CN115029729B - Chromium oxide/metal oxide composite material and preparation method and application thereof - Google Patents
Chromium oxide/metal oxide composite material and preparation method and application thereof Download PDFInfo
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- CN115029729B CN115029729B CN202210810861.0A CN202210810861A CN115029729B CN 115029729 B CN115029729 B CN 115029729B CN 202210810861 A CN202210810861 A CN 202210810861A CN 115029729 B CN115029729 B CN 115029729B
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- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910000423 chromium oxide Inorganic materials 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 41
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 97
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 239000006260 foam Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 239000002064 nanoplatelet Substances 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 3
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 abstract description 25
- 239000003054 catalyst Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 2
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000011651 chromium Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 230000010287 polarization Effects 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000001000 micrograph Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- OLFCLHDBKGQITG-UHFFFAOYSA-N chromium(3+) nickel(2+) oxygen(2-) Chemical compound [Ni+2].[O-2].[Cr+3] OLFCLHDBKGQITG-UHFFFAOYSA-N 0.000 description 7
- -1 for example Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001844 chromium Chemical class 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical group [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical group [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- QNMNQGSHNLYSLU-UHFFFAOYSA-N chromium(3+) cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Cr+3].[Co+2].[Ni+2] QNMNQGSHNLYSLU-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000006362 organocatalysis Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a chromium oxide/metal oxide composite material, a preparation method and application thereof, and belongs to the technical field of novel inorganic composite materials. The preparation method of the chromium oxide/metal oxide composite material comprises the following steps: dissolving metal salts and chromates in water; then transferring the mixture into a hydrothermal reaction kettle, adding a metal carrier into the reaction liquid, and performing hydrothermal reaction; separating, washing and drying the cooled reaction liquid to obtain a precursor binary or ternary metal oxide; and placing the precursor in a tube furnace, and calcining in a reducing gas atmosphere to obtain the chromium oxide/metal oxide composite material. The chromium oxide/metal oxide composite material prepared by the invention solves the problem of poor conductivity of the two-dimensional nano-sheet catalyst, further improves the intrinsic activity of the catalyst, shows excellent urea electro-oxidation catalytic performance and hydrogen evolution catalytic performance, and has wide application prospect.
Description
Technical Field
The invention relates to a chromium oxide/metal oxide composite material, a preparation method and application thereof, and belongs to the technical field of novel inorganic composite materials.
Background
The expensive cost of fossil fuels and the environmental pollution caused by the large-scale use of fossil fuels have become barriers for restricting the social development, and the exploration of renewable green hydrogen energy has important significance for relieving global energy crisis and environmental problems. Electrolyzed water is considered a widely promising hydrogen production technology, but the slow kinetics of the anodic oxygen evolution reaction severely limits the energy conversion efficiency of the overall water decomposition. The urea electrooxidation reaction (UOR) has a significantly reduced theoretical potential, can well replace oxygen evolution reactions, and can purify urea-rich wastewater, and thus has received a great deal of attention. Although some noble metal-based materials (e.g. Pt/C, ruO 2 And IrO 2 ) UOR can be efficiently catalyzed, but its high cost and scarcity motivates researchers to develop non-noble metal-based electrocatalysts with high benefits.
Nickel-based materials are widely available and inexpensive, are UOR and Hydrogen Evolution Reaction (HER) catalysts suitable for commercial applications, but their electrocatalytic properties are largely limited by intrinsic activity, limited active sites and poor electrical conductivity.
The multi-metal synergistic effect is an effective way for improving the intrinsic activity of the nickel-based material, for example, cobalt, chromium and the like can play a synergistic effect with nickel, so that the UOR and HER electrocatalytic activity of the nickel-based material is effectively improved; one of the effective methods to increase the number of active sites is to reduce the catalyst size, especially ultrafine nanoparticles, which can expose more metal atoms.
At present, the method for improving the conductivity of the nickel-based catalyst is mainly to compound with conductive substances such as carbon materials, metals and the like, wherein the method can not only improve the conductivity but also play a role of synergism of metal and metal oxide when being compounded with the metals.
