CN112481653B - Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof - Google Patents
Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN112481653B CN112481653B CN202011180973.XA CN202011180973A CN112481653B CN 112481653 B CN112481653 B CN 112481653B CN 202011180973 A CN202011180973 A CN 202011180973A CN 112481653 B CN112481653 B CN 112481653B
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- defect
- nano
- doped cobalt
- selenide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 230000007547 defect Effects 0.000 title claims abstract description 42
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 42
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001868 cobalt Chemical class 0.000 claims abstract description 18
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000011669 selenium Substances 0.000 description 30
- 229910052711 selenium Inorganic materials 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- -1 transition metal selenides Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 235000015393 sodium molybdate Nutrition 0.000 description 6
- 239000011684 sodium molybdate Substances 0.000 description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910017313 Mo—Co Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- IJUKXQRCJABGNO-UHFFFAOYSA-N [Se].[Ni]=[Se] Chemical compound [Se].[Ni]=[Se] IJUKXQRCJABGNO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明涉及电催化剂技术领域，公开一种富含缺陷的钼掺杂硒化钴/纳米碳电催化剂及其制备方法和应用，其制备方法包括如下步骤：(1)将钴盐、钼酸盐溶解后加入2‑甲基咪唑溶液，搅拌混合、离心干燥获得钼掺杂的钴基金属有机框架的前驱体；(2)将前驱体与硒粉混合，研磨后煅烧得到钼掺杂硒化钴/纳米碳电催化剂；(3)将步骤(2)制备的催化剂热处理，得到所述富含缺陷的钼掺杂硒化钴/纳米碳电催化剂。得到的催化剂在碱性条件下对于电解水阴极析氢反应具有优异的电催化活性，且长期工作下仍具有较好稳定性。
The invention relates to the technical field of electrocatalysts, and discloses a defect-rich molybdenum-doped cobalt selenide/nano-carbon electrocatalyst and a preparation method and application thereof. The preparation method includes the following steps: (1) combining cobalt salt and molybdate After dissolving, adding 2-methylimidazole solution, stirring and mixing, and centrifugal drying to obtain a precursor of a molybdenum-doped cobalt-based metal organic framework; (2) mixing the precursor with selenium powder, grinding and calcining to obtain molybdenum-doped cobalt selenide /nano-carbon electrocatalyst; (3) heat-treating the catalyst prepared in step (2) to obtain the defect-rich molybdenum-doped cobalt selenide/nano-carbon electrocatalyst. The obtained catalyst has excellent electrocatalytic activity for the cathodic hydrogen evolution reaction of electrolyzed water under alkaline conditions, and still has good stability under long-term operation.
Description
Technical Field
The invention relates to the technical field of electrocatalysts, in particular to a defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and a preparation method and application thereof.
Background
The hydrogen energy is used as a green renewable energy source, and compared with other traditional fossil fuels such as coal and the like, the hydrogen energy has the characteristics of cleanness, high efficiency and the like. At present, among various hydrogen evolution methods, electrochemical water decomposition hydrogen production is one of the most promising methods at present, and is extensively and deeply studied. However, among the effective electrocatalysts currently used for hydrogen evolution reactions, the best electrocatalysts are generally noble metal-based catalysts (e.g., Pt-based catalysts), but the scarcity and expensive price of noble metals limits their widespread development; the non-noble metal-based material is adopted to replace a noble metal catalyst to carry out high-efficiency electrolysis water hydrogen production, and has profound significance for hydrogen energy preparation. In recent years, much research effort has been devoted to the development of low cost non-noble metal hydrogen evolution electrocatalysts such as transition metal oxides, carbides, phosphides and selenides to replace traditional noble metal catalysts.
