materials and parameters are all unchanged. A composite material with a structure and morphology similar to Example 1 was obtained. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.67V; at an overpotential of 320mV, the TOF is 8.6s -1 .
实施例4：Example 4:
和实施例1相比，区别仅在于，金属钴盐与铁盐的摩尔比为1∶1；其他物料、参数取值均不变。得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.72V；在过电位为320mV下，TOF为4.2s-1。Compared with Example 1, the only difference is that the molar ratio of the metal cobalt salt to the iron salt is 1:1; the values of other materials and parameters remain unchanged. A composite material with a structure and morphology similar to Example 1 was obtained. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.72V; at an overpotential of 320mV, the TOF is 4.2s -1 .
实施例5：和实施例1相比，区别仅在于，煅烧温度为800℃；其他物料、参数取值均不变。得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.64V；在过电位为320mV下，TOF为14.6s-1。Example 5: Compared with Example 1, the only difference is that the calcination temperature is 800° C.; the values of other materials and parameters remain unchanged. A composite material with a structure and morphology similar to Example 1 was obtained. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.64V; at an overpotential of 320mV, the TOF is 14.6s -1 .
实施例6：Embodiment 6:
和实施例1相比，区别仅在于，煅烧温度为300℃；其他物料、参数取值均不变。得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.72V；在过电位为320mV下，TOF为8.4s-1。Compared with Example 1, the only difference is that the calcination temperature is 300°C; the values of other materials and parameters remain unchanged. A composite material with a structure and morphology similar to Example 1 was obtained. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.72V; at an overpotential of 320mV, the TOF is 8.4s -1 .
实施例7：Embodiment 7:
和实施例1相比，区别仅在于，煅烧过程的升温速率为8℃/min；其他物料、参数取值均不变。得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.57V；在过电位为320mV下，TOF为21.5s-1。Compared with Example 1, the only difference is that the heating rate of the calcination process is 8°C/min; other materials and parameters are kept unchanged. A composite material with a structure and morphology similar to Example 1 was obtained. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.57V; at an overpotential of 320mV, the TOF is 21.5s -1 .
实施例8：Embodiment 8:
和实施例1相比，区别仅在于，煅烧过程的升温速率为2℃/min；其他物料、参数取值均不变。得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.61V；在过电位为320mV下，TOF为18.7s-1。Compared with Example 1, the only difference is that the heating rate of the calcination process is 2° C./min; other materials and parameters are kept unchanged. A composite material with a structure and morphology similar to Example 1 was obtained. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.61V; at an overpotential of 320mV, the TOF is 18.7s -1 .
实施例9Example 9
取钴盐(硝酸钴)3mol、二甲基咪唑8mol(616mg)、镍盐(硝酸镍)1mol，分别溶解在40mL甲醇中，超声10min形成均匀溶液，再钴盐的甲醇溶液以5mL/min的滴加速率加入二甲基咪唑的甲醇溶液中，继续超声10min，接着镍盐的甲醇溶液以5mL/min的滴加速率加入上述溶液中，继续超声30min，然后转入高压反应釜中，加热至120℃处理4h，冷却至室温，水、无水乙醇交替洗涤离心三次，60℃真空干燥10h，得到中空Co/Ni双金属MOF；取10g中空Co/Ni双金属MOF与10g升华硫研磨均匀，在氩气氛围下，以4～6℃/min升温速率至500℃热处理3小时，冷却至室温，溶于40mL甲醇中超声30min，10000rpm离心5min，60℃干燥10h；得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.58V；在过电位为320mV下，TOF为17.3s-1。Take 3 mol of cobalt salt (cobalt nitrate), 8 mol (616 mg) of dimethylimidazole, and 1 mol of nickel salt (nickel nitrate), dissolve them in 40 mL of methanol respectively, and ultrasonicate for 10 min to form a uniform solution, and then dissolve the methanol solution of cobalt salt at 5 mL/min Add the methanol solution of dimethylimidazole at a dropping rate, continue to sonicate for 10 minutes, then add the methanol solution of nickel salt to the above solution at a dropping rate of 5 mL/min, continue to sonicate for 30 minutes, then transfer to a high-pressure reactor and heat to Treat at 120°C for 4 hours, cool to room temperature, alternately wash and centrifuge with water and absolute ethanol three times, and vacuum-dry at 60°C for 10 hours to obtain hollow Co/Ni bimetallic MOF; take 10g of hollow Co/Ni bimetallic MOF and 10g of sublimated sulfur to grind evenly, Under an argon atmosphere, heat-treat at a rate of 4-6°C/min to 500°C for 3 hours, cool to room temperature, dissolve in 40 mL of methanol and sonicate for 30 minutes, centrifuge at 10,000 rpm for 5 minutes, and dry at 60°C for 10 hours; a structure similar to that of Example 1 was obtained Shaped composite materials. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.58V; at an overpotential of 320mV, the TOF is 17.3s -1 .