The two-dimensional ultrathin nanosheets have the advantages of promoting electron transmission, having large specific surface area and the like, are widely applied to the fields of energy storage, electrocatalysis and the like, and are ideal catalytic platforms. For example, yan et al report on the use of a Ni/NiO core-shell nanoplatelet as a high efficiency HER electrocatalyst (crystal/amorphorus Ni/NiO core/shell nanosheets as highly active electrocatalysts for hydrogen evolution reaction); ji et al developed a carbon-coated Ni/NiO composite nanoplatelet for use as a UOR electrocatalyst (Oxygen vacuum-rich Ni/NiO@NCnanosheets with schottkyheterointerface for efficient urea oxidation reaction). At present, the Ni/NiO nano-sheet system has poor stability in an electrocatalytic environment, and the UOR catalytic activity of the Ni/NiO nano-sheet needs to be further improved. It has been reported that chromium oxide can improve the HER stability of Ni/NiO systems. Gong et al, cr 2 O 3 The surface of the Ni/NiO core-shell structure nano material is introduced, so that the HER stability (BlendingCr) of the material is greatly improved 2 O 3 introaNiO-NielectorocataystforsusatainedWatersepartting); huang Niu, et al, inspired by the above literature, prepared Ni/NiO/Cr by electrochemical reduction 2 O 3 Electrode material (preparation method of metal oxide passivated nickel/nickel oxide in-situ electrode, CN 113604839A). However, reported Ni/NiO/Cr 2 O 3 The composite material exists in the form of nano particlesAgglomeration between nanoparticles is liable to occur, resulting in a reduction of active sites. Furthermore, gong et al report Ni/NiO/Cr 2 O 3 The composite material is prepared by using a small amount of Cr 2 O 3 Coating Ni/NiO, resulting in Cr 2 O 3 The limited number of NiO interfaces is detrimental to UOR. Although Ni/NiO/Cr developed by Ji et al 2 O 3 The composite material is added with Cr 2 O 3 But the electrochemical reduction method has difficulty in precisely controlling the particle size and position of metal Ni, resulting in the development of Ni/NiO/Cr 2 O 3 HER performance of the composite material is far lower than Ni/NiO/Cr reported by Gong et al 2 O 3 A composite material.
Therefore, the invention aims to overcome the prior Ni/NiO/Cr 2 O 3 The system is insufficient, a simple and effective domain-limiting strategy is developed from a two-dimensional ultrathin nanosheet, ultrafine metal and metal oxide nanoparticles are limited in a chromium oxide nanosheet, agglomeration of the nanoparticles is effectively prevented, and further efficient preparation of the metal/metal oxide/chromium trioxide nanosheet catalyst is achieved.
Disclosure of Invention
[ technical problem ]
Ni/NiO/Cr prepared by the prior art 2 O 3 Composite material with limited number of active sites and Cr 2 O 3 The problem of limited number of NiO interfaces and the like is that the catalyst cannot be a high-efficiency UOR and HER bifunctional catalyst.
Technical scheme
In order to solve the problems, the invention firstly prepares the two-dimensional metal oxide nano-sheet by a hydrothermal method, and then synchronously realizes in-situ introduction of the superfine metal oxide nano-particles and the conductive superfine metal nano-particles by hydrogen heat treatment, thereby preparing the UOR and HER double-function nano-sheet catalyst with rich active sites. The further introduction of cobalt element not only improves the intrinsic activity of the nickel oxide catalyst, so that the prepared material has excellent UOR catalytic activity and can reach 200mA/cm under 1.386V voltage (vs reversible hydrogen electrode) 2 The high current density of (2) also improves the HER activity of the metallic nickel to reach 10mA/cm 2 Current density meterThe overpotential required is only 99mV.
