CN106824198A - Cobalt-based produces VPO catalysts and preparation method thereof and a kind of alkaline hydrogen manufacturing electrolytic cell - Google Patents
Cobalt-based produces VPO catalysts and preparation method thereof and a kind of alkaline hydrogen manufacturing electrolytic cell Download PDFInfo
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- CN106824198A CN106824198A CN201710142190.4A CN201710142190A CN106824198A CN 106824198 A CN106824198 A CN 106824198A CN 201710142190 A CN201710142190 A CN 201710142190A CN 106824198 A CN106824198 A CN 106824198A
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- cobalt
- presoma
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- comoo
- nanometer rods
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 50
- 239000010941 cobalt Substances 0.000 title claims abstract description 50
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 18
- 239000001257 hydrogen Substances 0.000 title claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229910018864 CoMoO4 Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001450 anions Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 9
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 9
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 8
- 150000003346 selenoethers Chemical class 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 83
- 239000000243 solution Substances 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000011684 sodium molybdate Substances 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 4
- 235000011009 potassium phosphates Nutrition 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- 229960001471 sodium selenite Drugs 0.000 claims description 4
- 239000011781 sodium selenite Substances 0.000 claims description 4
- 235000015921 sodium selenite Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- RNGFNLJMTFPHBS-UHFFFAOYSA-L dipotassium;selenite Chemical compound [K+].[K+].[O-][Se]([O-])=O RNGFNLJMTFPHBS-UHFFFAOYSA-L 0.000 claims description 3
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 238000005349 anion exchange Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000005518 electrochemistry Effects 0.000 abstract description 6
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 24
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229940065287 selenium compound Drugs 0.000 description 2
- 150000003343 selenium compounds Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018916 CoOOH Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 230000010613 Electrolyte Activity Effects 0.000 description 1
- 241001465805 Nymphalidae Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910018143 SeO3 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- -1 is as a result shown Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 239000003643 water by type Substances 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
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
-
- 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
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/40—
-
- 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
-
- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
-
- 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
Abstract
The invention provides the preparation method that a kind of cobalt-based produces VPO catalysts, comprise the following steps：A CoMoO) is prepared4Nanometer rods presoma；B) by the CoMoO4Nanometer rods presoma is distributed in the solution of anion presoma, and anion exchange is carried out by hydro-thermal reaction, obtains cobalt-base catalyst；The anion presoma is selected from metal hydroxides, metal sulfide, metal selenide or phosphate compounds.The present invention is by CoMoO4Nanometer rods presoma and anion presoma carry out hydro-thermal reaction, you can the cobalt-based for obtaining consistent appearance produces VPO catalysts, and method and step is simple, and operation is simple, with easily and fast the features such as.The catalytic performance of the catalyst that the present invention is provided is excellent, has good application prospect in fields such as electrochemistry complete solution water hydrogen manufacturing.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to cobalt-based produces VPO catalysts and preparation method thereof and one kind
Alkaline hydrogen manufacturing electrolytic cell.
Background technology
Hydrogen-oxygen fuel cell due to having the advantages that high-energy-density and almost zero carbon emission, as current energy field
Study hotspot.Practical hydrogen-oxygen fuel cell is developed to have great significance the energy and environment problem of the world today.Reduce hydrogen
Economy prepared by gas and the key link that Environmental costs are Developing Extension hydrogen-oxygen fuel cells.Prepare a kind of more environmental protection of hydrogen
Method be exactly water electrolysis hydrogen production, the hydrogen of oxygen evolution reaction and negative electrode that water electrolysis hydrogen production reaction is divided into anode separates out anti-
Should.Slow four electronic processes are one of central factors of restriction electrolysis water application in oxygen evolution reaction, and searching is suitably urged
Agent is the important channel of solve problem.The catalyst for being presently used for oxygen evolution reaction is still very rare earth reserves
The oxide of noble ruthenium and iridium.Therefore, efficient, stable and cheap non-noble metallic materials are developed to be reacted as oxygen evolution
Catalyst is one important research direction of modern chemistry Material Field.
