CN115029729A - 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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- CN115029729A CN115029729A CN202210810861.0A CN202210810861A CN115029729A CN 115029729 A CN115029729 A CN 115029729A CN 202210810861 A CN202210810861 A CN 202210810861A CN 115029729 A CN115029729 A CN 115029729A
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- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910000423 chromium oxide Inorganic materials 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 42
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002135 nanosheet Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 14
- 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 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 118
- 229910052759 nickel Inorganic materials 0.000 claims description 38
- 239000002105 nanoparticle Substances 0.000 claims description 14
- 239000006260 foam Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 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
- 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
- 238000010438 heat treatment Methods 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
- 238000006555 catalytic reaction Methods 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
- 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
- 238000004321 preservation Methods 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
- 239000003054 catalyst Substances 0.000 abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 239000007789 gas Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004202 carbamide Substances 0.000 abstract description 7
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 2
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 32
- 229910000480 nickel oxide Inorganic materials 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000011651 chromium Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 15
- 230000010287 polarization Effects 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- OLFCLHDBKGQITG-UHFFFAOYSA-N chromium(3+) nickel(2+) oxygen(2-) Chemical compound [Ni+2].[O-2].[Cr+3] OLFCLHDBKGQITG-UHFFFAOYSA-N 0.000 description 10
- -1 for example Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000002441 X-ray diffraction 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
- 239000003792 electrolyte Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 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
- 238000000840 electrochemical analysis Methods 0.000 description 4
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 150000001844 chromium Chemical class 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 150000002739 metals 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000011161 development Methods 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
- 239000002060 nanoflake Substances 0.000 description 2
- 239000002086 nanomaterial 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
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material 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
- 230000007547 defect Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 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
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 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
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- 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
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- 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
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C25B11/031—Porous electrodes
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- 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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a chromium oxide/metal oxide composite material and a preparation method and application thereof, belonging 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 a metal salt and a chromate salt in water; then transferring the mixture to a hydrothermal reaction kettle, adding a metal carrier into the reaction liquid, and carrying out hydrothermal reaction; separating, washing and drying the cooled reaction liquid to obtain a precursor binary or ternary metal oxide; and (3) placing the precursor in a tubular 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 nanosheet catalyst, further improves the intrinsic activity of the catalyst, shows excellent urea electrooxidation 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 and a preparation method and application thereof, belonging to the technical field of novel inorganic composite materials.
Background
The expensive cost of fossil fuel and the environmental pollution problem caused by the large use of fossil fuel become barriers restricting the social development, and the exploration of renewable green hydrogen energy has important significance for relieving the global energy crisis and the environmental problem. Electrolysis of water is considered to be a promising hydrogen production technique, but the slow kinetics of the anodic oxygen evolution reaction severely limits the energy conversion efficiency of the overall water splitting. The urea electrooxidation reaction (UOR) has a significantly reduced theoretical potential, can well replace oxygen evolution reaction, and can purify waste water rich in urea, thereby receiving wide attention. Although some precious metal-based materials (e.g., Pt/C, RuO) 2 And IrO 2 ) UOR can be effectively catalyzed, but its high cost and scarcity have prompted researchers to develop non-noble metal-based electrocatalysts with high benefit.
The nickel-based material has wide sources and low price, is a UOR and Hydrogen Evolution Reaction (HER) catalyst suitable for industrial application, but the electrocatalytic performance of the nickel-based material is limited by intrinsic activity, limited active sites and poor conductivity to a great extent.
The multi-metal synergistic effect is an effective mode 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 electrical catalytic activity of UOR and HER of the nickel-based material is effectively improved; one of the effective ways to increase the number of active sites is to reduce the size of the catalyst, especially the ultra-fine nanoparticles, to expose more metal atoms.
At present, the method for improving the conductivity of the nickel-based catalyst is mainly to compound the nickel-based catalyst with conductive substances such as carbon materials, metals and the like, wherein the compound with the metals can not only improve the conductivity, but also play a role in synergy of metal-metal oxides.