A first object of the present invention is to provide a method for preparing a chromium oxide/metal oxide composite material, the method comprising the steps of:
(1) Dissolving metal salt and chromate in water to obtain reaction liquid; the metal salt comprises nickel salt and cobalt salt;
(2) Transferring the reaction liquid prepared in the step (1) into a hydrothermal reaction kettle, adding a metal carrier into the reaction liquid, and performing hydrothermal reaction;
(3) Cooling, separating, washing and drying the liquid after the hydrothermal reaction in the step (2) to obtain a precursor binary or ternary metal oxide;
(4) Placing the precursor binary or ternary metal oxide obtained in the step (3) into a tube furnace, and calcining in a reducing gas atmosphere at 420-550 ℃ to obtain the chromium oxide/metal oxide composite CrO x Ni/NiO; the molar ratio of the metal salt to the chromate in the step (1) is 0.5-2.0: 1.
in one embodiment of the present invention, the nickel salt in step (1) comprises one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel acetate.
In one embodiment of the present invention, the cobalt salt in step (1) comprises CoF 2 ，CoCl 2 ，CoBr 2 ，CoI 2 ，Co(Ac) 2 ，Co(NO 3 ) 2 ，CoSO 4 One or more of the following.
In one embodiment of the invention, the chromate in step (1) comprises one or more of potassium chromate, ammonium chromate, or sodium chromate.
In one embodiment of the present invention, the molar ratio of the nickel salt, cobalt salt and chromate in step (1) is 0.25 to 1.0:0.25 to 1.0:1.
in one embodiment of the present invention, the metal carrier in step (2) is any one of nickel foam, cobalt foam or copper foam.
In one embodiment of the present invention, the hydrothermal reaction in step (2) is performed at a temperature of 100 to 200 ℃ for a time of 6 to 24 hours.
In one embodiment of the present invention, the drying temperature in step (3) is 60 to 80 ℃ for 2 to 6 hours.
In one embodiment of the present invention, the reducing gas in the step (4) is a mixture of hydrogen and argon, wherein the volume fraction of the hydrogen is 5-95%.
In one embodiment of the present invention, the setting parameters of the tube furnace in step (4) are: the temperature rising rate is 2-10 ℃/min, the temperature rises to 420-550 ℃, and the heat preservation time is 1-5 h.
A second object of the present invention is to provide a chromium oxide/metal oxide composite material prepared by the above-mentioned preparation method, which is a mixed phase of crystalline and amorphous state, in which chromium oxide exists in the form of amorphous nano-sheets, and ultrafine metal nano-particles and ultrafine metal oxide nano-particles are embedded in the amorphous chromium oxide nano-sheets in the form of crystalline state.
A third object of the present invention is to provide the use of the above-mentioned chromium oxide/metal oxide composite in the field of electrocatalysis, organocatalysis.
[ advantageous effects ]
(1) The invention prepares the high conductivity and high activity nickel-based dual-functional agent with a two-dimensional nano structure by adopting a hydro-thermal reduction method for the first time, and the preparation process is simple and efficient;
(2) The invention not only effectively utilizes the advantage of large specific surface area of the nano-sheet, but also effectively prevents the agglomeration of the ultrafine metal oxide nano-particles, thereby guaranteeing the exposure of a large number of active sites. More importantly, the nickel-chromium atoms and the nickel-cobalt atoms have synergistic effect, so that the local electronic environment of nickel ions can be effectively regulated, and the intrinsic activity of nickel oxide is improved;
(3) The chromium oxide nano-sheet has the functions of limiting the domain and protecting. The domain limiting effect effectively inhibits the aggregation and growth of metal particles and metal oxide particles, so that ultrafine metal and metal oxide nano particles are uniformly dispersed in the chromium oxide nano sheet; on the other hand, the uniform distribution of the metal particles effectively improves the overall conductivity of the nano-sheet; the protection effectively inhibits the reduction of the metal oxide, so that a large amount of ultrafine metal oxide nano particles are reserved, and finally, a metal/metal oxide/chromium oxide composite material is formed; on the other hand, the protection effect also effectively improves the stability of the nickel-based catalyst in the electrocatalytic process.