实施例10Example 10
钴盐(硝酸钴)3mol、二甲基咪唑8mol、铜盐(硝酸铜)1mol，分别溶解在40mL甲醇中，超声10min形成均匀溶液，再钴盐的甲醇溶液以5mL/min的滴加速率加入二甲基咪唑的甲醇溶液中，继续超声10min，接着铜盐的甲醇溶液以5mL/min的滴加速率加入上述溶液中，继续超声30min，然后转入高压反应釜中，加热至120℃处理4h，冷却至室温，水、无水乙醇交替洗涤离心三次，60℃真空干燥10h，得到中空Co/Cu双金属MOF；取10g中空Co/Cu双金属MOF与10g升华硫研磨均匀，在氩气氛围下，以4～6℃/min升温速率至500℃热处理3小时，冷却至室温，溶于40mL甲醇中超声30min，10000rpm离心5min，60℃干燥10h得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.61V；在过电位为320mV下，TOF为12.8s-1。Dissolve 3 mol of cobalt salt (cobalt nitrate), 8 mol of dimethylimidazole, and 1 mol of copper salt (copper nitrate) in 40 mL of methanol, and ultrasonicate for 10 minutes to form a uniform solution, then add the methanol solution of cobalt salt at a rate of 5 mL/min. In the methanol solution of dimethylimidazole, continue to sonicate for 10 minutes, then add the methanol solution of copper salt into the above solution at a dropping rate of 5mL/min, continue to sonicate for 30 minutes, then transfer to a high-pressure reactor, and heat to 120°C for 4 hours , cooled to room temperature, alternately washed with water and absolute ethanol and centrifuged three times, and vacuum-dried at 60°C for 10 hours to obtain a hollow Co/Cu bimetallic MOF; take 10g of hollow Co/Cu bimetallic MOF and 10g of sublimated sulfur to grind evenly, heat treatment at 500°C at a heating rate of 4-6°C/min for 3 hours, cooled to room temperature, dissolved in 40 mL of methanol, ultrasonicated for 30 minutes, centrifuged at 10,000 rpm for 5 minutes, and dried at 60°C for 10 hours to obtain a composite material with a structure similar to that of Example 1. . The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.61V; at an overpotential of 320mV, the TOF is 12.8s -1 .
实施例11Example 11
钴盐(硝酸钴)3mol、二甲基咪唑8mol、锌盐(硝酸锌)1mol，分别溶解在40mL甲醇中，超声10min形成均匀溶液，再钴盐的甲醇溶液以5mL/min的滴加速率加入二甲基咪唑的甲醇溶液中，继续超声10min，接着锌盐的甲醇溶液以5mL/min的滴加速率加入上述溶液中，继续超声30min，然后转入高压反应釜中，加热至120℃处理4h，冷却至室温，水、无水乙醇交替洗涤离心三次，60℃真空干燥10h，得到中空Co/Zn双金属MOF；取10g中空Co/Zn双金属MOF与10g升华硫研磨均匀，在氩气氛围下，以4～6℃/min升温速率至500℃热处理3小时，冷却至室温，溶于40mL甲醇中超声30min，10000rpm离心5min，60℃干燥10h得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.64V；在过电位为320mV下，TOF为14.8s-1。Dissolve 3 mol of cobalt salt (cobalt nitrate), 8 mol of dimethylimidazole, and 1 mol of zinc salt (zinc nitrate) in 40 mL of methanol, and ultrasonicate for 10 minutes to form a uniform solution, then add the methanol solution of cobalt salt at a rate of 5 mL/min. In the methanol solution of dimethylimidazole, continue to sonicate for 10 minutes, then add the methanol solution of zinc salt to the above solution at a dropping rate of 5mL/min, continue to sonicate for 30 minutes, then transfer to an autoclave, heat to 120°C for 4 hours , cooled to room temperature, alternately washed with water and absolute ethanol and centrifuged three times, and vacuum-dried at 60°C for 10 hours to obtain a hollow Co/Zn bimetallic MOF; take 10g of hollow Co/Zn bimetallic MOF and 10g of sublimated sulfur to grind evenly, and in argon atmosphere heat treatment at 500°C at a heating rate of 4-6°C/min for 3 hours, cooled to room temperature, dissolved in 40 mL of methanol, ultrasonicated for 30 minutes, centrifuged at 10,000 rpm for 5 minutes, and dried at 60°C for 10 hours to obtain a composite material with a structure similar to that of Example 1. . The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.64V; at an overpotential of 320mV, the TOF is 14.8s -1 .