Among these alternative catalysts, transition metal selenides such as CoSe2，Co0.85Se and NiSe2Isoelectric catalysts have been reported many times to have good catalytic performance in the electrolysis of water to produce hydrogen. For example, Chinese patent publication No. CN106558689A discloses a bicontinuous CoSe2/NiSe2The preparation method of the nano composite material comprises the steps of firstly using CoSO4·7H2O、NiSO4·6H2O, selenium powder, water, ethanol and hydrazine hydrate are used as raw materials, and the metal selenide nano composite material is prepared in situ by an electrochemical method; detailed description of the inventionThe following were used: (1) according to a certain mole ratio adding CoSO4·7H2O and NiSO4·6H2Adding O into water, and stirring until the O is completely dissolved; (2) adding ethanol into the solution obtained in the step (1), adding selenium powder, and fully stirring; carrying out solvothermal reaction to obtain CoNiSe4A solid solution material; then to CoNiSe4Performing smear, charging and discharging with constant current after battery loading to obtain CoSe2/NiSe2A nanocomposite material.
For example, Chinese patent publication No. CN111482189A discloses a core-shell NiSe structure2A preparation method of @ NC electrocatalytic material and application thereof are characterized in that hydrazine hydrate is adopted as a reducing agent, selenium powder is adopted as a selenium source, a metal organic framework substance is adopted as a precursor, and selective selenization reaction is carried out on the metal organic framework of a mixed ligand through hydrothermal reaction. And then a series of adjustable nitrogen-doped carbon-coated cubic phase core-shell nickel diselenide octahedral materials are prepared by further high-temperature calcination treatment. Yongqiang Zhao et al prepared a three-dimensional cobalt selenide electrode by simultaneously encapsulating cobalt foil and selenium powder and heat-treating the same, and showed a good electrocatalytic activity under an alkaline condition (adv. energy mater.2018,8,1801926).
However, the performance of pure cobalt selenide as an electrocatalyst is far from that of commercial noble metal catalysts such as Pt/C. Therefore, the transition metal doped cobalt selenide electrocatalyst coated by the carbon shell and having defects can effectively improve the adsorption and dissociation capability of the electrocatalyst on water molecules, and meanwhile, the transition metal doping can further optimize the electronic structure of cobalt selenide, so that the electrocatalytic activity is further improved, and the electrocatalyst is of great significance for replacing the traditional commercial noble metal catalyst.
Disclosure of Invention
Aiming at the problem that the catalytic activity of a pure cobalt selenide catalyst in the prior art needs to be improved, the invention provides a preparation method of a defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst, and the obtained catalyst has excellent electrocatalytic activity for cathode hydrogen evolution reaction of electrolyzed water under an alkaline condition and still has good stability under long-term work.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst comprises the following steps:
(1) dissolving cobalt salt and molybdate, adding a 2-methylimidazole solution, stirring, mixing, centrifuging and drying to obtain a molybdenum-doped cobalt-based metal organic framework precursor;
(2) mixing the precursor prepared in the step (1) with selenium powder, grinding and calcining to obtain a molybdenum-doped cobalt selenide/nano carbon electrocatalyst;
(3) and (3) carrying out heat treatment on the catalyst prepared in the step (2) to obtain the defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst.
The preparation principle of the defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst provided by the invention is as follows: through self-assembly, divalent cobalt and 2-methylimidazole coordinate to form an organic metal framework compound, molybdate ions are adsorbed at the same time to form a molybdenum-doped cobalt-based metal organic framework compound, the molybdenum-doped cobalt-based metal organic framework compound is uniformly mixed with selenium powder and then calcined at high temperature, and the molybdenum-doped cobalt selenide coated by nitrogen-doped nano carbon is constructed. Removing part of selenium in the cobalt selenide through low-temperature hydrogen heat treatment to form a selenium defect; the selenium defect in the catalyst is beneficial to the adsorption and the desorption of water molecules, and the electrocatalytic activity of the catalyst can be further improved.
Meanwhile, the doping of molybdenum and the selenium defect can further regulate and control d-orbital electrons of cobalt, and catalytic reaction is facilitated. Specifically, the selenium defect can better adsorb water molecules on the surface of the catalyst, so that hydrogen adsorption is more favorably formed, the molybdenum doping can weaken the adsorption of the adsorbed hydrogen on the catalyst, so that the generated hydrogen is easier to desorb, and the combined action of the selenium defect and the catalyst accelerates the whole hydrogen evolution process.