(4) And reported Ni/NiO/Cr 2 O 3 The composite material is different, in the metal/metal oxide/chromium oxide composite material prepared by the invention, the metal and the metal oxide are not in heterojunction state, but are respectively and independently dispersed in CrO x In the nanosheets, a large number of metal/chromium oxide heterojunction and metal oxide/chromium oxide heterojunction are formed simultaneously, wherein the metal/chromium oxide heterojunction is beneficial to HER and the metal oxide/chromium oxide heterojunction is beneficial to UOR, so that the efficient UOR and HER dual-function catalyst is prepared.
Drawings
FIG. 1 is an X-ray diffraction chart of a chromium oxide/nickel oxide composite material prepared in example 1 of the present invention;
FIG. 2 is an X-ray photoelectron spectrum of chromium element in the chromium oxide/nickel oxide composite material prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the chromium oxide/nickel oxide composite material prepared in example 1 of the present invention;
FIG. 4 is a transmission electron microscope image of the chromium oxide/nickel oxide composite material prepared in example 1 of the present invention;
FIG. 5 is a graph showing the polarization of UOR for the chromium oxide/nickel oxide composite material prepared in example 1 of the present invention;
FIG. 6 is a graph showing the HER polarization curve of the chromium oxide/nickel oxide composite material of example 1 of the present invention;
FIG. 7 is a graph showing the polarization of UOR for the chromium oxide/nickel cobalt oxide composite material prepared in example 2 of the present invention;
FIG. 8 is a graph showing the HER polarization curve of the chromium oxide/nickel cobalt oxide composite material of example 2;
FIG. 9 is an X-ray diffraction chart of the metallic nickel material produced in comparative example 1 of the present invention;
FIG. 10 is a graph showing the comparison of the UOR polarization curves of the metallic nickel material prepared in comparative example 1 and example 1 of the present invention;
FIG. 11 is an X-ray diffraction pattern of the chromium oxide/nickel oxide composite material according to comparative example 2 of the present invention;
FIG. 12 is a transmission electron microscope image of the chromium oxide/nickel oxide composite material according to comparative example 2 of the present invention;
FIG. 13 is a graph comparing the polarization curves of the UOR of comparative example 2 and example 1 for the chromium oxide/nickel oxide material of the present invention;
FIG. 14 is a graph showing the comparison of the UOR polarization curves of the chromium oxide/nickel oxide material produced in comparative example 3 of the present invention;
FIG. 15 is a scanning electron microscope image of the chromium oxide/nickel oxide composite material produced in comparative example 4 of the present invention;
FIG. 16 is a graph comparing the polarization curves of the UOR of comparative example 4 and example 1 for the chromium oxide/nickel oxide material produced according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto.
Example 1
(1) 1.0mmol of nickel nitrate and 1.0mmol of potassium chromate are added into the polytetrafluoroethylene lining, and 30mL of deionized water is added for dissolution;
(2) Adding a piece of washed foam nickel carrier into the lining in the step (1);
(3) Transferring the reaction lining in the step (2) into a metal reaction kettle, and performing hydrothermal reaction for 8 hours at 140 ℃;
(4) Cooling the reaction liquid in the step (3), taking out foam nickel, washing with deionized water and ethanol for 2 times respectively, and then drying in a 60 ℃ oven for 2 hours to obtain a precursor binary nickel-chromium oxide NiCrO x ；
(5) Placing the precursor oxide obtained in the step (4) in a tube furnace, and placing the precursor oxide in H 2 Calcining in Ar (20/80%) mixed gas for 3h at a heating rate of 2 ℃/min and a calcining temperature of 450 ℃ to obtain the chromium oxide/nickel oxide composite CrO x /Ni/NiO。
FIG. 1 is an X-ray diffraction chart of the chromium oxide/nickel oxide composite material prepared in example 1 of the present invention, wherein the presence of crystalline Ni and NiO is observed, while the chromium phase is amorphous;
FIG. 2 is a graph of the X-ray photoelectron spectrum of chromium element in the chromium oxide/nickel oxide composite material prepared in example 1 of the present invention, wherein the valence state of +3 indicates that the element Cr is not reduced and still exists in the oxidized state;
FIG. 3 is a scanning electron microscope image of the chromium oxide/nickel oxide composite material prepared in example 1 of the present invention, which shows a randomly arranged ultrathin nanosheet structure, and maintains a stable nanosheet morphology at high temperatures;
FIG. 4 is a transmission electron microscope image of the chromium oxide/nickel oxide composite material prepared in example 1 of the present invention, showing that amorphous chromium oxide exists in the form of nano-sheets, and crystalline metallic Ni and NiO are nano-particles and are embedded in the chromium oxide nano-sheets;
FIG. 5 is a graph showing the polarization of UOR for the chromium oxide/nickel oxide composite material prepared in example 1 of the present invention, wherein the electrochemical test was performed in a standard three-electrode system connected to a CHI760E electrochemical workstation, using the composite material grown in situ on nickel foam directly as the working electrode (1 cm. Times.1 cm), pt plate as the counter electrode, hg/HgO electrode as the reference electrode, and 1.0M KOH+0.33M urea as the electrolyte, with only 1.386V (vs reversible hydrogen electrode) being required to reach 200mA/cm 2 Exhibits excellent UOR properties.
FIG. 6 is a graph showing the HER polarization of the chromium oxide/nickel oxide composite prepared in accordance with example 1 of the present invention, the electrochemical test was performed in a standard three electrode system connected to a CHI760E electrochemical workstation, using the composite grown in situ on nickel foam directly as the working electrode (1 cm. Times.1 cm), pt plate as the counter electrode, hg/HgO electrode as the reference electrode, and 1.0M KOH as the electrolyte to 10mA/cm 2 The required overpotential for the current density was 111mV.
Example 2
(1) 0.6mmol of nickel nitrate, 0.4mmol of cobalt nitrate and 1.0mmol of potassium chromate are added into the polytetrafluoroethylene lining, and 30mL of deionized water is added for dissolution;
(2) Adding a piece of washed foam nickel carrier into the lining in the step (1);
(3) Transferring the reaction lining in the step (2) into a metal reaction kettle, and performing hydrothermal reaction for 8 hours at 140 ℃;
(4) Cooling the reaction liquid in the step (3), taking out foam nickel, washing with deionized water and ethanol for 2 times respectively, and then drying in a 60 ℃ oven for 2 hours to obtain a precursor ternary nickel cobalt chromium oxide NiCoCrO x ；
(5) Placing the precursor oxide obtained in the step (4) in a tube furnace, and placing the precursor oxide in H 2 Calcining in Ar (20/80%) mixed gas for 3h at a heating rate of 2 ℃/min and a calcining temperature of 450 ℃ to obtain the chromium oxide/nickel cobalt oxide composite CrO x /NiCo/NiCoO x 。
FIG. 7 shows CrO produced in example 2 of the present invention x /NiCo/NiCoO x UOR polarization curve of composite material, the electrochemical test is performed in a standard three-electrode system connected with CHI760E electrochemical workstation, the composite material grown in situ on foam nickel is directly used as a working electrode (1 cm multiplied by 1 cm), pt sheet is used as a counter electrode, hg/HgO electrode is used as a reference electrode, 1.0M KOH+0.33M urea is used as electrolyte, and only 1.337V voltage (vs reversible hydrogen electrode) is needed to reach 200mA/cm 2 Exhibits excellent UOR properties.
FIG. 8 is a graph showing the HER polarization of the chromium oxide/nickel cobalt oxide composite material prepared in example 2 of the present invention, the electrochemical test was performed in a standard three electrode system connected to a CHI760E electrochemical workstation, using the composite material grown in situ on foam nickel directly as the working electrode (1 cm. Times.1 cm), pt plate as the counter electrode, hg/HgO electrode as the reference electrode, and 1.0M KOH as the electrolyte to 10mA/cm 2 The overpotential required for the current density is 99mV.
Comparative example 1
(1) 1.0mmol of nickel nitrate and 2.0mmol of urea are added into a polytetrafluoroethylene lining, and 30mL of deionized water is added for dissolution;
(2) Adding a piece of washed foam nickel carrier into the lining in the step (1);
(3) Transferring the reaction lining in the step (2) into a metal reaction kettle, and performing hydrothermal reaction for 8 hours at 140 ℃;
(4) Cooling the reaction liquid in the step (3), taking out foam nickel, washing with deionized water and ethanol for 2 times respectively, drying, and calcining in a muffle furnace at 350 ℃ for 2 hours to obtain a precursor nickel oxide NiO;
(5) Placing the precursor obtained in the step (4) in a tube furnace, and placing the precursor in H 2 Calcining in Ar (20/80%) mixed gas for 30min, wherein the heating rate is 2 ℃/min, and the reduction temperature is 250 ℃, thus obtaining the metallic nickel material Ni.
FIG. 9 is an X-ray diffraction chart of the metallic nickel material produced in comparative example 1 of the present invention. As can be seen, niO is at H 2 The Ar (20/80%) mixture can be reduced to metallic nickel only at a reduction temperature of 250 ℃. From this, it is shown that example 1 has a protective effect compared with comparative example 1, and can greatly retard the reduction of NiO, thereby preparing CrO x Ni/NiO composite material.
FIG. 10 is a graph showing the comparison of the UOR polarization curves of the metallic nickel material prepared in comparative example 1 and example 1. As can be seen, a voltage of 1.446V is required to reach 200mA/cm 2 Is a current density of (a); the catalysts prepared in comparative example 1 and example 1 were capable of providing current densities of 104 and 275mA/cm, respectively, at a voltage of 1.4V 2 . It can be seen that the UOR activity of the catalyst formed by the reaction is greatly reduced without the presence of the chromia nanosheet substrate.
Comparative example 2
(1) 1.0mmol of nickel nitrate and 1.0mmol of potassium chromate are added into the polytetrafluoroethylene lining, and 30mL of deionized water is added for dissolution;
(2) Adding a piece of washed foam nickel carrier into the lining in the step (1);
(3) Transferring the reaction lining in the step (2) into a metal reaction kettle, and performing hydrothermal reaction for 8 hours at 140 ℃;
(4) Cooling the reaction liquid in the step (3), taking out foam nickel, washing with deionized water and ethanol for 2 times respectively, and then drying in a 60 ℃ oven for 2 hours to obtain a precursor binary nickel-chromium oxide NiCrO x ；
(5) Step (4)) The obtained precursor binary nickel-chromium oxide is placed in a tube furnace and is treated in H 2 Calcining in Ar (20/80%) mixed gas for 3h at a heating rate of 2 ℃/min and a calcining temperature of 400 ℃ to obtain the chromium oxide/nickel oxide material CrO x /NiO。
FIG. 11 is an X-ray diffraction pattern of the chromium oxide/nickel oxide composite material prepared in comparative example 2 of the present invention, in which the presence of metallic Ni was not observed, whereas comparative example 1 shows that NiO can be completely reduced to metallic Ni at a lower temperature of 250 ℃.
FIG. 12 shows CrO produced in comparative example 2 of the present invention x As can be seen from the transmission electron microscope image of the NiO composite material, the ultrafine NiO nano particles are uniformly distributed in the amorphous CrO x In the nanoplatelets, it is demonstrated that in example 1, example 2 and comparative example 2, amorphous CrO x Good encapsulation of NiO is achieved, so that the NiO is protected, the temperature at which NiO is reduced to metallic Ni is greatly increased, and in this comparative example, ultrafine NiO nanoparticles are not reduced to metallic Ni at 400 ℃.
FIG. 13 is a graph comparing the polarization curve of the UOR of comparative example 2 and example 1 of the chromium oxide/nickel oxide material produced according to the present invention. As can be seen, the catalyst requires 1.454V to provide 200mA/cm 2 And the corresponding current density at high potential drops greatly. It can be seen that the metallic Ni, which is a conductive material, is absent due to CrO x The conductivity of NiO is poor, resulting in a significantly lower UOR catalytic activity than CrO x /Ni/NiO。
Comparative example 3
(1) 1.0mmol of nickel nitrate and 1.0mmol of potassium chromate are added into the polytetrafluoroethylene lining, and 30mL of deionized water is added for dissolution;
(2) Adding a piece of washed foam nickel carrier into the lining in the step (1);
(3) Transferring the reaction lining in the step (2) into a metal reaction kettle, and performing hydrothermal reaction for 8 hours at 140 ℃;
(4) Cooling the reaction liquid in the step (3), taking out foam nickel, washing with deionized water and ethanol for 2 times respectively, and then drying in a 60 ℃ oven for 2 hours to obtain a precursor binary nickel-chromium oxide NiCrO x ；
(5) Placing the precursor binary nickel-chromium oxide obtained in the step (4) into a tube furnace, and placing the tube furnace in H 2 Calcining in Ar (20/80%) mixed gas for 3h at a heating rate of 2 ℃/min and a calcining temperature of 600 ℃ to obtain the chromium oxide/nickel composite CrO x /Ni。
As can be seen from FIG. 14, the chromium oxide/nickel oxide composite CrO prepared in comparative example 3 x The Ni catalyst required 1.444V voltage to provide 200mA/cm 2 Is used for the current density of the battery. It can be seen that in the absence of the active material NiO, the catalytic activity of the product UOR formed by the reaction is significantly reduced compared with example 1.
Comparative example 4
(1) 1.0mmol of nickel nitrate, 1.0mmol of chromium nitrate and 2.0mmol of urea are added into a polytetrafluoroethylene lining, and 30mL of deionized water is added for dissolution;
(2) Adding a piece of washed foam nickel carrier into the lining in the step (1);
(3) Transferring the reaction lining in the step (2) into a metal reaction kettle, and performing hydrothermal reaction for 8 hours at 140 ℃;
(4) Cooling the reaction liquid in the step (3), taking out foam nickel, washing with deionized water and ethanol for 2 times respectively, drying, and calcining in a muffle furnace at 350 ℃ for 2 hours to obtain a precursor binary nickel-chromium oxide NiCrO x ；
(5) Placing the precursor binary nickel-chromium oxide obtained in the step (4) into a tube furnace, and placing the tube furnace in H 2 Calcining in Ar (20/80%) mixed gas for 3h at a heating rate of 2 ℃/min and a calcining temperature of 450 ℃ to obtain the chromium oxide/nickel oxide composite CrO x /Ni/NiO。
FIG. 15 is a scanning electron microscope image of the chromium oxide/nickel oxide composite material prepared in comparative example 4 of the present invention, wherein the composite material prepared by using chromium nitrate as a chromium salt shows a network structure of nanowire stacking, which is significantly different from the nano-sheet structure prepared in example 1, indicating that the nano-sheet structure cannot be obtained when the conventional chromium salt is used instead of the chromate; in addition, crO prepared with low-valence chromium salts x Ni/NiO is similar to the materials reported in the literature and patents mentioned in the background art, crO x The coating of Ni and NiO cannot be achieved simultaneously.
FIG. 16 is a graph comparing the polarization curves of the UOR of comparative example 4 and example 1 for the chromium oxide/nickel oxide composite material produced according to the present invention. Comparative example 4A voltage of 1.449V was applied to achieve 200mA/cm 2 Is capable of providing current densities of 70 and 275mA/cm for comparative example 3 and example 1, respectively, at a voltage of 1.4V 2 。
It can be seen that the performance of comparative example 4 is significantly lower than that of example 1, probably because the nanowires are too loose to be isolated from each other, which is detrimental to the mass transfer process between nanowires, and the nanosheet structure can better perform the interaction of the conductive substrate and the active species when used as a reaction platform of the chromia/nickel oxide composite, thus exhibiting superior UOR performance.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for preparing a chromium oxide/metal oxide composite material, the method comprising the steps of:
(1) Dissolving metal salt and chromate in water to obtain reaction liquid; the metal salt comprises nickel salt and/or cobalt salt;
(2) Transferring the reaction liquid prepared in the step (1) into a hydrothermal reaction kettle, adding a metal carrier into the reaction liquid, and performing hydrothermal reaction;
(3) Cooling, separating, washing and drying the liquid after the hydrothermal reaction in the step (2) to obtain a precursor binary or ternary metal oxide;
(4) Placing the precursor binary or ternary metal oxide obtained in the step (3) into a tube furnace, and calcining in a reducing gas atmosphere at the calcining temperature of 420-550 ℃ to obtain a chromium oxide/metal oxide composite material; the molar ratio of the metal salt to the chromate in the step (1) is 0.5-2.0: 1.
2. the method of claim 1, wherein the cobalt salt in step (1) comprises CoF 2 、CoCl 2 、CoBr 2 、CoI 2 、Co(Ac) 2 、Co(NO 3 ) 2 、CoSO 4 One or more of the following.
3. The method of claim 1, wherein the nickel salt in step (1) comprises one or more of nickel sulfate, nickel chloride, nickel nitrate, and nickel acetate.
4. The method of claim 1, wherein the chromate in step (1) comprises one or more of potassium chromate, ammonium chromate, or sodium chromate.
5. The method according to claim 1, wherein the hydrothermal reaction in step (2) is carried out at a temperature of 100 to 200 ℃ for a time of 6 to 24 hours.
6. The method of claim 1, wherein the metal support in step (2) is any one of nickel foam, cobalt foam, or copper foam.
7. The method according to claim 1, wherein the drying temperature in the step (3) is 60 ℃ to 80 ℃ for 2 to 6 hours.
8. The method according to claim 1, wherein the setting parameters of the tube furnace in step (4) are: the temperature rising rate is 2-10 ℃/min, the temperature rises to 420-550 ℃, and the heat preservation time is 1-5 h.
9. The chromium oxide/metal oxide composite material produced by the production method according to any one of claims 1 to 8, wherein the chromium oxide/metal oxide composite material is in a mixed phase of crystalline and amorphous state, the chromium oxide exists in the form of amorphous nanoplatelets, and the ultrafine metal nanoparticles and the ultrafine metal oxide nanoparticles are embedded in the amorphous chromium oxide nanoplatelets in the form of crystalline.
10. Use of the chromium oxide/metal oxide composite material according to claim 9 in the fields of electrocatalytic hydrogen evolution and electrocatalytic urea oxidation.
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| CN101723460A (en) * | 2009-11-23 | 2010-06-09 | 中国科学院过程工程研究所 | Process for preparing chromium oxide from laterite-nickel ores |
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| CN110947374A (en) * | 2019-12-16 | 2020-04-03 | 佛山职业技术学院 | Hydroxyl metal oxide nano catalyst and preparation method thereof |
| CN113621987A (en) * | 2021-08-10 | 2021-11-09 | 江苏大学 | Cobalt-molybdenum alloy and cobalt-molybdenum mixed oxide electrocatalyst and preparation method and application thereof |
| CN114318358A (en) * | 2021-11-10 | 2022-04-12 | 青岛科技大学 | Modulated nickel/cobalt bimetallic MOF-based electrocatalyst, preparation method and application |
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| CN101723460A (en) * | 2009-11-23 | 2010-06-09 | 中国科学院过程工程研究所 | Process for preparing chromium oxide from laterite-nickel ores |
| CN110404564A (en) * | 2019-08-16 | 2019-11-05 | 澳门大学 | A kind of difunctional complete solution water power catalyst and the preparation method and application thereof |
| CN110947374A (en) * | 2019-12-16 | 2020-04-03 | 佛山职业技术学院 | Hydroxyl metal oxide nano catalyst and preparation method thereof |
| CN113621987A (en) * | 2021-08-10 | 2021-11-09 | 江苏大学 | Cobalt-molybdenum alloy and cobalt-molybdenum mixed oxide electrocatalyst and preparation method and application thereof |
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