CN106824198B - 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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- CN106824198B CN106824198B CN201710142190.4A CN201710142190A CN106824198B CN 106824198 B CN106824198 B CN 106824198B CN 201710142190 A CN201710142190 A CN 201710142190A CN 106824198 B CN106824198 B CN 106824198B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 48
- 239000010941 cobalt Substances 0.000 title claims abstract description 48
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 17
- 239000001257 hydrogen Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910018864 CoMoO4 Inorganic materials 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001450 anions Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 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
- 239000000243 solution Substances 0.000 claims description 21
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 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 7
- 239000011734 sodium Substances 0.000 claims description 6
- 239000011684 sodium molybdate Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 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
- 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
- 235000015921 sodium selenite Nutrition 0.000 claims description 4
- 239000011781 sodium selenite Substances 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
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 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
- 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
- 239000000126 substance Substances 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
- 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
- 239000000463 material Substances 0.000 description 80
- 230000005540 biological transmission Effects 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method 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
- 239000012153 distilled water Substances 0.000 description 2
- 230000005611 electricity 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
- 238000002156 mixing Methods 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
- 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
- 238000005119 centrifugation Methods 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 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
- -1 metal oxide Chemical compound 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 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
- 239000000047 product Substances 0.000 description 1
- 230000004044 response Effects 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
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004832 voltammetry 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
- 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 present invention provides the preparation methods that a kind of cobalt-based produces VPO catalysts, comprising the following steps: A) preparation CoMoO4Nanometer rods presoma；B) by the CoMoO4Nanometer rods presoma is distributed in the solution of anion presoma, is carried out anion exchange by hydro-thermal reaction, is obtained 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, and the cobalt-based that consistent appearance can be obtained produces VPO catalysts, and method and step is simple, and operation is simple, have the characteristics that easily and fast.The catalytic performance of catalyst provided by the invention 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 technique
Hydrogen-oxygen fuel cell becomes current energy field due to having the advantages that high-energy density and almost zero carbon emission
Research hotspot.Practical hydrogen-oxygen fuel cell is developed to have great significance to the energy and environment problem of the world today.Reduce hydrogen
The economy and Environmental costs of gas preparation are the key links of Developing Extension hydrogen-oxygen fuel cell.Prepare a kind of more environmentally friendly of hydrogen
Method be exactly water electrolysis hydrogen production, water electrolysis hydrogen production reaction is divided into the oxygen evolution reaction of anode and the hydrogen of cathode be precipitated it is anti-
It answers.Slow four electronic processes are one of the central factors for restricting electrolysis water application in oxygen evolution reaction, and searching is suitably urged
Agent is the important channel solved the problems, such as.Currently, the catalyst for oxygen evolution reaction is still that earth reserves are very rare
The oxide of noble ruthenium and iridium.Therefore, develop what efficient, stable and cheap non-noble metallic materials were reacted as oxygen evolution
Catalyst is one important research direction of modern chemistry Material Field.
The requirement of the transmission of fast ionic needed for strong acid and strong alkaline electrolytes can satisfy water decomposition.Relative to acid electricity
Solve liquid, alkaline electrolyte produces hydrogen, due to its with lower vapour pressure thus can obtain the hydrogen of higher purity, quilt extensively
Industry is received.And it is most of for producing the catalyst of oxygen, such as metal oxide, have in alkaline electrolyte higher
Activity, but have poor activity and stability in acidic electrolysis bath.Therefore under alkaline condition the research of catalyst by more
Widely to pay close attention to.
Between past decades, researcher explores the catalyst that numerous Co based compounds are reacted as oxygen evolution,
Including CoSe2Nanobelt, CoOOH nanometer rods, Co3S4Nanometer sheet, Co3(PO4)3·8H2O nanosphere, CoMoO4Nano wire.However
In each work, the pattern of material has notable difference and catalytic performance is lower.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide cobalt-based produce VPO catalysts and preparation method thereof and
A kind of alkalinity hydrogen manufacturing electrolytic cell produces VPO catalysts according to the cobalt-based that preparation method of the present invention can prepare consistent appearance, and
The catalytic performance that the cobalt-based produces VPO catalysts is excellent.
The present invention provides the preparation methods that cobalt-based produces VPO catalysts, comprising 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, obtain mixed solution；
It successively separated, washed and is dried after the mixed solution is reacted under conditions of 120~180 DEG C,
Obtain CoMoO4Nanometer rods presoma.