The cobalt salt or molybdate is soluble salt, and the molybdate comprises sodium molybdate, ammonium molybdate and the like.
The cobalt salt includes nitrate, chloride, sulfate, hydrate of cobalt, etc., such as cobalt nitrate hexahydrate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate, etc.
Compared with other rare metals, the catalyst disclosed by the invention has the advantages that the molybdenum doping is adopted, the electronic structure of cobalt metal can be better regulated and controlled, the over-strong adsorption capacity of the cobalt metal on hydrogen is weakened, the desorption of hydrogen is facilitated, and the hydrogen production rate can be improved.
The molar ratio of the cobalt salt to the molybdenum salt is 1-8: 1, when the content of molybdenum is too low, due to the fact that the doping amount of the molybdenum is too small, the electronic structure of cobalt which is a metal active site in the whole catalyst is affected, the catalytic activity of the cobalt is not obviously improved, and when the content of the molybdenum is too high, a molybdenum selenide and cobalt selenide compound is easily generated, the catalytic activity site of the molybdenum selenide and cobalt selenide compound is changed, the catalytic activity of the molybdenum selenide and cobalt selenide compound is reduced, and the follow-up research on a catalytic mechanism is not facilitated.
The ratio of the cobalt salt to the 2-methylimidazole is 1: 2-4 in a molar ratio. The ratio of the two determines the loading amount of the metal active sites in the final carbon electrocatalyst, for example, if the ratio of cobalt salt is too high, too much metal is loaded in the final metal framework, so that the accumulation is easy to occur and the specific surface area is reduced, thereby reducing the activity of the catalyst.
The stirring time in the step (1) is 2-6 hours, magnetic stirring and ultrasonic are adopted to promote the cobalt salt and the molybdate to be uniformly dispersed in the 2-methylimidazole, and the obtained catalyst has better dispersion of active sites and higher catalytic activity.
In the step (1), in the mixed solution obtained after the cobalt salt and the molybdate are dissolved, the mass concentration of the cobalt salt is 10-20 g/L, the mass concentration of the molybdate is 1-5 g/L, and the mass concentration of the added 2-methylimidazole solution is 15-45 g/L.
Preferably, in the mixed solution after the cobalt salt and the molybdate are dissolved, the mass concentration of the cobalt salt is 15g/L, the mass concentration of the molybdate is 2.75g/L, and the mass concentration of the added 2-methylimidazole solution is 32.5 g/L.
The mass ratio of the precursor to the selenium powder in the step (2) is 1: 1-4. When the content of the selenium powder is too small, the whole selenization degree is affected, so that the amount of the selenium powder is controlled to be sufficient.
The calcining temperature in the step (2) is 700-1000 ℃, and the calcining time is 1.5-3 h. High-temperature carbonization is beneficial to the electrical conductivity of the whole catalyst.
The temperature of the heat treatment in the step (3) is 300-500 ℃, and the heat treatment is carried outThe treatment time is 1.5-3H, and the atmosphere condition is H2and/Ar. Preferably, the atmosphere condition of the heat treatment is a mixed gas of hydrogen and helium in a volume ratio of 1: 8-9. The temperature and the time are controlled to better form selenium defects, metal cobalt particles can be reduced to form at an overhigh temperature, selenium cannot be taken away at a too low temperature, and the defects cannot be formed.
Preferably, the molar ratio of the cobalt salt to the molybdate is 3-5: 1, the mass ratio of the precursor to the selenium powder is 1: 1.5-3, the calcining temperature is 800-950 ℃, and the heat treatment temperature is 350-450 ℃. Under the condition, the proportion of the cobalt salt, the molybdate, the 2-methylimidazole and the selenium powder is optimal, and the obtained catalyst has excellent performance.
Further preferably, the molar ratio of the cobalt salt to the molybdate is 4:1, the mass ratio of the precursor to the selenium powder is 1:2, the calcining temperature is 850-900 ℃, and the heat treatment temperature is 400-450 ℃.