The two-dimensional ultrathin nanosheet has the advantages of promotion of electron transmission, large specific surface area and the like, is widely applied to the fields of energy storage, electrocatalysis and the like, and is an ideal catalytic platform. For example, Yan et al reported that a Ni/NiO core-shell nanosheet was used as a highly efficient HER electrocatalyst (Crystalline/amophorus Ni/NiO core/shell nanosheets)as high active electrolytes for hydrogen evolution reaction); ji et al developed a carbon-coated Ni/NiO composite nanosheet for use as a UOR electrocatalyst (Oxygen vacancy-rich Ni/NiO @ NCnanosheets with a schottky thermal interface for effect oxidation reaction). At present, the stability of the Ni/NiO nano-flake system under the electrocatalysis environment is poor, and the UOR catalytic activity of the Ni/NiO nano-flake system needs to be further improved. Chromium oxide has been reported to improve the HER stability of the Ni/NiO system. Gong et al transform Cr 2 O 3 The Ni/NiO core-shell structure nano material surface is introduced, and the HER stability (blending Cr) of the material is greatly improved 2 O 3 intoaNiO-Nielectrocatalytic for contained water splitting); inspired by the above documents, yellow girls and the like adopt an electrochemical reduction method to prepare Ni/NiO/Cr 2 O 3 Electrode material (preparation method of metal oxide passivated nickel/nickel oxide in-situ electrode, CN 113604839 a). However, Ni/NiO/Cr has been reported 2 O 3 The composite material exists in the form of nano particles, and the agglomeration phenomenon is easy to occur among the nano particles, so that the active sites are reduced. Furthermore, Gong et al reported Ni/NiO/Cr 2 O 3 The composite material is a small amount of Cr 2 O 3 Coating of Ni/NiO to result in Cr 2 O 3 The number of/NiO interfaces is limited, which is not favorable for UOR. Although the Ni/NiO/Cr developed by Ji et al 2 O 3 The composite material is added with Cr 2 O 3 However, it is difficult to precisely control the grain size and position of metallic Ni by electrochemical reduction, resulting in the development of Ni/NiO/Cr 2 O 3 The HER performance of the composite material is far lower than that of Ni/NiO/Cr reported by Gong et al 2 O 3 A composite material.
Therefore, the invention aims to overcome the existing Ni/NiO/Cr 2 O 3 The defects of the system are taken as a starting point for two-dimensional ultrathin nano sheets, a simple and effective confinement strategy is developed, superfine metal and metal oxide nano particles are confined in chromium oxide nano sheets, the agglomeration of the nano particles is effectively prevented, and the preparation of the high-efficiency metal/metal oxide/chromium trioxide nano sheet catalyst is further realized.
Disclosure of Invention
[ problem ] to
Ni/NiO/Cr prepared by prior art 2 O 3 The composite material has limited number of active sites and Cr 2 O 3 The number of/NiO interfaces is limited, and the catalyst cannot become a high-efficiency UOR and HER dual-function catalyst.
[ solution ]
In order to solve the problems, the invention firstly prepares a two-dimensional metal oxide nanosheet by a hydrothermal method, and then synchronously realizes in-situ introduction of superfine metal oxide nanoparticles and conductive superfine metal nanoparticles by hydrogen heat treatment to prepare the UOR and HER bifunctional nanosheet catalyst with rich active sites. The further introduction of the 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 the nickel alloy also improves the HER activity of the metal nickel to 10mA/cm 2 The overpotential required for the current density is only 99 mV.
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/or cobalt salt;
(2) transferring the reaction liquid prepared in the step (1) to a hydrothermal reaction kettle, adding a metal carrier into the reaction liquid, and carrying out hydrothermal reaction;
(3) cooling, separating, washing and drying the liquid obtained 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 the chromium oxide/metal oxide composite material CrO x /Ni/NiO; in the step (1), the molar ratio of the metal salt to the chromate 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 and 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 (a).
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, the cobalt salt and the chromate in the 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 the step (2) is any one of nickel foam, cobalt foam, or copper foam.
In one embodiment of the invention, the temperature of the hydrothermal reaction in the step (2) is 100-200 ℃ and the time is 6-24 h.
In one embodiment of the invention, the drying temperature in the step (3) is 60-80 ℃ and the time is 2-6 h.
In one embodiment of the invention, the reducing gas in the step (4) is a mixed gas of hydrogen and argon, wherein the volume fraction of hydrogen is 5-95%.
In one embodiment of the present invention, the setting parameters of the tube furnace in the step (4) are as follows: the heating rate is 2-10 ℃/min, the temperature is raised to 420-550 ℃, and the heat preservation time is 1-5 h.
The second purpose of the invention is to provide a chromium oxide/metal oxide composite material prepared by the preparation method, wherein the chromium oxide/metal oxide composite material is in a crystalline and amorphous mixed phase, the chromium oxide exists in the form of amorphous nanosheets, and the ultrafine metal nanoparticles and the ultrafine metal oxide nanoparticles are embedded in the amorphous chromium oxide nanosheets in the crystalline form.