实施例12Example 12
钴盐(硝酸钴)3mol、二甲基咪唑8mol、锰盐(硝酸锰)，分别溶解在40mL甲醇中，超声10min形成均匀溶液，再钴盐的甲醇溶液以5mL/min的滴加速率加入二甲基咪唑的甲醇溶液中，继续超声10min，接着锰盐的甲醇溶液以5mL/min的滴加速率加入上述溶液中，继续超声30min，然后转入高压反应釜中，加热至120℃处理4h，冷却至室温，水、无水乙醇交替洗涤离心三次，60℃真空干燥10h，得到中空Co/Mn双金属MOF；取10g中空Co/Mn双金属MOF与10g升华硫研磨均匀，在氩气氛围下，以4～6℃/min升温速率至500℃温度下处理3小时，冷却至室温，溶于40mL甲醇中超声30min，10000rpm离心5min，60℃干燥10h得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.66V；在过电位为320mV下，TOF为8.8s-1。3 mol of cobalt salt (cobalt nitrate), 8 mol of dimethylimidazole, and manganese salt (manganese nitrate) were dissolved in 40 mL of methanol respectively, and a uniform solution was formed by ultrasonication for 10 min. In the methanol solution of methylimidazole, continue to sonicate for 10 minutes, then add the methanol solution of manganese salt into the above solution at a dropping rate of 5mL/min, continue to sonicate for 30 minutes, then transfer to an autoclave, heat to 120°C for 4 hours, Cool to room temperature, alternately wash and centrifuge with water and absolute ethanol three times, and vacuum-dry at 60°C for 10 hours to obtain a hollow Co/Mn bimetallic MOF; take 10g of hollow Co/Mn bimetallic MOF and 10g of sublimated sulfur to grind evenly, , treated at a temperature of 500°C at a heating rate of 4-6°C/min for 3 hours, cooled to room temperature, dissolved in 40mL of methanol, ultrasonicated for 30min, centrifuged at 10,000rpm for 5min, and dried at 60°C for 10h to obtain a composite with a similar structure and appearance as in Example 1. Material. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.66V; at an overpotential of 320mV, the TOF is 8.8s -1 .
实施例13：Example 13:
和实施例1相比，区别仅在于，水热反应温度为60℃。得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.70V；在过电位为320mV下，TOF为5.4s-1。Compared with Example 1, the only difference is that the hydrothermal reaction temperature is 60°C. A composite material with a structure and morphology similar to Example 1 was obtained. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.70V; at an overpotential of 320mV, the TOF is 5.4s -1 .
实施例14：Example 14:
和实施例1相比，区别仅在于，水热反应温度为180℃。得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.67V；在过电位为320mV下，TOF为13.5s-1。Compared with Example 1, the only difference is that the hydrothermal reaction temperature is 180°C. A composite material with a structure and morphology similar to Example 1 was obtained. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.67V; at an overpotential of 320mV, the TOF is 13.5s -1 .
实施例15：Example 15:
和实施例1相比，区别仅在于，水热反应温度为140℃。得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.59V；在过电位为320mV下，TOF为15.2s-1。Compared with Example 1, the only difference is that the hydrothermal reaction temperature is 140°C. A composite material with a structure and morphology similar to Example 1 was obtained. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.59V; at an overpotential of 320mV, the TOF is 15.2s -1 .
实施例16Example 16
和实施例1相比，区别仅在于，双金属MOF和升华硫的质量比为4∶1。得到和实施例1类似结构形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.64V；在过电位为320mV下，TOF为9.1s-1。Compared with Example 1, the only difference is that the mass ratio of bimetallic MOF and sublimed sulfur is 4:1. A composite material with a structure and morphology similar to Example 1 was obtained. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.64V; at an overpotential of 320mV, the TOF is 9.1s -1 .