Strong acid and strong alkaline electrolytes can meet water decomposition needed for fast ionic transmission requirement.Relative to acid electricity
Solution liquid, alkaline electrolyte produces hydrogen, because it has lower vapour pressure thus can obtain the hydrogen of higher purity, quilt extensively
Industrial quarters is received.And most of catalyst for producing oxygen, such as metal oxide has higher in alkaline electrolyte
Activity, but have poor activity and stability in acidic electrolysis bath.Therefore the research of catalyst is subject to more under alkalescence condition
It is extensive concern.
Between past decades, researcher explores the catalyst that numerous Co based compounds react as oxygen evolution,
Including CoSe2Nanobelt, CoOOH nanometer rods, Co3S4Nanometer sheet, Co3(PO4)3·8H2O nanospheres, CoMoO4Nano wire.But
In each work, the pattern of material has notable difference and catalytic performance is relatively low.
The content of the invention
In view of this, the technical problem to be solved in the present invention be provide cobalt-based produce VPO catalysts and preparation method thereof and
A kind of alkaline hydrogen manufacturing electrolytic cell, the cobalt-based that can prepare consistent appearance according to preparation method of the present invention produces VPO catalysts, and
The catalytic performance that the cobalt-based produces VPO catalysts is excellent.
The invention provides the preparation method that cobalt-based produces VPO catalysts, comprise the following steps：
A CoMoO) is prepared4Nanometer rods presoma；
B) by the CoMoO4Nanometer rods presoma is distributed in the solution of anion presoma, is carried out by hydro-thermal reaction
Anion exchange, obtains cobalt-base catalyst；The anion presoma is selected from metal hydroxides, metal sulfide, metallic selenium
Compound or phosphate compounds.
Preferably, the CoMoO4Nanometer rods presoma is prepared as follows：
Cobalt salt, molybdate are mixed with deionized water, mixed solution is obtained；
Separated successively after the mixed solution is reacted under conditions of 120~180 DEG C, washed and dried,
Obtain CoMoO4Nanometer rods presoma.
Preferably, the cobalt salt be cobalt nitrate, cobalt chloride and cobalt acetate in one or more, molybdate be sodium molybdate and
One or more in ammonium molybdate.
Preferably, the metal hydroxides is selected from one or more in lithium hydroxide, NaOH and potassium hydroxide；
The metal sulfide is selected from one or more in vulcanized sodium and potassium sulfide；
The metal selenide is selected from one or more of sodium selenite and potassium selenite；
The phosphate compounds is selected from one or more in potassium phosphate, sodium phosphate and ammonium phosphate.
Preferably, step B) in, the solvent of the solution of the anion presoma is in water, ethanol and ethylene glycol
Plant or various.
Preferably, the CoMoO4The ratio of the amount of the material of nanometer rods presoma and anion presoma for (0.1~
2)：(0.2~40).
Preferably, the hydrothermal temperature is 80~160 DEG C, and the reaction time is 8~24h.
VPO catalysts are produced present invention also offers the cobalt-based that a kind of above-mentioned preparation method is prepared, the cobalt-based produces oxygen and urges
Agent is selected from Co (OH)2、Co3S4、CoSe2Or Co3(PO4)2。
Present invention also offers a kind of alkaline hydrogen manufacturing electrolytic cell, including anode, negative electrode, barrier film and electrolyte, the anode
VPO catalysts are produced including the cobalt-based that above-mentioned preparation method is prepared.
Compared with prior art, the invention provides the preparation method that a kind of cobalt-based produces VPO catalysts, comprise the following steps：
A CoMoO) is prepared4Nanometer rods presoma；B) by the CoMoO4Nanometer rods presoma is distributed in the solution of anion presoma,
Anion exchange is carried out by hydro-thermal reaction, cobalt-base catalyst is obtained；The anion presoma is selected from metal hydroxides, gold
Category sulfide, metal selenide or phosphate compounds.The present invention is by CoMoO4Nanometer rods presoma enters with anion presoma
Water-filling thermal response, you can the cobalt-based for obtaining consistent appearance produces VPO catalysts, and method and step is simple, and operation is simple, with convenient, fast
Fast the features such as.The catalytic performance of the catalyst that the present invention is provided is excellent, has well in fields such as electrochemistry complete solution water hydrogen manufacturing
Application prospect.