The third purpose of the invention is to provide the application of the chromium oxide/metal oxide composite material in the fields of electrocatalysis and organic catalysis.
[ advantageous effects ]
(1) The invention adopts the hydrogen thermal reduction method to prepare the high-conductivity and high-activity nickel-based bifunctional catalyst with the two-dimensional nano structure 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 ensuring the exposure of a large number of active sites. More importantly, the nickel-chromium atoms and the nickel-cobalt atoms have a synergistic effect, so that the electronic environment of the nickel ion local area can be effectively regulated, and the intrinsic activity of the 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 agglomeration and growth of metal particles and metal oxide particles, so that the ultrafine metal and metal oxide nanoparticles are uniformly dispersed in the chromium oxide nanosheets; on the other hand, the uniform distribution of the metal particles effectively improves the overall conductivity of the nanosheets; the protection effectively inhibits the reduction of metal oxide, so that a large amount of ultrafine metal oxide nano particles are reserved, and finally the 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 electrocatalysis process.
(4) With reported Ni/NiO/Cr 2 O 3 Different from composite materials, in the metal/metal oxide/chromium oxide composite material prepared by the invention, the metal and the metal oxide do not exist in a heterojunction state, but are respectively and independently dispersed in CrO x In the nano-sheet, a large number of metal/chromium oxide heterojunctions and metal oxide/chromium oxide heterojunctions are formed simultaneously, wherein the metal/chromium oxide heterojunctions are beneficial to HER, and the metal oxide/chromium oxide heterojunctions are beneficial to UOR, so that the high-efficiency UOR and HER bifunctional catalyst is prepared.
Drawings
FIG. 1 is an X-ray diffraction pattern of a chromium oxide/nickel oxide composite material obtained in example 1 of the present invention;
FIG. 2 is an X-ray photoelectron spectrum of chromium in a chromium oxide/nickel oxide composite material prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a composite material of chromium oxide/nickel oxide prepared in example 1 of the present invention;
FIG. 4 is a transmission electron microscope image of the composite material of chromium oxide/nickel oxide prepared in example 1;
FIG. 5 is a UOR polarization plot of a chromium oxide/nickel oxide composite material prepared in example 1 of the present invention;
FIG. 6 is a graph of HER polarization curves of a chromium oxide/nickel oxide composite material prepared in example 1 of the present invention;
FIG. 7 is a plot of the UOR polarization of the chromium oxide/nickel cobalt oxide composite material prepared in example 2 of the present invention;
FIG. 8 is a graph of the HER polarization curve of the composite material of chromium oxide/nickel cobalt oxide prepared in example 2 of the present invention;
FIG. 9 is an X-ray diffraction chart of a metallic nickel material obtained in comparative example 1 of the present invention;
FIG. 10 is a comparative plot of the UOR polarization curves of comparative example 1 metallic nickel material of the present invention and example 1;
FIG. 11 is an X-ray diffraction pattern of a chromium oxide/nickel oxide composite material according to comparative example 2 of the present invention;
FIG. 12 is a transmission electron micrograph of a chromium oxide/nickel oxide composite according to comparative example 2 of the present invention;
FIG. 13 is a plot comparing the UOR polarization curves of comparative example 2 of the present invention with those of example 1;
FIG. 14 is a comparative plot of the UOR polarization curve for the chromium oxide/nickel oxide material prepared in comparative example 3 of the present invention;
FIG. 15 is a scanning electron micrograph of a chromium oxide/nickel oxide composite according to comparative example 4 of the present invention;
FIG. 16 is a plot comparing the UOR polarization curves of comparative example 4 of the invention with that of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Adding 1.0mmol of nickel nitrate and 1.0mmol of potassium chromate into a polytetrafluoroethylene lining, and adding 30mL of deionized water for dissolving;
(2) adding a piece of cleaned 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 carrying out hydrothermal reaction for 8 hours at 140 ℃;
(4) cooling the reaction liquid obtained in the step (3), taking out the foamed nickel, washing the foamed nickel for 2 times by using deionized water and ethanol respectively, and then placing the washed foamed nickel in a 60 ℃ drying oven for drying for 2 hours to obtain a precursor binary nickel chromium oxide NiCrO x ；
(5) Putting the precursor oxide obtained in the step (4) into a tube furnace, and putting the precursor oxide in the tube furnace H 2 Calcining the mixture in/Ar (20/80%) for 3h at the temperature rise rate of 2 ℃/min and the calcining temperature of 450 ℃, thus obtaining the chromium oxide/nickel oxide composite material CrO x /Ni/NiO。
FIG. 1 is an X-ray diffraction pattern of a chromia/nickel oxide composite obtained in example 1 of the present invention, in which the presence of crystalline Ni and NiO is observed, while the chromium phase is amorphous;
FIG. 2 is an X-ray photoelectron spectrum of chromium in a chromium oxide/nickel oxide composite material prepared in example 1 according to the present invention, wherein the valence is +3, which indicates that the element Cr is not reduced and still exists in an oxidized state;
FIG. 3 is a scanning electron microscope image of the chromic 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 temperature;
FIG. 4 is a transmission electron microscope image of the composite material of chromium oxide/nickel oxide prepared in example 1, in which it can be seen that amorphous chromium oxide exists in the form of nanosheets, and crystalline metals Ni and NiO are in the form of nanoparticles and embedded in the chromium oxide nanosheets;
FIG. 5 is a graph of the UOR polarization of a composite of chromium oxide/nickel oxide obtained in example 1 of the present invention, in which electrochemical tests were carried out in a standard three-electrode system connected to an electrochemical workstation CHI760E, in situ on foamed nickelThe grown composite material is directly used as a working electrode (1cm multiplied by 1cm), a Pt sheet is used as a counter electrode, a Hg/HgO electrode is used as a reference electrode, 1.0M KOH +0.33M urea is used as electrolyte, and only 1.386V voltage (vs reversible hydrogen electrode) is needed to reach 200mA/cm 2 Exhibit excellent UOR performance.
FIG. 6 is a graph showing the HER polarization curves of the composite material of chromium oxide/nickel oxide prepared in example 1 of the present invention, in which the electrochemical test was performed in a standard three-electrode system connected to an electrochemical workstation CHI760E, and the composite material grown in situ on foamed nickel was directly used as a working electrode (1 cm. times.1 cm), a Pt sheet was used as a counter electrode, a Hg/HgO electrode was used as a reference electrode, 1.0M KOH was used as an electrolyte, and 10mA/cm was reached 2 The overpotential required for the current density was 111 mV.
Example 2
(1) Adding 0.6mmol of nickel nitrate, 0.4mmol of cobalt nitrate and 1.0mmol of potassium chromate into a polytetrafluoroethylene lining, and adding 30mL of deionized water for dissolving;
(2) adding a piece of cleaned 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 carrying out hydrothermal reaction for 8 hours at 140 ℃;
(4) cooling the reaction liquid obtained in the step (3), taking out the foamed nickel, washing the foamed nickel for 2 times by using deionized water and ethanol respectively, and then placing the washed foamed nickel in a 60 ℃ drying oven for drying for 2 hours to obtain a precursor of ternary nickel-cobalt-chromium oxide NiCoCrO x ；
(5) Putting the precursor oxide obtained in the step (4) into a tube furnace, and putting the precursor oxide in the tube furnace H 2 Calcining for 3h in an/Ar (20/80%) mixed gas at the temperature rise rate of 2 ℃/min and the calcining temperature of 450 ℃, thus obtaining the chromium oxide/nickel cobalt oxide composite material CrO x /NiCo/NiCoO x 。
FIG. 7 shows CrO obtained in example 2 of the present invention x /NiCo/NiCoO x UOR polarization profile of the composite material, the electrochemical test being carried out in a standard three-electrode system connected to CHI760E electrochemical workstation, using the composite material grown in situ on nickel foam as working electrode (1 cm. times.1 cm), Pt sheet as counter electrode, Hg/HgO electrode as reference electrode, 1.0MKOH +0.33M urea is taken as electrolyte, and only 1.337V voltage (vs reversible hydrogen electrode) is needed to reach 200mA/cm 2 Exhibit excellent UOR performance.
FIG. 8 is a graph showing the HER polarization curves of the composite material of chromium oxide/nickel cobalt oxide prepared in example 2 of the present invention, wherein the electrochemical test was performed in a standard three-electrode system connected to CHI760E electrochemical workstation, and the composite material grown in situ on foamed nickel was directly used as a working electrode (1 cm. times.1 cm), a Pt sheet was used as a counter electrode, a Hg/HgO electrode was used as a reference electrode, 1.0M KOH was used as an electrolyte, and 10mA/cm was reached 2 The overpotential required for the current density was 99 mV.
Comparative example 1
(1) Adding 1.0mmol of nickel nitrate and 2.0mmol of urea into a polytetrafluoroethylene lining, and adding 30mL of deionized water for dissolving;
(2) adding a piece of cleaned 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 carrying out hydrothermal reaction for 8 hours at 140 ℃;
(4) cooling the reaction liquid obtained in the step (3), taking out the foamed nickel, washing for 2 times by using deionized water and ethanol, drying, and calcining for 2 hours in a muffle furnace at 350 ℃ to obtain a precursor nickel oxide NiO;
(5) putting the precursor obtained in the step (4) into a tube furnace, and putting the precursor into a tube furnace in the presence of H 2 Calcining in mixed gas of/Ar (20/80%) 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 pattern of a metallic nickel material obtained in comparative example 1 of the present invention. As can be seen from the figure, NiO is in H 2 the/Ar (20/80%) mixed gas only needs a reduction temperature of 250 ℃ to be completely reduced into metallic nickel. Thus, in comparison with comparative example 1, example 1 shows that chromium oxide has a protective effect in the application, and can greatly delay the reduction of NiO, so that CrO can be prepared x a/Ni/NiO composite material.
FIG. 10 is a comparative graph of the UOR polarization curves of the metallic nickel material of comparative example 1 of the present invention and example 1. As can be seen, a voltage of 1.446V is required to reach 200mA/cm 2 Current density of (d); 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 activity of the catalyst UOR generated by the reaction is greatly reduced when no chromium oxide nanosheet substrate exists.
Comparative example 2
(1) Adding 1.0mmol of nickel nitrate and 1.0mmol of potassium chromate into a polytetrafluoroethylene lining, and adding 30mL of deionized water for dissolving;
(2) adding a piece of cleaned 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 carrying out hydrothermal reaction for 8 hours at 140 ℃;
(4) cooling the reaction liquid obtained in the step (3), taking out the foamed nickel, washing the foamed nickel for 2 times by using deionized water and ethanol respectively, and then placing the washed foamed nickel in a 60 ℃ drying oven for drying for 2 hours to obtain a precursor binary nickel chromium oxide NiCrO x ；
(5) Putting the precursor binary nickel chromium oxide obtained in the step (4) into a tube furnace, and putting the precursor binary nickel chromium oxide into the tube furnace in the presence of H 2 Calcining for 3h in/Ar (20/80%) mixed gas at the temperature rise rate of 2 ℃/min and the calcining temperature of 400 ℃, thus obtaining the chromium oxide/nickel oxide material CrO x /NiO。
FIG. 11 is an X-ray diffraction pattern of a chromium oxide/nickel oxide composite material obtained in comparative example 2 of the present invention, in which the presence of metallic Ni was not observed, whereas in comparative example 1, NiO was completely reduced to metallic nickel at a lower temperature of 250 ℃.
FIG. 12 shows CrO obtained in comparative example 2 of the present invention x The transmission electron microscope picture of the/NiO composite material shows that the superfine NiO nano particles are uniformly distributed in the amorphous CrO x In the nanosheets, it was demonstrated that in example 1, example 2 and comparative example 2, amorphous CrO x Good wrapping of NiO is achieved, so that NiO is protected, the temperature of reducing NiO into metal Ni is greatly increased, and the superfine NiO nanoparticles are not reduced into metal Ni at 400 ℃ in the comparative example.
FIG. 13 is a plot comparing the UOR polarization curves of comparative example 2 of the invention with those of example 1. Can be seen from the figureThe catalyst can provide 200mA/cm only by 1.454V voltage 2 And the corresponding current density at high potential is greatly reduced. It is seen that the lack of the conductive metal Ni is due to CrO x The poor conductivity of/NiO leads to a significantly lower UOR catalytic activity than CrO x /Ni/NiO。
Comparative example 3
(1) Adding 1.0mmol of nickel nitrate and 1.0mmol of potassium chromate into a polytetrafluoroethylene lining, and adding 30mL of deionized water for dissolving;
(2) adding a piece of cleaned 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 carrying out hydrothermal reaction for 8 hours at 140 ℃;
(4) cooling the reaction liquid obtained in the step (3), taking out the foamed nickel, washing the foamed nickel for 2 times by using deionized water and ethanol respectively, and then placing the washed foamed nickel in a 60 ℃ drying oven for drying for 2 hours to obtain a precursor binary nickel chromium oxide NiCrO x ；
(5) Putting the precursor binary nickel chromium oxide obtained in the step (4) into a tube furnace, and putting the precursor binary nickel chromium oxide into the tube furnace in the presence of H 2 Calcining for 3h in/Ar (20/80%) mixed gas at the temperature rise rate of 2 ℃/min and the calcining temperature of 600 ℃ to obtain the chromium oxide/nickel composite material CrO x /Ni。
As can be seen from FIG. 14, the chromium oxide/nickel composite CrO prepared in comparative example 3 x The voltage of the/Ni catalyst is 1.444V to provide 200mA/cm 2 The current density of (2). 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 to example 1.
Comparative example 4
(1) Adding 1.0mmol of nickel nitrate, 1.0mmol of chromium nitrate and 2.0mmol of urea into a polytetrafluoroethylene lining, and adding 30mL of deionized water for dissolving;
(2) adding a piece of cleaned 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 carrying out hydrothermal reaction for 8 hours at 140 ℃;
(4) cooling the reaction liquid in the step (3), taking out the foamed nickel, and respectively using deionized water and BWashing with alcohol for 2 times, drying, and calcining in a muffle furnace at 350 ℃ for 2h to obtain a precursor binary nickel-chromium oxide NiCrO x ；
(5) Putting the precursor binary nickel chromium oxide obtained in the step (4) into a tube furnace, and putting the precursor binary nickel chromium oxide into the tube furnace in the presence of H 2 Calcining for 3h in an/Ar (20/80%) mixed gas at the temperature rise rate of 2 ℃/min and the calcining temperature of 450 ℃, thus obtaining the chromium oxide/nickel oxide composite material 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, 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 nanosheet structure prepared in example 1, indicating that the nanosheet structure cannot be obtained when conventional chromium salt is used instead of chromate; in addition, CrO prepared using low-valent chromium salts x Similar to the materials reported in the literature and patents mentioned in the background, CrO x The coating of Ni and NiO cannot be realized at the same time.
FIG. 16 is a comparative plot of the UOR polarization curves of comparative example 4 of the present invention versus example 1. Comparative example 4 required 1.449V to reach 200mA/cm 2 Current densities of comparative example 3 and example 1 at a voltage of 1.4V were able to provide current densities of 70 and 275mA/cm, respectively 2 。
It can be seen that the performance of comparative example 4 is significantly lower than that of example 1, which may be caused by mutual isolation due to too loose of the nanowires, which is not beneficial to the mass transfer process between the nanowires, and the interaction between the conductive substrate and the active species can be better exerted when the nanosheet structure is used as a reaction platform of the chromium oxide/nickel oxide composite material, thereby showing superior UOR performance.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that 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 preparation method of a chromium oxide/metal oxide composite material is characterized by comprising the following steps:
(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) to a hydrothermal reaction kettle, adding a metal carrier into the reaction liquid, and carrying out hydrothermal reaction;
(3) cooling, separating, washing and drying the liquid obtained 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) in a tubular furnace, and calcining in a reducing gas atmosphere at the calcining temperature of 420-550 ℃, thus obtaining the chromium oxide/metal oxide composite material; in the step (1), the molar ratio of the metal salt to the chromate is 0.5-2.0: 1.
2. the method according to 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 (a).
3. The method according to 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 preparation method according to claim 1, wherein the temperature of the hydrothermal reaction in the step (2) is 100-200 ℃ and the time is 6-24 hours.
6. The method according to claim 1, wherein the metal carrier in the step (2) is any one of nickel foam, cobalt foam, or copper foam.
7. The preparation method according to claim 1, wherein the drying temperature in the step (3) is 60-80 ℃ and the drying time is 2-6 h.
8. The preparation method according to claim 1, wherein the setting parameters of the tube furnace in the step (4) are as follows: the heating rate is 2-10 ℃/min, the temperature is raised to 420-550 ℃, and the heat preservation time is 1-5 h.
9. The chromium oxide/metal oxide composite material prepared by the preparation method according to any one of claims 1 to 8, wherein the chromium oxide/metal oxide composite material is a mixed phase of crystalline and amorphous states, the chromium oxide exists in the form of amorphous nanosheets, and the ultrafine metal nanoparticles and the ultrafine metal oxide nanoparticles are embedded in the amorphous chromium oxide nanosheets in the form of crystalline states.
10. Use of the chromium oxide/metal oxide composite material according to claim 9 in the fields of electrocatalysis and organic catalysis.
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| 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 |
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