实施例17Example 17
和实施例1相比，区别仅在于，配体材料使用对苯二甲酸，得到了立方体形貌的复合材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.68V；在过电位为320mV下，TOF为11.5s-1。Compared with Example 1, the only difference is that terephthalic acid is used as the ligand material to obtain a composite material with a cubic shape. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.68V; at an overpotential of 320mV, the TOF is 11.5s -1 .
对比例1Comparative example 1
和实施例1相比，区别仅在于，省去水热反应过程；将钴盐、二甲基咪唑、铁盐超声处理后固液分离、干燥后直接和硫混合，进行后续的煅烧，得到实心材料。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.75V；在过电位为320mV下，TOF为0.7s-1。Compared with Example 1, the only difference is that the hydrothermal reaction process is omitted; the cobalt salt, dimethylimidazole, and iron salt are ultrasonically treated, solid-liquid separated, dried, and directly mixed with sulfur, followed by subsequent calcination to obtain a solid Material. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.75V; at an overpotential of 320mV, the TOF is 0.7s -1 .
对比例2：Comparative example 2:
和实施例1相比，区别仅在于，除去加升化硫研磨过程；即，将得到的双金属MOF直接进行后续的煅烧处理。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.88V；在过电位为320mV下，TOF为0.1s-1。Compared with Example 1, the only difference is that the grinding process of adding sulfur sulfide is removed; that is, the obtained bimetallic MOF is directly subjected to subsequent calcination treatment. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.88V; at an overpotential of 320mV, the TOF is 0.1s -1 .
对比例3：Comparative example 3:
和实施例1相比，区别仅在于，煅烧温度为200℃。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.84V；在过电位为320mV下，TOF为0.5s-1。Compared with Example 1, the only difference is that the calcination temperature is 200°C. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.84V; at an overpotential of 320mV, the TOF is 0.5s -1 .
对比例4Comparative example 4
和实施例1相比，区别仅在于，煅烧温度为900℃。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.59V；在过电位为320mV下，TOF为3.3s-1。Compared with Example 1, the only difference is that the calcination temperature is 900°C. The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.59V; at an overpotential of 320mV, the TOF is 3.3s -1 .
对比例5Comparative example 5
取二甲基咪唑、铁盐，分别溶解在40mL甲醇中，超声10min形成均匀溶液，再铁盐的甲醇溶液以5mL/min的滴加速率加入二甲基咪唑的甲醇溶液中，继续超声30min，然后转入高压反应釜中，加热至80～160℃处理4～8h，冷却至室温，水、无水乙醇交替洗涤离心三次，60℃真空干燥10h，得到中空Fe-MOF；取10g中空Fe-MOF与10g升华硫研磨均匀，在氩气氛围下，以4～6℃/min升温速率至500℃热处理3小时，冷却至室温，溶于40mL甲醇中超声30min，10000rpm离心5min，60℃干燥10h。氧气析出性能结果如下：在电流密度10mA/cm2下，氧气析出电位为0.74V；在过电位为320mV下，TOF为0.5s-1。和实施例1相比，采用单一金属，无法得到类似于本发明的双金属中空复合材料，OER催化性能明显差于本发明技术方案。Take dimethylimidazole and iron salt, dissolve them in 40mL of methanol respectively, and ultrasonicate for 10min to form a uniform solution, then add the methanol solution of iron salt into the methanol solution of dimethylimidazole at a dropping rate of 5mL/min, and continue to sonicate for 30min. Then transfer to a high-pressure reactor, heat to 80-160°C for 4-8 hours, cool to room temperature, wash and centrifuge three times alternately with water and absolute ethanol, and vacuum-dry at 60°C for 10 hours to obtain a hollow Fe-MOF; take 10g of hollow Fe- Grind MOF and 10g of sublimated sulfur evenly, heat-treat at 500°C for 3 hours at a heating rate of 4-6°C/min in an argon atmosphere, cool to room temperature, dissolve in 40mL of methanol and sonicate for 30min, centrifuge at 10,000rpm for 5min, and dry at 60°C for 10h . The oxygen evolution performance results are as follows: at a current density of 10mA/cm 2 , the oxygen evolution potential is 0.74V; at an overpotential of 320mV, the TOF is 0.5s -1 . Compared with Example 1, the bimetallic hollow composite material similar to the present invention cannot be obtained by using a single metal, and the OER catalytic performance is significantly worse than the technical solution of the present invention.
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