CN111841543A - Preparation method and application of spinel type oxide catalyst - Google Patents
Preparation method and application of spinel type oxide catalyst Download PDFInfo
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- CN111841543A CN111841543A CN202010796169.8A CN202010796169A CN111841543A CN 111841543 A CN111841543 A CN 111841543A CN 202010796169 A CN202010796169 A CN 202010796169A CN 111841543 A CN111841543 A CN 111841543A
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- spinel
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- oxide catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 50
- 239000011029 spinel Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 100
- 239000000956 alloy Substances 0.000 claims abstract description 100
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- 150000003624 transition metals Chemical class 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 12
- 239000011651 chromium Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 11
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000006722 reduction reaction Methods 0.000 claims abstract description 10
- 238000005266 casting Methods 0.000 claims abstract description 9
- 230000006698 induction Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000002074 melt spinning Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 47
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- -1 carbonic acid compound Chemical class 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims description 3
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims description 3
- 229910019114 CoAl2O4 Inorganic materials 0.000 claims description 2
- 229910018576 CuAl2O4 Inorganic materials 0.000 claims description 2
- 229910003430 FeCr2O4 Inorganic materials 0.000 claims description 2
- 229910003303 NiAl2O4 Inorganic materials 0.000 claims description 2
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims description 2
- 229910003264 NiFe2O4 Inorganic materials 0.000 claims description 2
- 229910005802 NiMn2O4 Inorganic materials 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001676 gahnite Inorganic materials 0.000 claims description 2
- 229910001677 galaxite Inorganic materials 0.000 claims description 2
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 9
- 238000003723 Smelting Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 description 14
- 238000007664 blowing Methods 0.000 description 12
- 229910000838 Al alloy Inorganic materials 0.000 description 11
- QRXDDLFGCDQOTA-UHFFFAOYSA-N cobalt(2+) iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Co+2].[O-2] QRXDDLFGCDQOTA-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000010287 polarization Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- UNRNJMFGIMDYKL-UHFFFAOYSA-N aluminum copper oxygen(2-) Chemical compound [O-2].[Al+3].[Cu+2] UNRNJMFGIMDYKL-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 4
- 238000004832 voltammetry Methods 0.000 description 4
- 229910003321 CoFe Inorganic materials 0.000 description 3
- 229910000604 Ferrochrome Inorganic materials 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 2
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 2
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 2
- ZCUGDIDVQFWDHU-UHFFFAOYSA-I aluminum;copper;pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Cu+2] ZCUGDIDVQFWDHU-UHFFFAOYSA-I 0.000 description 2
- BLMJOHVPLFFDMH-UHFFFAOYSA-I aluminum;zinc;pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Zn+2] BLMJOHVPLFFDMH-UHFFFAOYSA-I 0.000 description 2
- HSQIWKNMXNBSTL-UHFFFAOYSA-J cobalt(2+);iron(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Co+2] HSQIWKNMXNBSTL-UHFFFAOYSA-J 0.000 description 2
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 210000003041 ligament Anatomy 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018565 CuAl Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- QEFDIAQGSDRHQW-UHFFFAOYSA-N [O-2].[Cr+3].[Fe+2] Chemical compound [O-2].[Cr+3].[Fe+2] QEFDIAQGSDRHQW-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZORBNWTXWBGAQH-UHFFFAOYSA-I chromium(3+);iron(2+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Cr+3].[Fe+2] ZORBNWTXWBGAQH-UHFFFAOYSA-I 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004070 electrodeposition 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
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
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- B01J35/33—
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- B01J35/61—
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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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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a spinel type oxide catalyst, which comprises the steps of heating one or two transition metals of cobalt, iron, nickel, manganese, copper, chromium and zinc and aluminum to a molten state by adopting a vacuum induction smelting furnace, cooling to a rod-shaped alloy ingot, melting the alloy ingot by using a vacuum melt spinning device, blow-casting the rod-shaped alloy ingot into a corresponding alloy strip, placing the alloy strip into an alkaline solution for dealloying to obtain a dealloyed product, placing the dealloyed product into a tubular furnace for high-temperature annealing in an air atmosphere to obtain the spinel type oxide catalyst. The invention also relates to application of the electrode material, the obtained catalyst has a multi-metal mixed valence state, can obviously enhance the conductivity of the material, has good electrocatalytic activity on Oxygen Evolution Reaction (OER) and Oxygen Reduction Reaction (ORR) in an alkaline environment, has good stability, and can be used as a cathode catalyst of a chargeable and dischargeable metal-air battery.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method and application of a spinel type oxide catalyst.
Background
At present, excessive exploitation and use of traditional fossil fuels are the main causes of environmental pollution and energy shortage worldwide, and it is seen that the development of renewable green new energy is the most urgent need of the society today. In recent years, a chargeable and dischargeable metal-air battery is considered to be one of the most promising energy storage and conversion devices due to the advantages of high energy density, low cost, no pollution, and the like, but the Oxygen Evolution Reaction (OER) and the Oxygen Reduction Reaction (ORR) generated at the cathode significantly affect the charge and discharge rate, the energy efficiency, and the cycle life of the battery due to slow kinetics. Currently, the best OER and ORR electrocatalysts are primarily IrO2/RuO2And noble metal Pt-based materials, but the cost is high, the storage capacity is low, the stability is poor, and the large-scale application of the catalyst is hindered.
Researches show that the spinel oxide is a catalyst material with low cost, oxidation resistance and environmental protection, is very stable under alkaline or oxidation conditions, is usually prepared by a traditional solid-phase sintering method, generally needs higher heating temperature and longer reaction time, consumes energy and time, and has large product particle size, small specific surface area and low electrochemical activity.
Therefore, it is highly desirable to provide a mild preparation method for flexibly regulating and controlling the active phase composition and the microstructure of the spinel-type oxide, so as to obtain an inexpensive, efficient and durable OER/ORR bifunctional catalyst, which is a difficult problem that must be overcome to realize commercialization of a chargeable and dischargeable metal-air battery.
Disclosure of Invention
In view of the above, the first objective of the present invention is to provide a preparation method of a spinel-type oxide catalyst, which can flexibly control the composition and microstructure of an active phase of the spinel-type oxide by using a mild preparation method, so as to obtain an inexpensive, efficient and durable OER/ORR dual-function catalyst.
A second object of the present invention is to provide a spinel-type oxide catalyst obtained by the above-mentioned preparation method.
The third object of the present invention is to provide an application of the spinel-type oxide catalyst obtained by the above preparation method
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a spinel oxide catalyst, comprising the steps of:
(1) putting one or two transition metals of cobalt, iron, nickel, manganese, copper, chromium and zinc and aluminum into a quartz tube in a vacuum induction melting furnace together, heating to a molten state to obtain an alloy liquid, and directly cooling the alloy liquid in an inert atmosphere to form a rod-shaped alloy ingot; or the obtained alloy liquid is flushed into a graphite crucible to form a rod-shaped alloy ingot, then the alloy ingot is melted by adopting a vacuum melt-spinning device to obtain the alloy liquid again, the alloy liquid is blown onto a copper roller rotating at a high speed by utilizing the air pressure difference, the cooling speed is controlled by adjusting the rotating speed of the copper roller, and an alloy strip can be formed after the alloy liquid is rapidly cooled;
(2) the alloy strip is placed in alkaline solution for dealloying treatment, and because the proportion of aluminum element in the initial alloy strip is large, when dealloying treatment is carried out in the alkaline solution, most of components are dissolved and corroded, so that the alloy strip cannot realize self-supporting, and the alloy strip is washed by ultrapure water for multiple times and then dried to obtain a powdery dealloying product;
(3) and placing the dealloying product in a tubular annealing furnace, heating the tubular annealing furnace to 300-1100 ℃ in the air atmosphere, preserving the heat for 0.5-24 h, and cooling to room temperature to obtain the spinel type oxide catalyst.
The beneficial effects of the above technical scheme are: one or two of transition metals of cobalt, iron, nickel, manganese, copper, chromium and zinc and aluminum are smelted together to prepare a master alloy, the source of raw materials is wide, the components are adjustable, the price is low, and the production cost can be greatly reduced; according to the invention, the smelting furnace is adopted for alloying treatment, the reaction time is only dozens of seconds to several minutes, the energy consumption is obviously reduced, and simultaneously the formed alloy phase is uniformly distributed, so that a uniform porous structure is formed in the subsequent dealloying treatment; the spinel type oxide precursor is prepared by adopting a mild dealloying method, so that energy and time are saved, and the composition and microstructure of an active phase can be flexibly regulated and controlled according to the components of a master alloy, the concentration of a corrosive liquid and the dealloying time; the high-temperature annealing treatment can not only keep the original micro/nano structure, but also improve the crystallinity and stability of the material; the spinel oxide is usually synthesized by a hydrothermal method, a sol-gel method, an electrodeposition method, a coprecipitation method and the like, but the process cost is high, the synthesis speed is low, and the large-scale production is difficult.
Preferably, in the preparation method of the spinel-type oxide catalyst, the atomic percentage of aluminum in the alloy strip in the step (1) is 60 to 95%.
The beneficial effects of the above technical scheme are: the aluminum element in the alloy strip has a large proportion, and the aim is to facilitate the dissolution of aluminum in the subsequent dealloying process.
Preferably, in the above method for preparing a spinel oxide catalyst, if the alloy strip element in step (1) is a transition metal selected from cobalt, iron, nickel, manganese, copper, chromium and zinc and aluminum, the atomic percentage of aluminum in the formed alloy strip is controlled, and the spinel oxide having a general formula a is obtained3O4Or AAl2O4E.g. Co3O4、Fe3O4、Mn3O4Or NiAl2O4、CoAl2O4、MnAl2O4、CuAl2O4、ZnAl2O4Etc., wherein Al is not only a dealloying component, but also a constituent element of the spinel-type oxide; if the alloy strip elements consist of two transition metals of cobalt, iron, nickel, manganese, copper and chromium and aluminum, the atomic ratio of the two transition metals must be controlled to be 1:2, otherwise, spinel-type oxides cannot be formed, and the general formula of the obtained spinel-type oxides is AB2O4E.g. CoFe2O4、NiCo2O4、NiFe2O4、NiMn2O4、FeCr2O4Etc.; if the alloy strip element is composed of one transition metal of cobalt, iron, nickel, manganese, copper and chromium, and zinc and aluminum, zinc is easily evaporated in the smelting process due to low boiling point, which is not favorable for forming spinel type oxide.
The beneficial effects of the above technical scheme are: any one or two of transition metals of cobalt, iron, nickel, manganese, copper, chromium and zinc and aluminum are smelted together to form binary or ternary initial alloy, no noble metal is used, and the preparation cost is reduced.
Preferably, in the preparation method of the spinel type oxide catalyst, the rotation speed of a copper roller of the vacuum melt-spinning device in the step (1) is 1000-5000 r/min.
The beneficial effects of the above technical scheme are: is beneficial to the rapid cooling of the alloy liquid and forms alloy strips with evenly distributed phases.
Preferably, in the preparation method of the spinel-type oxide catalyst, the width of the alloy strip in the step (1) is 1-10 mm, and the thickness is 10-100 μm.
The beneficial effects of the above technical scheme are: is beneficial to the rapid dissolution of aluminum in the process of dealloying and shortens the time of dealloying treatment.
Preferably, in the above preparation method of a spinel-type oxide catalyst, the molar concentration of the alkaline solution in step (2) is 1 to 10mol/L, and the alkaline solution is any one of sodium hydroxide or potassium hydroxide.
The beneficial effects of the above technical scheme are: the aluminum is amphoteric metal, can be selectively dissolved in alkaline solution to form porous transition metal material, and in alkaline solution with different molar concentration, the dissolution rate of the aluminum is different, and the pore diameter or ligament size of the formed porous transition metal material is also different.
Preferably, in the preparation method of the spinel type oxide catalyst, the dealloying time in the step (2) is 1-72 hours, and the dealloying product is one or more of transition metal hydroxide, oxyhydroxide and carbonic acid compound.
The beneficial effects of the above technical scheme are: under different dealloying treatment time, the dissolution amount of aluminum is different, the pore diameter, ligament size and phase composition of the formed porous transition metal material are different, the solution can provide hydroxide ions when dealloying reaction is carried out in alkaline solution, free oxygen ions and carbonate ions in air can spontaneously form one or more of transition metal hydroxide, oxyhydroxide and carbonic acid compounds with the transition metal.
Preferably, in the preparation method of the spinel type oxide catalyst, the drying in the step (2) is drying in a vacuum drying oven at a temperature of 50-90 ℃ for 1-24 hours.
Preferably, in the preparation method of the spinel oxide catalyst, in the step (3), the temperature rise rate is 1-10 ℃/min, and the temperature drop rate is 1-5 ℃/min.
The beneficial effects of the above technical scheme are: in thatDuring the high-temperature annealing process, hydroxyl ions, oxygen ions, carbonate ions and the like in the dealloying product can be changed into H2O or CO2Form of the transition metal oxide, thereby improving the crystallinity and stability of the material.
A spinel oxide catalyst obtainable by any of the above-mentioned preparation methods.
The beneficial effects of the above technical scheme are: the spinel oxide presents a micro/nano scale structure, can greatly increase the reaction contact area of the electrode material and improve the utilization rate of the catalyst.
The spinel oxide is used as a working electrode, a platinum wire is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode, and an electrocatalytic oxygen evolution reaction and an oxygen reduction reaction test are carried out through a three-electrode system.
The beneficial effects of the above technical scheme are: the spinel oxide has a multi-metal mixed valence state, can promote electron transition, remarkably improve the conductivity of the material, has good electrocatalytic activity on both OER and ORR, and can become a dual-function catalyst.
In summary, the beneficial effects of the invention at least include:
1. the invention prepares the master alloy by smelting one or two of transition metals of cobalt, iron, nickel, manganese, copper, chromium and zinc and aluminum together, and has the advantages of wide raw material source, adjustable components, low price and capability of greatly reducing the production cost.
The invention adopts the smelting furnace to carry out alloy treatment, the reaction time is only dozens of seconds to several minutes, the energy consumption is obviously reduced, simultaneously the formed alloy phase is uniformly distributed, and the invention is beneficial to the subsequent dealloying treatment to form a uniform porous structure
3. The spinel type oxide precursor is prepared by adopting a mild dealloying method, so that the energy and the time are saved, the composition and the microstructure of an active phase can be flexibly regulated and controlled according to the components of a master alloy, the concentration of a corrosive liquid and the dealloying time, more active interfaces and sites are derived from the surface, and the industrial application can be realized.
4. The high-temperature annealing treatment involved in the invention not only can keep the original micro/nano structure, but also can improve the crystallinity and stability of the material.
5. The spinel oxide prepared by the invention has a micro/nano scale structure, can greatly increase the reaction contact area of electrode materials, and improves the utilization rate of the catalyst.
6. The spinel oxide has a multi-metal mixed valence state, can promote electron transition, remarkably improves the conductivity of the material, and shows good electrocatalytic activity on both OER and ORR.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a spinel-type cobalt iron oxide catalyst prepared in example 1;
FIG. 2 is an X-ray diffraction (XRD) pattern of the spinel-type cobalt iron oxide catalyst prepared in example 1;
FIG. 3 is a graph showing the polarization of electrocatalytic oxygen evolution of the spinel-type cobalt iron oxide catalyst prepared in example 1 in 0.1mol/L potassium hydroxide solution;
FIG. 4 is a graph showing the stability of the spinel-type cobalt iron oxide catalyst prepared in example 1 in the presence of 0.1mol/L KOH solution in terms of electrocatalytic oxygen evolution;
FIG. 5 is a graph showing the electrocatalytic oxygen reduction polarization of the spinel-type cobalt iron oxide catalyst prepared in example 1 in 0.1mol/L potassium hydroxide solution;
FIG. 6 is a graph showing the electrocatalytic oxygen reduction stability of the spinel-type cobalt iron oxide catalyst prepared in example 1 in 0.1mol/L KOH solution;
FIG. 7 is a graph showing the polarization of electrocatalytic oxygen evolution of the spinel-type manganese oxide catalyst prepared in example 2 in a 0.1mol/L potassium hydroxide solution;
FIG. 8 is a graph showing the electrocatalytic oxygen reduction polarization of the spinel-type manganese oxide catalyst prepared in example 2 in 0.1mol/L KOH solution;
FIG. 9 is a graph showing the polarization of electrocatalytic oxygen evolution of the spinel nickel cobalt oxide catalyst prepared in example 3 in 0.1mol/L KOH solution;
FIG. 10 is a graph of the electrocatalytic oxygen reduction polarization of the spinel nickel cobalt oxide catalyst prepared in example 3 in 0.1mol/L potassium hydroxide solution;
FIG. 11 is a graph showing the polarization of electrocatalytic oxygen evolution of the spinel copper aluminum oxide catalyst prepared in example 4 in 0.1mol/L potassium hydroxide solution;
FIG. 12 is a graph showing the electrocatalytic oxygen reduction polarization of the spinel copper aluminum oxide catalyst prepared in example 4 in 0.1mol/L potassium hydroxide solution.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a preparation method of a spinel type oxide catalyst and application of the material.
Example 1
A preparation method of a spinel type cobalt iron oxide catalyst comprises the following steps:
step one, heating cobalt, iron and aluminum (the atomic ratio is 5:10:85) to a molten state together by using a vacuum induction melting furnace to obtain an alloy liquid, directly cooling the alloy liquid in an argon atmosphere to form a rod-shaped alloy ingot, then melting the alloy ingot by using a vacuum belt-throwing device to obtain the alloy liquid again, blowing the alloy liquid onto a copper roller with the rotating speed of 1500r/min by using air pressure difference, and blowing and casting the alloy liquid to form an alloy strip with the width of 2mm and the thickness of 50 mu m after the alloy liquid is rapidly cooled;
secondly, placing the cobalt-iron-aluminum alloy strip obtained in the first step into a sodium hydroxide solution with the molar concentration of 2mol/L for dealloying, wherein the reaction time is 36h, and drying the cobalt-iron-aluminum alloy strip after washing the cobalt-iron-aluminum alloy strip with ultrapure water for multiple times to obtain a cobalt-iron hydroxide powder sample;
step three, placing the cobalt-iron hydroxide obtained in the step two into a tubular annealing furnace, heating the tubular furnace to 300 ℃ at the heating rate of 5 ℃/min in the air atmosphere, preserving the heat for 1h, and cooling the tubular furnace to room temperature at the cooling rate of 3 ℃/min to obtain the spinel type cobalt-iron oxide (CoFe)2O4) A catalyst.
Through SEM observation, the spinel type cobalt iron oxide presents a rod-shaped structure, and ultrathin nanosheets grow on the surface, and the structure provides more active sites, so that CoFe is generated2O4The whole body shows excellent oxygen precipitation and oxygen reduction catalytic performance (see figure 1); XRD analysis shows that the phase generated on the surface of the electrode is combined with CoFe2O4Corresponds to the standard diffraction peak of (1), indicating that CoFe is obtained2O4Spinel type oxides (see fig. 2); the electrode is used as a working electrode, a platinum wire is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode, and electrochemical voltammetry scanning is carried out to find that the electrode shows excellent electrocatalytic OER activity (at 10 mA/cm) in 0.1mol/L potassium hydroxide solution2The required potential at current density was 1.55V, see FIG. 3) and stability (at 10mA/cm2After constant current scanning is carried out for 40h under the current density, the potential is not obviously increased, and the potential is shown in figure 4); the electrode shows excellent electrocatalytic ORR activity (half-wave potential of 0.84V, see figure 5) and stability (current density attenuation is not obvious after constant potential scanning for 40h at 0.8V, see figure 6) in 0.1mol/L potassium hydroxide solution.
Example 2
A preparation method of a spinel-type manganese oxide catalyst comprises the following steps:
step one, heating manganese and aluminum (with an atomic ratio of 10:90) to a molten state together by using a vacuum induction melting furnace to obtain an alloy liquid, directly cooling the alloy liquid in an argon atmosphere to form a rod-shaped alloy ingot, then melting the alloy ingot by using a vacuum strip throwing device to obtain the alloy liquid again, blowing the alloy liquid onto a copper roller with the rotating speed of 1000r/min by using air pressure difference, and blowing and casting the alloy liquid to form an alloy strip with the width of 3mm and the thickness of 30 mu m after the alloy liquid is rapidly cooled;
step two, placing the manganese-aluminum alloy strip obtained in the step one in a potassium hydroxide solution with the molar concentration of 6mol/L for dealloying treatment, wherein the reaction time is 12 hours, and drying the manganese-aluminum alloy strip after being washed by ultrapure water for multiple times to obtain a manganese hydroxide or carbonic acid compound powder sample;
step three, putting the manganese hydroxide or carbonic acid compound obtained in the step two into a tubular annealing furnace, heating the tubular furnace to 600 ℃ at the heating rate of 10 ℃/min in the air atmosphere, preserving the heat for 2 hours, and cooling the tubular furnace to room temperature at the cooling rate of 5 ℃/min to obtain the spinel manganese oxide (Mn)3O4) A catalyst.
The electrode is used as a working electrode, a platinum wire is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode, and electrochemical voltammetry scanning is carried out to find that the electrode shows excellent electrocatalytic OER activity (at 10 mA/cm) in 0.1mol/L potassium hydroxide solution2The required potential at current density was 1.6V, see fig. 7) and ORR activity (half-wave potential 0.79V, see fig. 8).
Example 3
A preparation method of a spinel nickel-cobalt oxide catalyst comprises the following steps:
step one, heating nickel, cobalt and aluminum (the atomic ratio is 10:20:70) to a molten state together by using a vacuum induction melting furnace to obtain an alloy liquid, directly cooling the alloy liquid in an argon atmosphere to form a rod-shaped alloy ingot, then melting the alloy ingot by using a vacuum belt-throwing device to obtain the alloy liquid again, blowing the alloy liquid onto a copper roller with the rotating speed of 2000r/min by using air pressure difference, and blowing and casting the alloy liquid to form an alloy strip with the width of 3mm and the thickness of 60 mu m after the alloy liquid is rapidly cooled;
secondly, placing the nickel-cobalt-aluminum alloy strip obtained in the first step into a sodium hydroxide solution with the molar concentration of 4mol/L for dealloying treatment, wherein the reaction time is 24 hours, and drying the nickel-cobalt-aluminum alloy strip after being washed by ultrapure water for multiple times to obtain a nickel-cobalt hydroxide or oxyhydroxide powder sample;
step three, placing the nickel cobalt hydroxide or oxyhydroxide obtained in the step two into a tube annealing furnace, heating the tube furnace to 500 ℃ at the heating rate of 8 ℃/min in the air atmosphere, preserving the heat for 2 hours, and cooling the tube furnace to room temperature at the cooling rate of 5 ℃/min to obtain the spinel nickel cobalt oxide (NiCo)2O4) A catalyst.
The electrode is used as a working electrode, a platinum wire is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode, and electrochemical voltammetry scanning is carried out to find that the electrode shows excellent electrocatalytic OER activity (at 10 mA/cm) in 0.1mol/L potassium hydroxide solution2The required potential at current density was 1.63V, see fig. 9) and ORR activity (half-wave potential 0.82V, see fig. 10).
Example 4
A preparation method of a spinel type copper-aluminum oxide catalyst comprises the following steps:
step one, heating copper and aluminum (the atomic ratio is 5:95) to a molten state by adopting a vacuum induction smelting furnace to obtain an alloy liquid, directly cooling the alloy liquid in an argon atmosphere to form a rod-shaped alloy ingot, then melting the alloy ingot by adopting a vacuum strip throwing device to obtain the alloy liquid again, blowing the alloy liquid onto a copper roller with the rotating speed of 2500r/min by utilizing the air pressure difference, and blowing and casting the alloy liquid to form an alloy strip with the width of 5mm and the thickness of 40 mu m after the alloy liquid is rapidly cooled;
secondly, placing the copper-aluminum alloy strip obtained in the first step into a potassium hydroxide solution with the molar concentration of 8mol/L for dealloying treatment, wherein the reaction time is 10 hours, and drying the copper-aluminum alloy strip after being washed by ultrapure water for multiple times to obtain a copper-aluminum hydroxide or oxyhydroxide powder sample;
step three, placing the copper-aluminum hydroxide or oxyhydroxide obtained in the step two into a tube annealing furnace, and heating the tube annealing furnace in an air atmosphereRaising the temperature to 600 ℃ at the speed of 6 ℃/min, preserving the heat for 1.5h, and preparing the spinel copper-aluminum oxide (CuAl) when the temperature of the tube furnace is reduced to room temperature at the rate of 4 ℃/min2O4) A catalyst.
The electrode is used as a working electrode, a platinum wire is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode, and electrochemical voltammetry scanning is carried out to find that the electrode shows excellent electrocatalytic OER activity (at 10 mA/cm) in 0.1mol/L potassium hydroxide solution2The required potential at current density was 1.61V, see FIG. 11) and ORR activity (half-wave potential 0.72V, see FIG. 12).
Example 5
A preparation method of a spinel type iron-chromium oxide catalyst comprises the following steps:
step one, heating iron, chromium and aluminum (the atomic ratio is 2:4:94) to a molten state together by using a vacuum induction melting furnace to obtain an alloy liquid, directly cooling the alloy liquid in an argon atmosphere to form a rod-shaped alloy ingot, then melting the alloy ingot by using a vacuum strip casting device to obtain the alloy liquid again, blowing the alloy liquid onto a copper roller with the rotation speed of 1200r/min by using air pressure difference, and blowing and casting the alloy liquid to form an alloy strip with the width of 2mm and the thickness of 60 mu m after the alloy liquid is rapidly cooled;
step two, placing the iron-chromium-aluminum alloy strip obtained in the step one in a potassium hydroxide solution with the molar concentration of 10mol/L for dealloying treatment, wherein the reaction time is 12 hours, and drying the iron-chromium-aluminum alloy strip after being washed by ultrapure water for multiple times to obtain an iron-chromium hydroxide oxide or carbonic acid compound powder sample;
step three, placing the ferrochrome oxyhydroxide or carbonic acid compound obtained in the step two into a tubular annealing furnace, heating the tubular furnace to 700 ℃ at the heating rate of 7 ℃/min in the air atmosphere, preserving the heat for 1h, and cooling the tubular furnace to room temperature at the cooling rate of 5 ℃/min to obtain the spinel type ferrochrome oxide (FeCr)2O4) A catalyst.
Example 6
A preparation method of a spinel type zinc-aluminum oxide catalyst comprises the following steps:
step one, heating zinc and aluminum (the atomic ratio is 20:80) to a molten state together by using a vacuum induction melting furnace to obtain an alloy liquid, directly cooling the alloy liquid in an argon atmosphere to form a rod-shaped alloy ingot, then melting the alloy ingot by using a vacuum strip throwing device to obtain the alloy liquid again, blowing the alloy liquid onto a copper roller with the rotating speed of 3000r/min by using air pressure difference, and blowing and casting the alloy liquid to form an alloy strip with the width of 6mm and the thickness of 20 mu m after the alloy liquid is rapidly cooled;
secondly, the zinc-aluminum alloy strip obtained in the first step is placed in a potassium hydroxide solution with the molar concentration of 6mol/L for dealloying treatment, the reaction time is 24 hours, and the zinc-aluminum alloy strip is washed by ultrapure water for multiple times and then dried to obtain a zinc-aluminum hydroxide or oxyhydroxide powder sample;
step three, placing the zinc-aluminum hydroxide or oxyhydroxide obtained in the step two into a tube-type annealing furnace, heating the tube-type annealing furnace to 400 ℃ at the heating rate of 8 ℃/min in the air atmosphere, preserving the heat for 1h, and cooling the tube-type annealing furnace to room temperature at the cooling rate of 4 ℃/min to obtain the spinel-type zinc-aluminum oxide (ZnAl)2O4) A catalyst.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the scheme disclosed by the embodiment, the scheme corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing a spinel oxide catalyst, comprising the steps of:
(1) putting one or two transition metals of cobalt, iron, nickel, manganese, copper, chromium and zinc and aluminum into a vacuum induction melting furnace together, heating to a molten state to obtain an alloy liquid, cooling the alloy liquid in an inert atmosphere to form a rod-shaped alloy ingot, then melting the alloy ingot by using a vacuum melt-spinning device, and performing blow casting to form an alloy strip;
(2) placing the alloy strip in an alkaline solution for dealloying, washing with ultrapure water for multiple times, and drying to obtain a dealloying product;
(3) and placing the dealloying product in a tubular annealing furnace, heating the tubular annealing furnace to 300-1100 ℃ in the air atmosphere, preserving the heat for 0.5-24 h, and cooling to room temperature to obtain the spinel type oxide catalyst.
2. The method of claim 1, wherein the aluminum atom percentage of the alloy strip in step (1) is 60-95%.
3. The method of claim 1, wherein when the alloy strip element in step (1) is a transition metal selected from the group consisting of cobalt, iron, nickel, manganese, copper, chromium, and zinc, and aluminum, the spinel oxide has a general formula A3O4Or AAl2O4(ii) a When the alloy strip elements consist of two transition metals of cobalt, iron, nickel, manganese, copper and chromium and aluminum, the atomic ratio of the two transition metals is 1:2, and the general formula of the obtained spinel-type oxide is AB2O4。
4. The method of claim 3, wherein the spinel oxide comprises Co3O4、Fe3O4、Mn3O4、NiAl2O4、CoAl2O4、MnAl2O4、CuAl2O4、ZnAl2O4、CoFe2O4、NiCo2O4、NiFe2O4、NiMn2O4、FeCr2O4。
5. The method of claim 1, wherein the alloy strip in step (1) has a width of 1-10 mm and a thickness of 10-100 μm.
6. The method of claim 1, wherein the molar concentration of the alkaline solution in step (2) is 1-10 mol/L, and the alkaline solution is one of sodium hydroxide and potassium hydroxide.
7. The preparation method of the spinel oxide catalyst according to claim 1, wherein the dealloying time in the step (2) is 1-72 hours, and the dealloying product is one or more of transition metal hydroxide, oxyhydroxide and carbonic acid compound.
8. The method for preparing a spinel oxide catalyst according to claim 1, wherein the temperature rise rate in step (3) is 1-10 ℃/min, and the temperature drop rate is 1-5 ℃/min.
9. A spinel oxide catalyst prepared by the method of any one of claims 1 to 8.
10. The application of the spinel oxide catalyst prepared by the method of any one of claims 1 to 8 is characterized in that the spinel oxide is used as a working electrode, a platinum wire is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode, and an electrocatalytic oxygen evolution reaction and an oxygen reduction reaction test are carried out by a three-electrode system.
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