Result shows that the cobalt-based that the present invention is provided produces VPO catalysts consistent appearance, with one-dimensional rod-like pattern, and diameter
It is more homogeneous, it is 200~400nm.Wherein cobalt-based produces VPO catalysts Co (OH)2、Co3S4、CoSe2And Co3(PO4)2It is respectively required for
Wanting the overpotential of 388mV, 393mV, 349mV, 332mV and 346mV can just reach 10mA/cm2Current density, hence it is evident that better than business
The best RuO of industry2Catalyst (395mV).
Brief description of the drawings
Fig. 1 is the CoMoO that embodiment 1 is obtained4The transmission electron microscope photo of nanometer rods presoma；
Fig. 2 is the Co (OH) that embodiment 1 is obtained2The stereoscan photograph of material；
Fig. 3 is the Co (OH) that embodiment 1 is obtained2The transmission electron microscope photo of material；
Fig. 4 is the Co (OH) that embodiment 2 is obtained2The stereoscan photograph of material；
Fig. 5 is the Co (OH) that embodiment 3 is obtained2The transmission electron microscope photo of material；
Fig. 6 is the Co (OH) that embodiment 4 is obtained2The transmission electron microscope photo of material；
Fig. 7 is the Co (OH) that embodiment 5 is obtained2The transmission electron microscope photo of material；
Fig. 8 is the Co that embodiment 6 is obtained3S4The stereoscan photograph of material；
Fig. 9 is the Co that embodiment 6 is obtained3S4The transmission electron microscope photo of material；
Figure 10 is the CoSe that embodiment 7 is obtained2The stereoscan photograph of material；
Figure 11 is the CoSe that embodiment 7 is obtained2The transmission electron microscope photo of material；
Figure 12 is the Co that embodiment 8 is obtained3(PO4)2The stereoscan photograph of material；
Figure 13 is the Co that embodiment 7 is obtained3(PO4)2The transmission electron microscope photo of material；
Figure 14 is the XRD spectra that serial cobalt-based prepared by the embodiment of the present invention 1,6,7,8 produces VPO catalysts material；
Figure 15 is that serial cobalt-based prepared by embodiment 1,6,7,8 produces linear scan of the VPO catalysts material in oxygen reaction is produced
The Dependence Results of voltammetry test.
Specific embodiment
The invention provides the preparation method that a kind of cobalt-based produces VPO catalysts, comprise the following steps：
A CoMoO) is prepared4Nanometer rods presoma；
B) by the CoMoO4Nanometer rods presoma is distributed in the solution of anion presoma, is carried out by hydro-thermal reaction
Anion exchange, obtains cobalt-base catalyst；The anion presoma is selected from metal hydroxides, metal sulfide, metallic selenium
Compound or phosphate compounds.
The method comprises the steps of firstly, preparing CoMoO4Nanometer rods presoma, the CoMoO4Nanometer rods presoma enters as follows
It is prepared by row：
Cobalt salt, molybdate are mixed with deionized water, mixed solution is obtained；
Separated successively after the mixed solution is reacted under conditions of 120~180 DEG C, washed and dried,
Obtain CoMoO4Nanometer rods presoma.
Specifically, cobalt salt and molybdate are added in deionized water, mixed solution is obtained.Wherein, cobalt salt and molybdate
Mol ratio be preferably (1~4)：(1~4), more preferably 1:1.In some specific embodiments of the invention, the cobalt salt,
The amount ratio of molybdate and water is preferably (1~4) mmol：(1~4) mmol：35mL.Wherein, the cobalt salt in methods described is preferred
It is one or more in cobalt nitrate, cobalt chloride and cobalt acetate, more preferably one or more in cobalt nitrate and cobalt chloride.Its
In, molybdate is preferably one or two in sodium molybdate and ammonium molybdate, more preferably sodium molybdate.