The invention also provides a defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst prepared by the preparation method, and the catalyst can be represented by the chemical formula: Mo-Co0.85SeVSeand/NC represents, wherein, Mo-Co0.85Se is molybdenum-doped cobalt selenide; VSe selenium defect, NC nitrogen doped carbon shell; the catalyst consists of a nitrogen-doped nano carbon shell and molybdenum-doped cobalt selenide particles which are embedded in the carbon shell and have defects, and due to the doping of molybdenum and the defects of selenium, the adsorption of the surface of the catalyst on water molecules is improved, the adsorption capacity of adsorbed hydrogen on the surface of the catalyst is weakened, the desorption process of hydrogen is facilitated, and the catalytic activity of the catalyst is obviously improved.
The defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst can be used as a working electrode in the application of electrolysis water cathode hydrogen evolution reaction in alkaline solution.
In the electrolytic water cathode hydrogen evolution reaction, a three-electrode system is adopted, specifically, an Ag/AgCl electrode is used as a reference electrode, a carbon rod is used as a counter electrode, a glassy carbon electrode covered by the defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst provided by the invention is used as a working electrode, and a 1.0M potassium hydroxide solution is used as an electrolyte.
The defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst provided by the invention is coated on the surface of the defect-rich molybdenum-doped cobalt selenide by using nitrogen-doped nano carbon, so that the electrode material shows good conductivity, and meanwhile, the nitrogen-doped nano carbon material has a higher specific surface area, which is beneficial to the dispersion of catalytic active sites, and further the electrocatalytic activity of the defect-rich molybdenum-doped cobalt selenide is increased.
Compared with the prior art, the invention has the following beneficial effects:
(1) the defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst provided by the invention can be used for electrolyzing water to produce hydrogen in an alkaline electrolyte and has high electrocatalytic activity and good stability. At a current density of 10mA cm-2In the process, the overpotential of the cathode is only about 160mV, and the 12h can be maintained without obvious potential attenuation, so that the possibility is provided for further improving the development and utilization of hydrogen energy;
(2) according to the defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst, the electronic structure of cobalt selenide is optimized by doping molybdenum, so that the hydrogen evolution reaction is facilitated;
(3) according to the defect-rich molybdenum-doped cobalt selenide/nanocarbon electrocatalyst provided by the invention, partial selenium defects appear on the surface of cobalt selenide through low-temperature hydrogen heat treatment, so that adsorption and dissociation of water molecules are facilitated, and the reaction rate of electrolyzing water to produce hydrogen is further accelerated.
Drawings
FIG. 1 shows Mo-Co catalyst prepared in example 10.85SeVSeSEM image of/NC;
FIG. 2 shows Mo-Co catalyst prepared in example 10.85SeVSeTEM image of transmission electron microscope of/NC;
FIG. 3 shows Mo-Co catalyst prepared in example 10.85SeVSeX-ray diffraction XRD pattern of/NC;
FIG. 4 is a polarization curve diagram of the electrolytic water hydrogen evolution reaction of the catalysts prepared in example 1 and comparative examples 1-4 in an application example;
FIG. 5 shows Mo-Co catalyst prepared in example 10.85SeVSeVoltage versus time plot at constant current for NC electrolyzed water reduction.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention. The raw materials used in the following embodiments are all commercially available.