Preferably, the cobalt salt is one of cobalt nitrate, cobalt chloride and cobalt acetate or a variety of, molybdate be sodium molybdate and
One of ammonium molybdate is a variety of.
Preferably, the metal hydroxides is selected from one of lithium hydroxide, sodium hydroxide and potassium hydroxide or a variety of；
The metal sulfide is selected from one of vulcanized sodium and potassium sulfide or a variety of；
The metal selenide is selected from the one or more of sodium selenite and potassium selenite；
The phosphate compounds is selected from one of potassium phosphate, sodium phosphate and ammonium phosphate or a variety of.
Preferably, step B) in, the solvent of the solution of the anion presoma is one in water, ethyl alcohol and ethylene glycol
Kind is a variety of.
Preferably, the CoMoO4The ratio of the amount of the substance of nanometer rods presoma and anion presoma be (0.1~
2): (0.2~40).
Preferably, the hydrothermal temperature be 80~160 DEG C, the reaction time be 8~for 24 hours.
The present invention also provides a kind of cobalt-baseds that above-mentioned preparation method is prepared to produce VPO catalysts, and the cobalt-based produces oxygen and urges
Agent is selected from Co (OH)2、Co3S4、CoSe2Or Co3(PO4)2。
The present invention also provides a kind of alkaline hydrogen manufacturing electrolytic cell, including anode, cathode, diaphragm and electrolyte, the anodes
VPO catalysts are produced including the cobalt-based that above-mentioned preparation method is prepared.
Compared with prior art, the present invention provides the preparation methods that a kind of cobalt-based produces VPO catalysts, comprising 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, obtains cobalt-base catalyst；The anion presoma is selected from metal hydroxides, gold
Belong to sulfide, metal selenide or phosphate compounds.The present invention is by CoMoO4Nanometer rods presoma and anion presoma into
Row hydro-thermal reaction, the cobalt-based that consistent appearance can be obtained produce VPO catalysts, and method and step is simple, and operation is simple, have convenient, fast
The features such as fast.The catalytic performance of catalyst provided by the invention is excellent, has well in fields such as electrochemistry complete solution water hydrogen manufacturing
Application prospect.
The result shows that cobalt-based provided by the invention produces VPO catalysts consistent appearance, there is one-dimensional rod-like pattern, and diameter
It is more uniform, it is 200~400nm.Wherein cobalt-based produces VPO catalysts Co (OH)2、Co3S4、CoSe2And Co3(PO4)2It is respectively required for
10mA/cm can be reached by wanting the overpotential of 388mV, 393mV, 349mV, 332mV and 346mV2Current density, hence it is evident that be better than quotient
The best RuO of industry2Catalyst (395mV).
Detailed description of the invention
Fig. 1 is the CoMoO that embodiment 1 obtains4The transmission electron microscope photo of nanometer rods presoma；
Fig. 2 is the Co (OH) that embodiment 1 obtains2The stereoscan photograph of material；
Fig. 3 is the Co (OH) that embodiment 1 obtains2The transmission electron microscope photo of material；
Fig. 4 is the Co (OH) that embodiment 2 obtains2The stereoscan photograph of material；
Fig. 5 is the Co (OH) that embodiment 3 obtains2The transmission electron microscope photo of material；
Fig. 6 is the Co (OH) that embodiment 4 obtains2The transmission electron microscope photo of material；
Fig. 7 is the Co (OH) that embodiment 5 obtains2The transmission electron microscope photo of material；
Fig. 8 is the Co that embodiment 6 obtains3S4The stereoscan photograph of material；
Fig. 9 is the Co that embodiment 6 obtains3S4The transmission electron microscope photo of material；
Figure 10 is the CoSe that embodiment 7 obtains2The stereoscan photograph of material；
Figure 11 is the CoSe that embodiment 7 obtains2The transmission electron microscope photo of material；
Figure 12 is the Co that embodiment 8 obtains3(PO4)2The stereoscan photograph of material；
Figure 13 is the Co that embodiment 7 obtains3(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 production oxygen reaction
The Dependence Results of voltammetry test.