The present invention is not particularly limited to the charging sequence of cobalt salt and molybdate and water.Mode of the present invention to the mixing
Not specifically limited, well known to a person skilled in the art mixed method, stirring makes mixing equal such as on magnetic stirring apparatus
Mixed solution that is even, being clarified.
After obtaining mixed solution, divided successively after the mixed solution is reacted under conditions of 120~180 DEG C
From, washing and dry, obtain CoMoO4Nanometer rods presoma.
In the present invention, described 120~180 DEG C of heating means are not specifically limited, preferably carry out in an oven
It is heated to 120~180 DEG C to be reacted, the temperature of the reaction is preferably 130~160 DEG C, more preferably 150 DEG C；It is described anti-
The time answered is 4~12h, more preferably 6h~10h.
After heating response, product is obtained, the product is precipitated for purple.Purple precipitation is carried out successively
Separate, wash and dry, obtain CoMoO4Nanometer rods presoma.The present invention to the separation, washing and dry method not
Have specifically limited, well known to a person skilled in the art separation, washing and dry method.In the present invention, the separation
Preferably centrifugation；The dry temperature is preferably 50 DEG C~100 DEG C, more preferably 60 DEG C~90 DEG C.It is described dry
Time is preferably 4h~24h, most preferably more preferably 6h~20h, 12h~15h.
Then, by the CoMoO4Nanometer rods presoma is distributed in the solution of anion presoma, by hydro-thermal reaction
Anion exchange is carried out, cobalt-base catalyst is obtained；The anion presoma is selected from metal hydroxides, metal sulfide, gold
Category selenides or phosphate compounds.
The embodiment of the present invention is preferably by CoMoO4Nanometer rods are distributed in the precursor solution of anion, obtain mixing molten
Liquid.Wherein, CoMoO4The ratio of the amount of the material of nanometer rods presoma and anion presoma is preferably (0.1~2)：(0.2~
40), more preferably (0.1~0.5)：(0.2~10).
Wherein, metal hydroxides is preferably one or more in lithium hydroxide, NaOH and potassium hydroxide, more excellent
Elect the one or two kinds of in NaOH and potassium hydroxide as；The metal sulfide is preferably in vulcanized sodium and potassium sulfide
One or more, more preferably vulcanized sodium；The metal selenide is preferably the one kind or many in sodium selenite and potassium selenite
Plant, more preferably sodium selenite.The phosphate compounds is preferably the one kind or many in potassium phosphate, sodium phosphate and ammonium phosphate
Plant, more preferably potassium phosphate.
The solvent of the solution of the anion presoma is one or more in water, ethanol and ethylene glycol, more preferably
It is the one or two kinds of in water and ethylene glycol.
CoMoO will be obtained4Nanometer rods presoma is heated with the mixed solution of anion presoma, is carried out by hydro-thermal reaction
Anion exchange, wherein, the temperature of the hydro-thermal reaction is preferably 80 DEG C~160 DEG C, more preferably 80~140 DEG C；The water
The time of thermal response is preferably 8h~24h, more preferably 8h~12h.
The product of hydro-thermal reaction is centrifuged, is washed, dried in vacuum drying chamber, obtained cobalt-base catalyst.
Wherein, the centrifugation is separate mode commonly used in the art；The washing is technological means well known to those skilled in the art, this
Invention is not particularly limited.In the present invention, the dry temperature is preferably 50 DEG C~100 DEG C, more preferably 60 DEG C~90
℃.The dry time is preferably 4h~24h, most preferably more preferably 6h~20h, 12h~15h.
Electronic microscope photos is carried out to it after obtaining cobalt-base catalyst, is as a result shown, cobalt-based prepared by the present invention produces VPO catalysts
Consistent appearance, with one-dimensional rod-like pattern, and size is more homogeneous, is 200~400nm.
Present invention also offers a kind of alkaline hydrogen manufacturing electrolytic cell, including anode, negative electrode, barrier film and electrolyte, the anode
VPO catalysts are produced including the cobalt-based that above-mentioned preparation method is prepared.