Example 1
(1) Weighing 0.6g of cobalt nitrate hexahydrate solid particles and 0.11g of sodium molybdate solid particles, dissolving in 40mL of deionized water solution, and carrying out ultrasonic treatment for 20min for later use; weighing 1.3g of 2-methylimidazole powder, dissolving in 40mL of deionized water solution, and uniformly stirring;
(2) pouring the mixed solution of cobalt nitrate and sodium molybdate into the prepared 2-methylimidazole solution, and stirring for 4 hours; centrifugally washing, and drying at 60 ℃ for 20h to obtain a precursor of the cobalt-based metal organic framework doped with molybdenum;
(3) weighing the prepared molybdenum-doped cobalt-based organic metal framework precursor and selenium powder, uniformly mixing according to the mass ratio of 1:2, placing in a tubular furnace for high-temperature calcination, and heating at 900 ℃ for 2 h; after the reaction is finished, cooling to room temperature to obtain the molybdenum-doped cobalt selenide/nano carbon catalyst;
(4) the prepared molybdenum-doped cobalt selenide/nano carbon is placed in a tube furnace and put in H2Heating at 400 ℃ for 2h under the atmosphere of/Ar (10%/90%); after the reaction is finished, cooling to room temperature to obtain the defect-rich molybdenum-doped cobalt selenide/nano carbon catalyst which is marked as Mo-Co0.85SeVSe/NC。
The prepared catalyst is observed for the microscopic morphology through a scanning electron microscope SEM and a transmission electron microscope TEM, the SEM result is shown in figure 1, and the TEM image is shown in figure 2. From fig. 1-2, it can be seen that the defect-rich molybdenum-doped cobalt selenide/nanocarbon nanoparticles are uniformly wrapped by the nanocarbon shell. The X-ray diffraction XRD pattern of the molybdenum-doped cobalt selenide/nanocarbon catalyst rich in defects prepared in this example is shown in fig. 3, and it can be seen that the catalyst still well compounds the characteristic peak of cobalt selenide, which proves that the main structure of the molybdenum-doped catalyst is not changed and the cobalt selenide molybdenum selenide complex is not formed.
Comparative example 1
According to the process of the example 1, the molybdenum-doped cobalt selenide/nano carbon catalyst is obtained without the step (4) and is marked as Mo-Co0.85Se/NC。
Comparative example 2
The process of example 1 was followed except that sodium molybdate was not added in step (1) and step (4) was not performed to obtain cobalt selenide/nanocarbon catalyst, noted as Co0.85Se/NC。
Comparative example 3
The procedure was followed as in example 1 except that in step (1) sodium molybdate was replaced with 0.15g of nickel nitrate hexahydrate to yield the nickel-doped cobalt selenide/nanocarbon catalyst, noted Ni-Co0.85Se/NC。
Comparative example 4
The process as in example 1 except that in step (1) sodium molybdate was replaced with 0.2g of nickel iron nitrate nonahydrate to obtain the iron-doped cobalt selenide/nanocarbon catalyst noted as Fe-Co0.85Se/NC。
Application example
(1) Using a three-electrode system, the glassy carbon electrode covered with the catalyst prepared in example 1 or comparative examples 1-4 was the working electrode, the counter electrode was a carbon rod, the reference electrode was a saturated Ag/AgCl electrode, and the electrolyte was 1.0M KOH;
(2) CV activation: the electrochemical workstation of Shanghai Chenghua CHI 760E was used, and nitrogen was introduced into the electrolyte for 30min before the test. Adopting CV program, the test interval is 0-0.8V vs. RHE, and the sweep rate is 50mV s-1And the electrode reaches a steady state after 40 cycles.
After the catalysts prepared in example 1 and comparative examples 1 to 4 were activated by the Linear Sweep Voltammetry (LSV) test, the switching procedure was the LSV procedure, the test interval was 0 to-0.8V vs. RHE, the sweep rate was 5mV/s, and the overpotential was 0V and 10mA cm with respect to the reversible hydrogen electrode-2The difference in potential was measured. As shown in FIG. 4, the present example provides Mo-Co0.85SeVSecatalyst/NC and Mo-Co0.85Se/NC，Ni-Co0.85Se/NC，Fe-Co0.85Se/NC and Co0.85The polarization curve of the hydrogen evolution reaction of Se/NC in 1.0M KOH solution by electrolysis of water is shown in FIG. 4. from FIG. 4, it can be seen that in alkaline electrolyte, Mo-Co0.85SeVSeThe overpotential of the/NC catalyst is only 160mV, and the effect is obviously better than that of the nickel or iron doped catalyst.