Specific embodiment
The present invention provides the preparation methods that a kind of cobalt-based produces VPO catalysts, comprising 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 as follows into
Row preparation:
Cobalt salt, molybdate are mixed with deionized water, obtain mixed solution；
It successively separated, washed and is dried after the mixed solution is reacted under conditions of 120~180 DEG C,
Obtain CoMoO4Nanometer rods presoma.
Specifically, cobalt salt and molybdate are add to deionized water, mixed solution is obtained.Wherein, cobalt salt and molybdate
Molar ratio be preferably (1~4): (1~4), more preferably 1:1.In some 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 the method is preferred
For one of cobalt nitrate, cobalt chloride and cobalt acetate or a variety of, more preferably one of cobalt nitrate and cobalt chloride or a variety of.Its
In, molybdate is preferably one or both of sodium molybdate and ammonium molybdate, more preferably sodium molybdate.
The present invention is not particularly limited the charging sequence of cobalt salt and molybdate and water.The present invention is to the mixed mode
Not specifically limited, well known to a person skilled in the art mixed methods, and stirring keeps mixing equal such as on magnetic stirring apparatus
It is even, obtain clear mixed solution.
After obtaining mixed solution, successively divided after the mixed solution is reacted under conditions of 120~180 DEG C
From, washing and dry, CoMoO is obtained4Nanometer rods presoma.
In the present invention, 120~180 DEG C of the heating means are preferably carried out in an oven there is no specifically limited
120~180 DEG C are heated to be reacted, the temperature of the reaction is preferably 130~160 DEG C, and more preferably 150 DEG C；It is described anti-
The time answered is 4~12h, more preferably 6h~10h.
After heating reaction, reaction product is obtained, the reaction product is purple precipitating.Purple precipitating is successively carried out
Separation, washing and drying, 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 the methods of separation, washing and drying.In the present invention, the separation
Preferably it is centrifugated；The temperature of the drying is preferably 50 DEG C~100 DEG C, more preferably 60 DEG C~90 DEG C.The drying
Time is preferably 4h~for 24 hours, more preferably 6h~20h, most preferably 12h~15h.
Then, by the CoMoO4Nanometer rods presoma is distributed in the solution of anion presoma, passes through hydro-thermal reaction
Anion exchange is carried out, cobalt-base catalyst is obtained；The anion presoma is selected from metal hydroxides, metal sulfide, gold
Belong to 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 substance 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 of lithium hydroxide, sodium hydroxide and potassium hydroxide or a variety of, more excellent
It is selected as one of sodium hydroxide and potassium hydroxide or two kinds；The metal sulfide is preferably in vulcanized sodium and potassium sulfide
It is one or more, more preferably vulcanized sodium；The metal selenide is preferably one of sodium selenite and potassium selenite or more
Kind, more preferably sodium selenite.The phosphate compounds is preferably one of potassium phosphate, sodium phosphate and ammonium phosphate or more
Kind, more preferably potassium phosphate.
The solvent of the solution of the anion presoma is one of water, ethyl alcohol and ethylene glycol or a variety of, more preferably
For one of water and ethylene glycol or two kinds.
It will obtain CoMoO4The mixed solution of nanometer rods presoma and anion presoma heats, and 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~for 24 hours, more preferably 8h~12h.
The reaction product of hydro-thermal reaction is centrifuged, is washed, is dried in a vacuum drying oven, cobalt-base catalyst is obtained.
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 temperature of the drying is preferably 50 DEG C~100 DEG C, more preferably 60 DEG C~90
℃.The time of the drying is preferably 4h~for 24 hours, more preferably 6h~20h, most preferably 12h~15h.
Electron microscope analysis is carried out to it after obtaining cobalt-base catalyst, the results show that cobalt-based prepared by the present invention produces VPO catalysts
Consistent appearance has one-dimensional rod-like pattern, and size is more uniform, is 200~400nm.
The present invention also provides a kind of alkaline hydrogen manufacturing electrolytic cell, including anode, cathode, diaphragm and electrolyte, the anodes
VPO catalysts are produced including the cobalt-based that above-mentioned preparation method is prepared.
The present invention also provides a kind of cobalt-baseds to produce application of the VPO catalysts as catalyst in electrochemistry production oxygen field.
The present invention is by CoMoO4Nanometer rods presoma and anion presoma carry out hydro-thermal reaction, and consistent appearance can be obtained
Cobalt-based produce VPO catalysts, method and step is simple, and operation is simple, has the characteristics that easily and fast.Catalyst provided by the invention
Catalytic performance it is excellent, have good application prospect in fields such as electrochemistry complete solution water.
The result shows that cobalt-based provided by the invention produces VPO catalysts consistent appearance, there is one-dimensional rod-like pattern, and size
It is more uniform, it is 200~400nm.Wherein, cobalt-based produces VPO catalysts Co (OH)2、Co3S4、CoSe2And Co3(PO4)2It is respectively required for
10mA/cm can be reached by wanting the overpotential of 388mV, 393mV, 349mV, 332mV and 346mV2Current density, hence it is evident that be better than quotient
The best RuO of industry2Catalyst (395mV).
For a further understanding of the present invention, VPO catalysts and its system are produced to cobalt-based provided by the invention below 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 respectively in 17.5ml deionized water,
Stirring sufficiently dissolution；By above-mentioned Na2MoO4Solution is added to Co (NO3)2It in solution, stirs 10 minutes, formation uniformly mixes molten
Liquid；The mixed solution is transferred in 50ml reaction kettle, is put into 150 DEG C of baking ovens, 6h is reacted；Take out reaction kettle, observation discovery
A large amount of purple precipitatings, are centrifuged and then are washed with distilled water twice, with ethanol washing one time, are placed in 60 DEG C of vacuum ovens and do
Dry 12h, obtains CoMoO4Nanometer rods presoma.
To above-mentioned CoMoO4Nanometer rods presoma carries out projection Electronic Speculum observation, and the result is shown in Figure 1, Fig. 1 is what embodiment 1 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, a few micrometers of length, diameter is about 200~300nm.
(2) cobalt-based produces VPO catalysts Co (OH)2The preparation of material:
The solution of the KOH containing 0.2mmol is prepared, solvent is the mixed solution of 20mL water and ethylene glycol, the body of water and ethylene glycol
Product is than being 1:1；By 0.1mmol CoMoO4Nanometer rods presoma ultrasonic disperse is into above-mentioned solution；Then said mixture is turned
It moves on in 50ml reaction kettle, puts into 120 DEG C of baking ovens, react 12h；Reaction kettle is taken out, observation discovery has a large amount of precipitatings to occur, from
It is washed with distilled water after the heart twice, with ethanol washing one time, is placed in 60 DEG C of vacuum ovens dry 12h, obtains cobalt-based production
VPO catalysts Co (OH)2Material.
To above-mentioned Co (OH)2Material is scanned Electronic Speculum and transmission electron microscope observing, as a result sees that Fig. 2 and Fig. 3, Fig. 2 are to implement
The Co (OH) that example 1 obtains2The stereoscan photograph of material, Fig. 3 are the Co (OH) that embodiment 1 obtains2The 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 of a large amount of nanometer sheets, and forms porous structure, and is maintained
One-dimentional structure, diameter be about 300~400nm, form Co (OH)2The size of the nanometer sheet of material surface is 50~100nm.
Embodiment 2
According to embodiment 1 preparation method carry out cobalt-based produce VPO catalysts preparation, have following difference: prepare yin from
It when sub- precursor solution, selects 20mL water for reaction dissolvent, obtains Co (OH)2Material.
Obtained material is scanned electron microscope analysis, as a result referring to fig. 4, Fig. 4 is the Co (OH) that embodiment 2 obtains2Material
The stereoscan photograph of material.The Co (OH) obtained with embodiment 12Material is compared, the Co (OH) that the present embodiment 2 obtains2Material morphology
Without significant difference, the one-dimentional structure still formed for nanometer sheet, diameter is about 300~400nm, is formed Co (OH)2Material surface
The size of nanometer sheet is 50~100nm.
Embodiment 3
According to embodiment 1 preparation method carry out cobalt-based produce VPO catalysts preparation, have following difference: prepare yin from
It when sub- precursor solution, selects 0.2mmol NaOH for presoma, obtains Co (OH)2Material.
Obtained material is subjected to transmission electron microscope analysis, is as a result the Co (OH) that embodiment 3 obtains referring to Fig. 5, Fig. 52Material
The transmission electron microscope photo of material.The Co (OH) obtained with embodiment 12Material is compared, the Co (OH) that the present embodiment 3 obtains2Material morphology
Without significant difference, the one-dimentional structure still formed for nanometer sheet, diameter is about 300~400nm, is formed Co (OH)2Material surface
The size of nanometer sheet is 50~100nm.
Embodiment 4
According to embodiment 1 preparation method carry out cobalt-based produce VPO catalysts preparation, have following difference: carry out yin from
When son exchange hydro-thermal reaction, reaction temperature is 80 DEG C, obtains Co (OH)2Material.
Obtained material is subjected to transmission electron microscope analysis, is as a result the Co (OH) that embodiment 4 obtains referring to Fig. 6, Fig. 62Material
The transmission electron microscope photo of material.The Co (OH) obtained with embodiment 12Material is compared, the Co (OH) that the present embodiment 4 obtains2Material morphology
Without significant difference, the one-dimentional structure still formed for nanometer sheet, diameter is about 300~400nm, is formed Co (OH)2Material surface
The size of nanometer sheet is 50~100nm.
Embodiment 5
According to embodiment 1 preparation method carry out cobalt-based produce VPO catalysts preparation, have following difference: carry out yin from
When son exchange hydro-thermal reaction, reaction temperature is 100 DEG C, obtains Co (OH)2Material.
Obtained material is subjected to transmission electron microscope analysis, is as a result the Co (OH) that embodiment 5 obtains referring to Fig. 7, Fig. 72Material
The transmission electron microscope photo of material.The Co (OH) obtained with embodiment 12Material is compared, the Co (OH) that the present embodiment 5 obtains2Material morphology
Without significant difference, the one-dimentional structure still formed for nanometer sheet, diameter is about 300~400nm, is formed Co (OH)2Material surface
The size of nanometer sheet is 50~100nm.
Embodiment 6
According to embodiment 1 preparation method carry out cobalt-based produce VPO catalysts preparation, have following difference: prepare yin from
When sub- precursor solution, 1mmol Na is selected2S is presoma, and cobalt-based can be obtained and produce VPO catalysts Co3S4Material.
Obtained material is scanned electromicroscopic photograph and transmission electron microscope analysis, is as a result to implement referring to Fig. 8 and Fig. 9, Fig. 8
The Co that example 6 obtains3S4The stereoscan photograph of material, Fig. 9 are the Co that embodiment 6 obtains3S4The transmission electron microscope photo of material.From
Fig. 8 and Fig. 9 can be seen that Co3S4Than more uniform, surface is made of the pattern of material a large amount of particles, and no apparent nano aperture goes out
It is existing, and one-dimentional structure is maintain, diameter is about 200~300nm, forms Co3S4The size of the nano particle of material surface be 5~
20nm。
Embodiment 7
According to embodiment 1 preparation method carry out cobalt-based produce VPO catalysts preparation, have following difference: prepare yin from
When sub- precursor solution, 0.2mmol Na is selected2SeO3With 0.4mmol NaBH4Mixed solution is presoma, and cobalt-based can be obtained
Produce VPO catalysts CoSe2Material.
Obtained material 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 obtains2The stereoscan photograph of material, Figure 11 are the CoSe that embodiment 7 obtains2The transmission electron microscope of material shines
Piece.It can be seen that CoSe from Figure 10 and Figure 112Than more uniform, surface is made of the pattern of material a large amount of nanometer sheets, and maintains
One-dimentional structure, diameter are about 300~400nm, form Co3S4The size of the nanometer sheet of material surface is 10~50nm.With embodiment
1 obtained Co (OH)2Material is compared, and the nanometer sheet is smaller.
Embodiment 8
According to embodiment 1 preparation method carry out cobalt-based produce VPO catalysts preparation, have following difference: prepare yin from
When sub- precursor solution, 0.2mmol K is selected3PO4·3H2O is presoma, and cobalt-based can be obtained and produce VPO catalysts Co3(PO4)2
Material.
Obtained material 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 obtains3(PO4)2The stereoscan photograph of material, Figure 13 are the Co that embodiment 7 obtains3(PO4)2The transmission of material
Electromicroscopic photograph.It can be seen that Co from Figure 12 and Figure 133(PO4)2The pattern of material is than more uniform, surface smoother, nanometer rods
Inside has a large amount 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 produce the XRD spectra of VPO catalysts material for serial cobalt-based prepared by the embodiment of the present invention 1,6,7,8.It can be with from Figure 14
Find out, original CoMoO4The XRD diffraction pattern of nanometer rods presoma has sharp strong peak, it is meant that its crystallinity is preferable.
By different anion exchange reactions, it includes Co (OH) that obtained serial cobalt-based, which produces VPO catalysts material,2、Co3S4、CoSe2And
Co3(PO4)2There is the peak XRD of wideizationr, it is meant that the successful generation of the anion exchange reaction.Crystallinity poor simultaneously
It is primarily due to anion exchange reaction and destroys original CoMoO4The crystallinity of high-sequential.
Embodiment 10
VPO catalysts material and commercially best RuO are produced with serial cobalt-based prepared by embodiment 1,6,7,8 respectively2Material
As catalyst, the activity for carrying out electrochemistry production oxygen reaction is detected, method particularly includes: it measures, revolves under three electrode conditions
Turn disk electrode supported catalyst as working electrode, wherein the load capacity of catalyst is 0.5mg/cm2, platinized platinum is as to electricity
Pole, saturated calomel electrode is 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 production VPO catalysts material prepared by embodiment 1,6,7,8 is producing
The Dependence Results of linear sweep voltammetry test in oxygen reaction.It can be seen from fig. 15 that relative to our cobalt-based material, quotient
Industry RuO2Material has obvious low take-off potential, but it performs poor at higher current densities, than system provided by the invention
Column 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)2It is only necessary to the mistakes of 388mV, 393mV, 349mV, 332mV and 346mV
Potential can reach.And the RuO of business2Catalyst but needs overpotential to be up to 395mV.Meanwhile it being reported before catalytic performance ratio
The Mn in road3O4/CoSe2(J.Am.Chem.Soc.2012,134,2930.) and CoSe2-Graphene(Acs Nano 2014,8,
3970-3978.) catalytic performance of material will get well.
As seen from the above embodiment, method and step provided by the invention is simple, and operation is simple, has in large scale preparation.Together
When, there is series cobalt-base catalyst prepared by the present invention excellent electrochemistry to produce oxygen catalytic performance, have in industrial electrolysis water field
There is potential application value.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (6)
1. the preparation method that a kind of cobalt-based produces VPO catalysts, which comprises 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 yin from
Son exchange, obtains cobalt-base catalyst；The anion presoma is selected from metal hydroxides, metal sulfide, metal selenide
Or phosphate compounds；
The metal hydroxides is selected from one of lithium hydroxide, sodium hydroxide and potassium hydroxide or a variety of；
The metal sulfide is selected from one of vulcanized sodium and potassium sulfide or a variety of；
The metal selenide is selected from the one or more of sodium selenite and potassium selenite；
The phosphate compounds is selected from one of potassium phosphate, sodium phosphate and ammonium phosphate or a variety of；
The CoMoO4The ratio of the amount of the substance of nanometer rods presoma and anion presoma is (0.1~2): (0.2~40)；
The hydrothermal temperature be 80~160 DEG C, the reaction time be 8~for 24 hours.
2. preparation method according to claim 1, which is characterized in that the CoMoO4Nanometer rods presoma is according to such as lower section
It is prepared by method:
Cobalt salt, molybdate are mixed with deionized water, obtain mixed solution；
It successively separated, washed and is dried after the mixed solution is reacted under conditions of 120~180 DEG C, obtained
CoMoO4Nanometer rods presoma.
3. preparation method according to claim 2, which is characterized in that the cobalt salt is cobalt nitrate, cobalt chloride and cobalt acetate
One of or it is a variety of, molybdate be one of sodium molybdate and ammonium molybdate or a variety of.
4. preparation method according to claim 1, which is characterized in that step B) in, the solution of the anion presoma
Solvent be one of water, ethyl alcohol and ethylene glycol or a variety of.
5. a kind of cobalt-based being prepared such as the described in any item preparation methods of Claims 1 to 4 produces VPO catalysts, the cobalt-based
It produces VPO catalysts and is selected from Co (OH)2、Co3S4、CoSe2Or Co3(PO4)2。
6. a kind of alkalinity hydrogen manufacturing electrolytic cell, which is characterized in that including anode, cathode, diaphragm and electrolyte, the anode includes power
The cobalt-based that benefit requires preparation method described in 1~4 any one to be prepared produces VPO catalysts.
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| CN107663637B (en) * | 2017-09-05 | 2019-10-29 | 中国科学院福建物质结构研究所 | Molybdate nanocomposite and its preparation method and application |
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