The application that VPO catalysts produce oxygen field as catalyst in electrochemistry is produced present invention also offers a kind of cobalt-based.
The present invention is by CoMoO4Nanometer rods presoma carries out hydro-thermal reaction with anion presoma, you can obtain consistent appearance
Cobalt-based produce VPO catalysts, method and step is simple, and operation is simple, with easily and fast the features such as.The catalyst that the present invention is provided
Catalytic performance it is excellent, have good application prospect in fields such as electrochemistry complete solution water.
Result shows that the cobalt-based that the present invention is provided produces VPO catalysts consistent appearance, with one-dimensional rod-like pattern, and size
It is more homogeneous, it is 200~400nm.Wherein, cobalt-based produces VPO catalysts Co (OH)2、Co3S4、CoSe2And Co3(PO4)2It is respectively required for
Wanting the overpotential of 388mV, 393mV, 349mV, 332mV and 346mV can just reach 10mA/cm2Current density, hence it is evident that better than business
The best RuO of industry2Catalyst (395mV).
For a further understanding of the present invention, VPO catalysts and its system are produced to the cobalt-based that the present invention is provided with reference to embodiment
Preparation Method and alkaline hydrogen manufacturing electrolytic cell are illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
(1)CoMoO4The preparation of nanometer rods presoma：
By 2mmol Co (NO3)2·6H2O and 2mmol Na2MoO4·2H2O is dissolved in 17.5ml deionized waters respectively,
Stirring fully dissolving；By above-mentioned Na2MoO4Solution is added to Co (NO3)2In solution, stir 10 minutes, formation uniformly mixes molten
Liquid；The mixed solution is transferred in 50ml reactors, is put into 150 DEG C of baking ovens, react 6h；Reactor is taken out, observation finds
A large amount of purples precipitations, centrifugation and then with twice of distillation water washing wash one time with ethanol, is placed on dry in 60 DEG C of vacuum drying chambers
Dry 12h, obtains CoMoO4Nanometer rods presoma.
To above-mentioned CoMoO4Nanometer rods presoma carries out projection electron microscopic observation, as a result sees that Fig. 1, Fig. 1 are what embodiment 1 was obtained
CoMoO4The transmission electron microscope photo of nanometer rods presoma.It will be seen from figure 1 that CoMoO4Nanometer rods have consistent one-dimensional pattern,
And surface is smooth, length is a few micrometers, and diameter is about 200~300nm.
(2) cobalt-based produces VPO catalysts Co (OH)2The preparation of material：
The solution containing 0.2mmol KOH is prepared, solvent is the body of the mixed solution of 20mL water and ethylene glycol, water and ethylene glycol
Product is than being 1:1；By 0.1mmol CoMoO4Nanometer rods presoma ultrasonic disperse is in above-mentioned solution；Then said mixture is turned
Move on in 50ml reactors, put into 120 DEG C of baking ovens, react 12h；Reactor is taken out, observation discovery there are a large amount of precipitations to occur, from
With twice of water washing of distillation after the heart, wash with ethanol one time, be placed in 60 DEG C of vacuum drying chambers and dry 12h, obtained cobalt-based and produce
VPO catalysts Co (OH)2Material.
To above-mentioned Co (OH)2Material is scanned Electronic Speculum and transmission electron microscope observing, as a result sees Fig. 2 and Fig. 3, Fig. 2 to implement
The Co (OH) that example 1 is obtained2The stereoscan photograph of material, Fig. 3 is the Co (OH) that embodiment 1 is obtained2The transmission electron microscope of material shines
Piece, from figures 2 and 3, it will be seen that Co (OH)2The surface of material is made up of a large amount of nanometer sheets, and forms loose structure, and maintains
One-dimentional structure, diameter is about 300~400nm, composition Co (OH)2The size of the nanometer sheet of material surface is 50~100nm.
Embodiment 2
Preparation method according to embodiment 1 carries out the preparation that cobalt-based produces VPO catalysts, there is following difference：Prepare it is cloudy from
During sub- precursor solution, selection 20mL water is reaction dissolvent, obtains Co (OH)2Material.