The catalyst prepared in example 1 was subjected to stability test
After CV activation, the switching process was an ISTEP process with current set to 0.014A and time set to 43200 s. As shown in fig. 5, the defect-rich molybdenum-doped cobalt selenide/nanocarbon catalyst showed little potential change, demonstrating its good catalytic stability.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011180973.XA CN112481653B (en) | 2020-10-29 | 2020-10-29 | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011180973.XA CN112481653B (en) | 2020-10-29 | 2020-10-29 | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112481653A CN112481653A (en) | 2021-03-12 |
| CN112481653B true CN112481653B (en) | 2022-04-01 |
Family
ID=74927614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011180973.XA Active CN112481653B (en) | 2020-10-29 | 2020-10-29 | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112481653B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113089014B (en) * | 2021-04-07 | 2022-05-13 | 西南石油大学 | A kind of core-shell structure superhydrophilic superhydrophobic high-efficiency hydrogen evolution catalyst and preparation method thereof |
| CN113281318B (en) * | 2021-05-26 | 2022-06-14 | 四川中科微纳科技有限公司 | Fluorescent-colorimetric dual-signal detection of Fe by MoSe2@ Fe nano composite material3+And GSH |
| CN113818039B (en) * | 2021-09-29 | 2023-05-02 | 西安交通大学 | Three-dimensional carbon material/molybdenum diselenide electrocatalytic hydrogen evolution material and preparation method thereof |
| CN114717599B (en) * | 2022-04-26 | 2024-05-17 | 浙江大学衢州研究院 | A ruthenium-loaded nickel metal three-dimensional carbon sphere electrocatalyst and its preparation method and application |
| CN114774976A (en) * | 2022-05-04 | 2022-07-22 | 台州学院 | Spherical S-doped CoSe2/CoOOH and preparation method thereof |
| CN115198301A (en) * | 2022-07-29 | 2022-10-18 | 陕西科技大学 | Defect-rich transition metal nanostructure catalyst and preparation method thereof |
| CN116081579B (en) * | 2022-12-30 | 2024-04-26 | 青岛科技大学 | Preparation method of cubic cobalt selenide rich in Se defects and application of cubic cobalt selenide in preparing hydrogen peroxide through electrocatalytic oxygen reduction |
| CN116581307B (en) * | 2023-06-19 | 2024-01-30 | 广东格林赛福能源科技有限公司 | S-doped NC/Co/Cs 2 Se/CoSe catalyst, preparation method and application thereof |
| CN118880388B (en) * | 2024-09-30 | 2025-01-28 | 宁波光明橡塑有限公司 | Preparation method and application of tungsten-molybdenum carbide nanosheet heterojunction catalyst |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0585973A (en) * | 1990-12-26 | 1993-04-06 | Mitsui Toatsu Chem Inc | Coproduction of aromatic hydroxyl compound and carbonyl compound |
| WO2011123795A1 (en) * | 2010-04-02 | 2011-10-06 | Battelle Memorial Institute | Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, and gas separation assemblies |
| CN105498811A (en) * | 2015-12-23 | 2016-04-20 | 信阳师范学院 | Preparation method of molybdenum selenide-acetylene black composite material and application of molybdenum selenide-acetylene black composite material as catalyst in hydrogen evolution reaction |
| CN107694580A (en) * | 2017-09-07 | 2018-02-16 | 电子科技大学 | A kind of nano combined selenides and preparation method thereof |
| WO2018087281A1 (en) * | 2016-11-11 | 2018-05-17 | Danmarks Tekniske Universitet | Fabrication of large-area multi-element two-dimensional materials |
| CN108374179A (en) * | 2018-02-07 | 2018-08-07 | 浙江大学 | A kind of preparation method and application of the compound nitrogen-doped carbon material of two cobaltous selenide of Fe2O3 doping |
| CN109759120A (en) * | 2019-03-07 | 2019-05-17 | 燕山大学 | A kind of nitrogen, nickel co-doped cobalt selenide ultrathin nanosheet and its preparation method and application |