The material that will be obtained is scanned electronic microscope photos, and as a result referring to Fig. 4, Fig. 4 is the Co (OH) that embodiment 2 is obtained2Material
The stereoscan photograph of material.The Co (OH) obtained with embodiment 12Material is compared, the Co (OH) that the present embodiment 2 is obtained2Material morphology
Still it is the one-dimentional structure of nanometer sheet composition without significant difference, diameter is about 300~400nm, composition Co (OH)2Material surface
The size of nanometer sheet is 50~100nm.
Embodiment 3
Preparation method according to embodiment 1 carries out the preparation that cobalt-based produces VPO catalysts, there is following difference：Prepare it is cloudy from
During sub- precursor solution, selection 0.2mmol NaOH are presoma, obtain Co (OH)2Material.
The material that will be obtained carries out transmission electron microscope analysis, and as a result referring to Fig. 5, Fig. 5 is the Co (OH) that embodiment 3 is obtained2Material
The transmission electron microscope photo of material.The Co (OH) obtained with embodiment 12Material is compared, the Co (OH) that the present embodiment 3 is obtained2Material morphology
Still it is the one-dimentional structure of nanometer sheet composition without significant difference, diameter is about 300~400nm, composition Co (OH)2Material surface
The size of nanometer sheet is 50~100nm.
Embodiment 4
Preparation method according to embodiment 1 carries out the preparation that cobalt-based produces VPO catalysts, there is following difference：Carry out it is cloudy from
When son exchanges hydro-thermal reaction, reaction temperature is 80 DEG C, obtains Co (OH)2Material.
The material that will be obtained carries out transmission electron microscope analysis, and as a result referring to Fig. 6, Fig. 6 is the Co (OH) that embodiment 4 is obtained2Material
The transmission electron microscope photo of material.The Co (OH) obtained with embodiment 12Material is compared, the Co (OH) that the present embodiment 4 is obtained2Material morphology
Still it is the one-dimentional structure of nanometer sheet composition without significant difference, diameter is about 300~400nm, composition Co (OH)2Material surface
The size of nanometer sheet is 50~100nm.
Embodiment 5
Preparation method according to embodiment 1 carries out the preparation that cobalt-based produces VPO catalysts, there is following difference：Carry out it is cloudy from
When son exchanges hydro-thermal reaction, reaction temperature is 100 DEG C, obtains Co (OH)2Material.
The material that will be obtained carries out transmission electron microscope analysis, and as a result referring to Fig. 7, Fig. 7 is the Co (OH) that embodiment 5 is obtained2Material
The transmission electron microscope photo of material.The Co (OH) obtained with embodiment 12Material is compared, the Co (OH) that the present embodiment 5 is obtained2Material morphology
Still it is the one-dimentional structure of nanometer sheet composition without significant difference, diameter is about 300~400nm, composition Co (OH)2Material surface
The size of nanometer sheet is 50~100nm.
Embodiment 6
Preparation method according to embodiment 1 carries out the preparation that cobalt-based produces VPO catalysts, there is following difference：Prepare it is cloudy from
During sub- precursor solution, 1mmol Na are selected2S is presoma, you can obtains cobalt-based and produces VPO catalysts Co3S4Material.
The material that will be obtained is scanned electromicroscopic photograph and transmission electron microscope analysis, is as a result implementation referring to Fig. 8 and Fig. 9, Fig. 8
The Co that example 6 is obtained3S4The stereoscan photograph of material, Fig. 9 is the Co that embodiment 6 is obtained3S4The transmission electron microscope photo of material.From
Fig. 8 and Fig. 9 can be seen that Co3S4Than more uniform, surface is made up of the pattern of material a large amount of particles, goes out without obvious nano aperture
It is existing, and one-dimentional structure is maintain, diameter is about 200~300nm, constitutes Co3S4The size of the nano particle of material surface be 5~
20nm。
Embodiment 7
Preparation method according to embodiment 1 carries out the preparation that cobalt-based produces VPO catalysts, there is following difference：Prepare it is cloudy from
During sub- precursor solution, 0.2mmol Na are selected2SeO3With 0.4mmol NaBH4Mixed solution is presoma, you can obtain cobalt-based
Produce VPO catalysts CoSe2Material.
The material that will be obtained is scanned electromicroscopic photograph and transmission electron microscope analysis, as a result referring to Figure 10 and Figure 11, Tu10Wei
The CoSe that embodiment 7 is obtained2The stereoscan photograph of material, Figure 11 is the CoSe that embodiment 7 is obtained2The transmission electron microscope of material shines
Piece.CoSe is can be seen that from Figure 10 and Figure 112Than more uniform, surface is made up of the pattern of material a large amount of nanometer sheets, and maintains
One-dimentional structure, diameter is about 300~400nm, constitutes Co3S4The size of the nanometer sheet of material surface is 10~50nm.With embodiment
1 Co for obtaining (OH)2Material is compared, and the nanometer sheet is smaller.
Embodiment 8
Preparation method according to embodiment 1 carries out the preparation that cobalt-based produces VPO catalysts, there is following difference：Prepare it is cloudy from
During sub- precursor solution, 0.2mmol K are selected3PO4·3H2O is presoma, you can obtains cobalt-based and produces VPO catalysts Co3(PO4)2
Material.
The material that will be obtained is scanned electromicroscopic photograph and transmission electron microscope analysis, as a result referring to Figure 12 and Figure 13, Tu12Wei
The Co that embodiment 8 is obtained3(PO4)2The stereoscan photograph of material, Figure 13 is the Co that embodiment 7 is obtained3(PO4)2The transmission of material
Electromicroscopic photograph.Co is can be seen that from Figure 12 and Figure 133(PO4)2The pattern of material is than more uniform, surface smoother, nanometer rods
Inside has substantial amounts of nano aperture to occur, and maintains one-dimentional structure, and diameter is about 200~300nm.
Embodiment 9
Serial cobalt-based prepared by embodiment 1,6,7,8 produces VPO catalysts material and carries out XRD characterized by techniques, as a result referring to figure
14, Figure 14 is the XRD spectra that serial cobalt-based prepared by the embodiment of the present invention 1,6,7,8 produces VPO catalysts material.Can be with from Figure 14
Find out, original CoMoO4The XRD diffraction patterns of nanometer rods presoma have sharp strong peak, it is meant that its crystallinity is preferable.
By different anion exchange reactions, the serial cobalt-based for obtaining produces VPO catalysts material includes Co (OH)2、Co3S4、CoSe2And
Co3(PO4)2There are the XRD peaks of relatively wideization, it is meant that the successful generation of the anion exchange reaction.Simultaneously poor crystallinity
It is primarily due to anion exchange reaction and destroys original CoMoO4The crystallinity of high-sequential.
Embodiment 10
The serial cobalt-based for being prepared with embodiment 1,6,7,8 respectively produces VPO catalysts material and the best RuO of business2Material
Used as catalyst, the activity for carrying out electrochemistry product oxygen reaction is detected that specific method is：Determined under three electrode conditions, rotation
Turn disk electrode supported catalyst as working electrode, the wherein load capacity of catalyst is 0.5mg/cm2, platinized platinum is used as to electricity
Pole, saturated calomel electrode is used as reference electrode.The electrolyte of electrochemical reaction is the KOH solution of 0.1mol/L, polarization curve
Sweep speed is 2mV/s.
Testing result is referring to Figure 15.Figure 15 is that serial cobalt-based prepared by embodiment 1,6,7,8 produces VPO catalysts material in product
The Dependence Results of the linear sweep voltammetry test in oxygen reaction.It can be seen from fig. 15 that relative to our cobalt-based material, business
Industry RuO2Material has substantially low take-off potential, but it performs poor at higher current densities, is than what the present invention was provided
Row cobalt-based produces VPO catalysts material will be poor.For example, in 10mA/cm2Current density under, serial cobalt-based produces VPO catalysts material
CoMoO4、Co(OH)2、Co3S4、CoSe2And Co3(PO4)2Need only to the mistake of 388mV, 393mV, 349mV, 332mV and 346mV
Potential can just reach.And the RuO of business2Catalyst but needs overpotential up to 395mV.Meanwhile, the catalytic performance was reported than before
The Mn in road3O4/CoSe2And CoSe (J.Am.Chem.Soc.2012,134,2930.)2-Graphene(Acs Nano 2014,8,
3970-3978.) catalytic performance of material will get well.
As seen from the above embodiment, the method and step that the present invention is provided is simple, and operation is simple, has in extensive preparation.Together
When, there is serial cobalt-base catalyst prepared by the present invention excellent electrochemistry to produce oxygen catalytic performance, in industrial electrolysis water field tool
There is potential application value.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of cobalt-based produces the preparation method of VPO catalysts, it is characterised in that comprise the following steps：
A CoMoO) is prepared4Nanometer rods presoma；
B) by the CoMoO4Nanometer rods presoma is distributed in the solution of anion presoma, by hydro-thermal reaction carry out it is cloudy from
Son is exchanged, and obtains cobalt-base catalyst；The anion presoma is selected from metal hydroxides, metal sulfide, metal selenide
Or phosphate compounds.
2. preparation method according to claim 1, it is characterised in that the CoMoO4Nanometer rods presoma is according to such as lower section
Method is prepared：
Cobalt salt, molybdate are mixed with deionized water, mixed solution is obtained；
Separated successively after the mixed solution is reacted under conditions of 120~180 DEG C, washed and dried, obtained
CoMoO4Nanometer rods presoma.
3. preparation method according to claim 2, it is characterised in that the cobalt salt is cobalt nitrate, cobalt chloride and cobalt acetate
In one or more, molybdate be sodium molybdate and ammonium molybdate in one or more.
4. preparation method according to claim 1, it is characterised in that the metal hydroxides is selected from lithium hydroxide, hydrogen
One or more in sodium oxide molybdena and potassium hydroxide；
The metal sulfide is selected from one or more in vulcanized sodium and potassium sulfide；
The metal selenide is selected from one or more of sodium selenite and potassium selenite；
The phosphate compounds is selected from one or more in potassium phosphate, sodium phosphate and ammonium phosphate.
5. preparation method according to claim 1, it is characterised in that step B) in, the solution of the anion presoma
Solvent be one or more in water, ethanol and ethylene glycol.
6. preparation method according to claim 1, it is characterised in that the CoMoO4Before nanometer rods presoma and anion
The ratio for driving the amount of the material of body is (0.1~2)：(0.2~40).
7. preparation method according to claim 1, it is characterised in that the hydrothermal temperature is 80~160 DEG C, reaction
Time is 8~24h.
8. the cobalt-based that a kind of preparation method as described in any one of claim 1~7 is prepared produces VPO catalysts, the cobalt-based
Produce VPO catalysts and be selected from Co (OH)2、Co3S4、CoSe2Or Co3(PO4)2。
9. a kind of alkaline hydrogen manufacturing electrolytic cell, it is characterised in that including anode, negative electrode, barrier film and electrolyte, the anode includes power
Profit requires that the cobalt-based that the preparation method described in 1~7 any one is prepared produces VPO catalysts.
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| CN113403641A (en) * | 2021-05-19 | 2021-09-17 | 中山大学 | Electrocatalytic material and preparation method and application thereof |
| CN113529132A (en) * | 2021-08-09 | 2021-10-22 | 中国科学院海洋研究所 | Cobalt-based catalyst electrode and preparation method thereof |
| CN116516392A (en) * | 2023-07-03 | 2023-08-01 | 北京化工大学 | CoSe nano-sheet electrocatalyst with cation vacancy and preparation method and application thereof |
| CN116516392B (en) * | 2023-07-03 | 2023-10-13 | 北京化工大学 | CoSe nano-sheet electrocatalyst with cation vacancy and preparation method and application thereof |
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