| CN110624573A (en) * | 2019-10-18 | 2019-12-31 | 哈尔滨工业大学 | A kind of nickel-doped cobalt selenide electrocatalytic hydrogen evolution catalyst and preparation method thereof |
| CN110846680A (en) * | 2019-11-29 | 2020-02-28 | 哈尔滨工业大学 | Preparation method of multi-defect and active site electrocatalyst |
| CN111101151A (en) * | 2019-12-16 | 2020-05-05 | 湖南大学 | Preparation and application of molybdenum-doped cobalt selenide foam nickel composite electrode for water electrolysis |
| CN111482189A (en) * | 2020-04-14 | 2020-08-04 | 中国石油大学(华东) | NiSe with core-shell structure2@ NC electrocatalytic material and preparation method and application thereof |
| CN111514909A (en) * | 2020-03-27 | 2020-08-11 | 电子科技大学 | A kind of preparation method of two-dimensional material VSe2 with different degree of defect |
| CN112072125A (en) * | 2020-08-20 | 2020-12-11 | 浙江工业大学 | Preparation method and application of cobalt diselenide/carbon-based flexible electrode material with interface enhancement structure |
-
2020
- 2020-10-29 CN CN202011180973.XA patent/CN112481653B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0585973A (en) * | 1990-12-26 | 1993-04-06 | Mitsui Toatsu Chem Inc | Coproduction of aromatic hydroxyl compound and carbonyl compound |
| WO2011123795A1 (en) * | 2010-04-02 | 2011-10-06 | Battelle Memorial Institute | Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, and gas separation assemblies |
| CN105498811A (en) * | 2015-12-23 | 2016-04-20 | 信阳师范学院 | Preparation method of molybdenum selenide-acetylene black composite material and application of molybdenum selenide-acetylene black composite material as catalyst in hydrogen evolution reaction |
| WO2018087281A1 (en) * | 2016-11-11 | 2018-05-17 | Danmarks Tekniske Universitet | Fabrication of large-area multi-element two-dimensional materials |
| CN107694580A (en) * | 2017-09-07 | 2018-02-16 | 电子科技大学 | A kind of nano combined selenides and preparation method thereof |
| CN108374179A (en) * | 2018-02-07 | 2018-08-07 | 浙江大学 | A kind of preparation method and application of the compound nitrogen-doped carbon material of two cobaltous selenide of Fe2O3 doping |
| CN109759120A (en) * | 2019-03-07 | 2019-05-17 | 燕山大学 | A kind of nitrogen, nickel co-doped cobalt selenide ultrathin nanosheet and its preparation method and application |
| CN110624573A (en) * | 2019-10-18 | 2019-12-31 | 哈尔滨工业大学 | A kind of nickel-doped cobalt selenide electrocatalytic hydrogen evolution catalyst and preparation method thereof |
| CN110846680A (en) * | 2019-11-29 | 2020-02-28 | 哈尔滨工业大学 | Preparation method of multi-defect and active site electrocatalyst |
| CN111101151A (en) * | 2019-12-16 | 2020-05-05 | 湖南大学 | Preparation and application of molybdenum-doped cobalt selenide foam nickel composite electrode for water electrolysis |
| CN111514909A (en) * | 2020-03-27 | 2020-08-11 | 电子科技大学 | A kind of preparation method of two-dimensional material VSe2 with different degree of defect |
| CN111482189A (en) * | 2020-04-14 | 2020-08-04 | 中国石油大学(华东) | NiSe with core-shell structure2@ NC electrocatalytic material and preparation method and application thereof |
| CN112072125A (en) * | 2020-08-20 | 2020-12-11 | 浙江工业大学 | Preparation method and application of cobalt diselenide/carbon-based flexible electrode material with interface enhancement structure |
Non-Patent Citations (5)
| Title |
|---|
| "Facile Synthesis of Metal-Organic Framework-Derived CoSe2 Nanoparticles Embedded in the N-Doped Carbon Nanosheet Array and Application for Supercapacitors";Miao, Chenxu 等;《ACS APPLIED MATERIALS & INTERFACES》;20200226;第12卷(第8期);第9365-9375页 * |
| "In situ coupling of Co0.85Se and N-doped carbon via one-step selenization of metal–organic frameworks as a trifunctional catalyst foroverall water splitting and Zn–air batteries";Meng T 等;《Journal of Materials Chemistry A》;20170421;第5卷(第15期);第7001-7014页 * |
| "不同碳化温度对ZIF-8碳化物催化活性的影响";曹凤丽 等;《山东化工》;20180408(第07期);第4-6、9页 * |
| "基于钴基过渡金属化合物的电催化剂研究及应用";王诗乐 等;《中国优秀硕士学位论文全文数据库》;20190115(第1期);第B014-1990页 * |
| "镍钴基氧族催化电极的制备及其电解水性能研究";吴晓琳;《中国博士学位论文全文数据库》;20190115(第1期);第B014-312页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112481653A (en) | 2021-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112481653B (en) | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof | |
| CN112005413B (en) | Ni-Fe-N-doped carbon material trifunctional electrocatalyst based on ZIF-8 and its preparation method and application | |
| CN109841854B (en) | Nitrogen-doped carbon-supported monatomic oxygen reduction catalyst and preparation method thereof | |
| CN110148762B (en) | A kind of carbon material with nitrogen, fluorine and transition metal co-doped graphene structure and its one-step carbonization preparation method | |
| CN113445072B (en) | Foamed nickel composite electrode and preparation method and application thereof | |
| CN113862693B (en) | Preparation method and application of nitrogen-doped mesoporous carbon-loaded high-dispersion Ru nanoparticle catalyst | |
| CN108671948A (en) | A kind of preparation method of the flower-shaped nickel cobalt phosphide electrocatalysis material of self-assembling ultrathin | |
| CN108385124A (en) | A kind of preparation method of magnesium-yttrium-transition metal/carbon pipe/graphene elctro-catalyst for evolving hydrogen reaction | |
| CN114452982B (en) | W (W) 18 O 49 /CoO/CoWO 4 Self-supporting electro-catalytic material of/NF and preparation method thereof | |
| CN113955728B (en) | Preparation of cobalt phosphide/cobalt manganese phosphide with hollow grade structure and application of electrolytic water | |
| CN112221530A (en) | Preparation method and application of a non-precious metal single-atom bifunctional electrocatalyst | |
| CN112058293A (en) | Preparation method, product and application of nitrogen-phosphorus co-doped foam-like carbon nanosheet-supported NiCo nanoparticle composites | |
| CN114892206B (en) | Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof | |
| CN112080759A (en) | Preparation method of bismuth-doped bimetallic sulfide electrode for electrocatalytic oxidation of urea | |
| CN116742023A (en) | Nitrogen-doped carbon nano-tube supported metal alloy nitrogen-doped carbon nano-sheet catalyst and preparation method and application thereof | |
| CN113201759A (en) | Three-dimensional porous carbon supported bismuth sulfide/bismuth oxide composite catalyst and preparation method and application thereof | |
| CN118645642B (en) | Nitrogen-doped carbon nanotube-supported carbon-coated iron selenide bifunctional catalyst and preparation method and application thereof | |
| Yan et al. | HMTA-assisted formation of hierarchical Co-based materials built by low-dimensional substructures as water oxidation electrocatalysts | |
| CN112058297B (en) | Nickel-based electro-catalytic material and preparation method and application thereof | |
| CN116404179B (en) | Preparation method and application of zinc single atom loaded porous carbon nanotubes | |
| CN114807963B (en) | Copper-doped cobalt sulfide porous nano sheet/nickel foam electrode and preparation method and application thereof | |
| CN115896849B (en) | Cobalt diselenide and tungsten diselenide composite nano material, preparation method and application thereof | |
| CN116715217A (en) | Iron phosphide modified porous carbon sphere composite material, preparation and application thereof | |
| CN114843529B (en) | Porous carbon sphere derived based on water system ZIF, and preparation method and application thereof | |
| CN116544430A (en) | Transition metal-rare earth composite bi-component oxygen reduction electrocatalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |