CN114232028A - Preparation method of cobalt-based multilayer hollow heterojunction water electrolysis catalyst - Google Patents
Preparation method of cobalt-based multilayer hollow heterojunction water electrolysis catalyst Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 44
- 239000010941 cobalt Substances 0.000 title claims abstract description 44
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002077 nanosphere Substances 0.000 claims abstract description 20
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000011669 selenium Substances 0.000 claims abstract description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 229910052711 selenium Inorganic materials 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 2
- 239000011787 zinc oxide Substances 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a cobalt-based multilayer hollow heterojunction water electrolysis catalyst, which specifically comprises the following steps: (1) dissolving cobalt nitrate hexahydrate and acetylacetone in deionized water, then adding hydrazine hydrate to perform low-temperature hydrothermal reaction, drying, and performing heat treatment in air atmosphere to obtain multilayer hollow cobaltosic oxide nanospheres; (2) dispersing the multilayer hollow cobaltosic oxide nanospheres and sodium sulfide in deionized water for low-temperature hydrothermal reaction, drying, and then carrying out heat treatment in argon atmosphere to obtain multilayer hollow CoO/Co9S8(ii) a (3) Mixing multi-layer hollow CoO/Co9S8And further heat treating the selenium powder to obtain the selenium-enriched zinc oxide. The cobalt-based multilayer hollow composite structure is prepared by combining solvothermal reaction and heat treatment, and each layer of shell of the hollow structure is a mirror symmetry heterojunction structure; the prepared catalyst has rich catalytic reaction sites and optimized surface electricityThe substructure can effectively improve the oxygen evolution reaction efficiency of the catalyst.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a preparation method of a cobalt-based multilayer hollow heterojunction water electrolysis catalyst.
Background
With the progress of society and the development of human beings, the energy crisis and environmental problems caused by the traditional fossil energy pose a threat to the sustainable development of human beings. Hydrogen is considered to be a promising energy carrier due to the advantages of higher energy density, green cleanness and the like.
Currently, thermochemical reforming from traditional fossil resources remains the primary route for hydrogen production, but this process also produces large quantities of carbon dioxide. In contrast, the hydrogen production by electrolyzing water through renewable power can not only solve the problems of intermittency and regionality of new energy, but also is expected to realize distributed hydrogen production in the future. The water electrolysis reaction comprises a cathodic hydrogen evolution reaction and an anodic oxygen evolution reaction, and compared with a two-electron transfer hydrogen evolution reaction, the four-electron oxygen evolution reaction has slow kinetics and seriously restricts the water electrolysis efficiency. Therefore, the development of an efficient oxygen evolution catalyst has important significance for the large-scale application of the electrolyzed water in the future.
At present, iridium dioxide, ruthenium dioxide and other noble metal-based oxides are accepted as high-efficiency oxygen evolution catalysts, but the high cost and the low storage capacity greatly restrict the development of electrolyzed water. Based on this, it is the key point to design and prepare the oxygen evolution catalyst which is cheap, efficient and stable.
Transition metal-based catalysts are of great interest for their abundant and good electrocatalytic properties, however their properties still do not meet the requirements of practical applications. Constructing a multi-component heterojunction structure to achieve electronic reconstruction of the catalyst surface is considered to be one of effective ways to improve the catalytic performance.
However, the preparation of transition metal-based heterojunction electrocatalysts with high specific surface area still faces certain challenges.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a cobalt-based multilayer hollow heterojunction electrolytic water catalyst, so as to solve the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a cobalt-based multilayer hollow heterojunction water electrolysis catalyst comprises the following steps:
(1) dissolving cobalt nitrate hexahydrate and acetylacetone in deionized water, then adding hydrazine hydrate to perform low-temperature hydrothermal reaction, drying, and performing heat treatment in air atmosphere to obtain multilayer hollow cobaltosic oxide nanospheres;
(2) dispersing the multilayer hollow cobaltosic oxide nanospheres and sodium sulfide in deionized water for low-temperature hydrothermal reaction, drying, and then carrying out heat treatment in argon atmosphere to obtain multilayer hollow CoO/Co9S8;
(3) Mixing multi-layer hollow CoO/Co9S8And further carrying out heat treatment on the cobalt-based multilayer hollow heterojunction electrolytic water catalyst and selenium powder to obtain the cobalt-based multilayer hollow heterojunction electrolytic water catalyst.
Further, in the step (1), the mass ratio of the cobalt nitrate hexahydrate, the acetylacetone, the hydrazine hydrate and the deionized water is 14.55:0.049:0.05: 1; the temperature of the low-temperature hydrothermal reaction is 80 ℃, and the time is 1-24 h; the heating rate of the heat treatment is 1 ℃/min, the temperature is 450 ℃, and the time is 1-7 h.
The technical scheme has the beneficial effects that the cobalt-based complex is formed under the condition of low-temperature hydrothermal reaction, and the multilayer hollow cobaltosic oxide nanospheres are formed through further air heat treatment.
Further, in the step (2), the mass ratio of the multilayer hollow cobaltosic oxide nanospheres to the sodium sulfide to the deionized water is 0.144:0.23: 50; the temperature of the low-temperature hydrothermal reaction is 90 ℃ and the time is 30-40 h; the temperature of the heat treatment is 400 ℃ and the time is 1 h.
The technical scheme has the advantages that the cobaltosic oxide is partially vulcanized after low-temperature hydrothermal treatment and is further subjected to heat treatment to finally form the multilayer hollow CoO/Co9S8And (5) structure.
Further, in the step (3), the multilayer hollow CoO/Co9S8The mass ratio of the selenium powder to the selenium powder is 1: 1; the heating rate of the heat treatment is 2 ℃/min, the temperature is 400 ℃, and the time is 1 h; the cobalt-based multilayer hollow heterojunction water electrolysis catalyst is of a multilayer hollow nanosphere structure; the composition of each layer of heterojunction is sequentially CoO/Co from the center to the outer9S8/Co9Se8(ii) a Each layer is of a hollow structureAnd the components are in mirror symmetry.
The beneficial effect of adopting the further technical scheme is that the multilayer hollow CoO/Co9S8After heat treatment, the surface of each layer of structure is partially selenized to finally form the multilayer hollow CoO/Co9S8/Co9Se8And (5) structure.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the cobalt-based multilayer hollow composite structure is prepared by combining solvothermal reaction and heat treatment, and each layer of shell of the hollow structure is a mirror symmetry heterojunction structure; the prepared catalyst has abundant catalytic reaction sites and an optimized surface electronic structure, and can effectively improve the oxygen evolution reaction efficiency of the catalyst.
2. IrO which is expensive compared to commercialization2The electrode material adopts the cobalt-based multilayer hollow heterojunction electrolytic water catalyst as the anode catalyst for electrolyzing water, effectively improves the reaction activity while reducing the cost, is easy to operate, and is expected to be used for large-scale production.
Drawings
FIG. 1 is a transmission electron microscope image of a cobalt-based multilayer hollow heterojunction electrolytic water catalyst prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope photograph of the outermost layer of a cobalt-based multilayer hollow heterojunction electrolytic water catalyst prepared in example 1 of the present invention at a higher magnification;
FIG. 3 is a high resolution transmission electron microscope image of the outermost layer of a cobalt-based multilayer hollow heterojunction electrolytic water catalyst prepared in example 1 of the present invention;
FIG. 4 is an elemental mapping chart of a cobalt-based multilayer hollow heterojunction electrolytic water catalyst prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are 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.
Example 1
The preparation method of the cobalt-based multilayer hollow heterojunction water electrolysis catalyst specifically comprises the following steps:
(1) dissolving 14.55g of cobalt nitrate hexahydrate and 0.049g of acetylacetone in 1mL of deionized water, then adding 0.05g of hydrazine hydrate, carrying out low-temperature hydrothermal reaction for 12h at 80 ℃, drying, and then heating to 450 ℃ at a heating rate of 1 ℃/min in an air atmosphere for heat treatment for 4h to obtain multilayer hollow cobaltosic oxide nanospheres;
(2) dispersing 0.144g of multilayer hollow cobaltosic oxide nanosphere and 0.23g of sodium sulfide in 50mL of deionized water, carrying out low-temperature hydrothermal reaction for 35h at 90 ℃, drying, heating to 400 ℃ in argon atmosphere, and carrying out heat treatment for 1h to obtain multilayer hollow CoO/Co9S8;
(3) 1g of multilayer hollow CoO/Co9S8And 1g of selenium powder is heated to 400 ℃ at the heating rate of 2 ℃/min for heat treatment for 1h (wherein the selenium powder is at the upstream of the airflow direction, and the multilayer hollow CoO/Co is9S8Downstream), obtaining the cobalt-based multilayer hollow heterojunction electrolytic water catalyst;
the catalyst is of a multilayer hollow nanosphere structure; the composition of each layer of heterojunction is sequentially CoO/Co from the center to the outer9S8/Co9Se8(ii) a Each layer is of a hollow structure, and the components are in mirror symmetry.
Example 2
The preparation method of the cobalt-based multilayer hollow heterojunction water electrolysis catalyst specifically comprises the following steps:
(1) dissolving 14.55g of cobalt nitrate hexahydrate and 0.049g of acetylacetone in 1mL of deionized water, then adding 0.05g of hydrazine hydrate, carrying out low-temperature hydrothermal reaction for 1h at 80 ℃, drying, and then heating to 450 ℃ at a heating rate of 1 ℃/min in an air atmosphere for heat treatment for 1h to obtain multilayer hollow cobaltosic oxide nanospheres;
(2) 0.144g of multi-layer hollow cobaltosic oxide nanosphere and 0.23g of sodium sulfide are dispersed in 50mL of deionized water and are cooled at 90 DEG CCarrying out a warm water-heat reaction for 30h, drying, heating to 400 ℃ in an argon atmosphere, and carrying out heat treatment for 1h to obtain the multilayer hollow CoO/Co9S8;
(3) 1g of multilayer hollow CoO/Co9S8And 1g of selenium powder is heated to 400 ℃ at the heating rate of 2 ℃/min for heat treatment for 1h (wherein the selenium powder is at the upstream of the airflow direction, and the multilayer hollow CoO/Co is9S8Downstream), obtaining the cobalt-based multilayer hollow heterojunction electrolytic water catalyst;
the catalyst is of a multilayer hollow nanosphere structure; the composition of each layer of heterojunction is sequentially CoO/Co from the center to the outer9S8/Co9Se8(ii) a Each layer is of a hollow structure, and the components are in mirror symmetry.
Example 3
The preparation method of the cobalt-based multilayer hollow heterojunction water electrolysis catalyst specifically comprises the following steps:
(1) dissolving 14.55g of cobalt nitrate hexahydrate and 0.049g of acetylacetone in 1mL of deionized water, then adding 0.05g of hydrazine hydrate, carrying out low-temperature hydrothermal reaction for 24h at 80 ℃, drying, and then heating to 450 ℃ at a heating rate of 1 ℃/min in an air atmosphere for heat treatment for 7h to obtain multilayer hollow cobaltosic oxide nanospheres;
(2) dispersing 0.144g of multilayer hollow cobaltosic oxide nanosphere and 0.23g of sodium sulfide in 50mL of deionized water, carrying out low-temperature hydrothermal reaction for 40h at 90 ℃, drying, heating to 400 ℃ in argon atmosphere, and carrying out heat treatment for 1h to obtain multilayer hollow CoO/Co9S8;
(3) 1g of multilayer hollow CoO/Co9S8And 1g of selenium powder is heated to 400 ℃ at the heating rate of 2 ℃/min for heat treatment for 1h (wherein the selenium powder is at the upstream of the airflow direction, and the multilayer hollow CoO/Co is9S8Downstream), obtaining the cobalt-based multilayer hollow heterojunction electrolytic water catalyst;
the catalyst is of a multilayer hollow nanosphere structure; the composition of each layer of heterojunction is sequentially CoO/Co from the center to the outer9S8/Co9Se8(ii) a Each layer is of a hollow structure, and the components are in mirror symmetry.
Performance testing
1. The cobalt-based multilayer hollow heterojunction electrolytic water catalyst prepared in example 1 was taken and placed in a transmission electron microscope (TEM for short) for observation. The results are shown in FIG. 1.
FIG. 1 is a transmission electron microscope image of a cobalt-based multilayer hollow heterojunction electrolytic water catalyst prepared in example 1 of the present invention. As can be seen from fig. 1, the entire structure exhibits a multilayer hollow structure, and each layer of structure is a mirror-symmetric heterojunction structure.
2. The cobalt-based multilayer hollow heterojunction electrolytic water catalyst prepared in example 1 was taken and placed in a transmission electron microscope, and the outermost layer thereof was observed at a higher magnification. The results are shown in FIG. 2.
FIG. 2 is a transmission electron microscope image of the outermost layer of the cobalt-based multilayer hollow heterojunction electrolytic water catalyst prepared in example 1 of the invention at a higher magnification. As can be seen from fig. 2, the hollow pitch in each layer of hollow structure is about 10 nm.
3. The cobalt-based multilayer hollow heterojunction electrolytic water catalyst prepared in example 1 was taken and placed in a transmission electron microscope, and the outermost layer thereof was observed at high resolution. The results are shown in FIG. 3.
FIG. 3 is a high-resolution transmission electron microscope image of the outermost layer of the cobalt-based multilayer hollow heterojunction electrolytic water catalyst prepared in example 1 of the invention. As can be seen from FIG. 3, the surface is Co9S8And Co9Se8A heterojunction structure is formed.
4. The cobalt-based multilayer hollow heterojunction electrolytic water catalyst prepared in example 1 was taken and subjected to an element mapping test. The results are shown in FIG. 4.
FIG. 4 is an elemental mapping chart of a cobalt-based multilayer hollow heterojunction electrolytic water catalyst prepared in example 1 of the present invention. As can be seen from FIG. 4, the elements Co, S and Se are uniformly distributed in the structure, and the structure is proved to be as described.
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. The preparation method of the cobalt-based multilayer hollow heterojunction water electrolysis catalyst is characterized by comprising the following steps:
(1) dissolving cobalt nitrate hexahydrate and acetylacetone in deionized water, then adding hydrazine hydrate to perform low-temperature hydrothermal reaction, drying, and performing heat treatment in air atmosphere to obtain multilayer hollow cobaltosic oxide nanospheres;
(2) dispersing the multilayer hollow cobaltosic oxide nanospheres and sodium sulfide in deionized water for low-temperature hydrothermal reaction, drying, and then carrying out heat treatment in argon atmosphere to obtain multilayer hollow CoO/Co9S8;
(3) Mixing multi-layer hollow CoO/Co9S8And further carrying out heat treatment on the cobalt-based multilayer hollow heterojunction electrolytic water catalyst and selenium powder to obtain the cobalt-based multilayer hollow heterojunction electrolytic water catalyst.
2. The preparation method of the cobalt-based multilayer hollow heterojunction electrolytic water catalyst as claimed in claim 1, wherein in the step (1), the mass ratio of the cobalt nitrate hexahydrate, the acetylacetone, the hydrazine hydrate and the deionized water is 14.55:0.049:0.05: 1.
3. The preparation method of the cobalt-based multilayer hollow heterojunction electrolytic water catalyst as claimed in claim 1, wherein in the step (1), the temperature of the low-temperature hydrothermal reaction is 80 ℃ and the time is 1-24 h.
4. The preparation method of the cobalt-based multilayer hollow heterojunction electrolytic water catalyst as claimed in claim 1, wherein in the step (1), the temperature rise rate of the heat treatment is 1 ℃/min, the temperature is 450 ℃, and the time is 1-7 h.
5. The preparation method of the cobalt-based multilayer hollow heterojunction electrolytic water catalyst as claimed in claim 1, wherein in the step (2), the mass ratio of the multilayer hollow cobaltosic oxide nanospheres to the sodium sulfide to the deionized water is 0.144:0.23: 50.
6. The preparation method of the cobalt-based multilayer hollow heterojunction electrolytic water catalyst as claimed in claim 1, wherein in the step (2), the temperature of the low-temperature hydrothermal reaction is 90 ℃ and the time is 30-40 h.
7. The method for preparing a cobalt-based multilayer hollow heterojunction electrolytic water catalyst as claimed in claim 1, wherein in the step (2), the temperature of the heat treatment is 400 ℃ and the time is 1 h.
8. The method for preparing the cobalt-based multilayer hollow heterojunction electrolytic water catalyst as claimed in claim 1, wherein in the step (3), the multilayer hollow CoO/Co9S8The mass ratio of the selenium powder to the selenium powder is 1: 1.
9. The preparation method of the cobalt-based multilayer hollow heterojunction electrolytic water catalyst as claimed in claim 1, wherein in the step (3), the temperature rise rate of the heat treatment is 2 ℃/min, the temperature is 400 ℃, and the time is 1 h.
10. The preparation method of the cobalt-based multilayer hollow heterojunction electrolytic water catalyst according to claim 1, wherein in the step (3), the cobalt-based multilayer hollow heterojunction electrolytic water catalyst is of a multilayer hollow nanosphere structure; the composition of each layer of heterojunction is sequentially CoO/Co from the center to the outer9S8/Co9Se8(ii) a Each layer is of a hollow structure, and the components are in mirror symmetry.
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WO2021195957A1 (en) * | 2020-03-31 | 2021-10-07 | 中国科学院宁波材料技术与工程研究所 | Cobalt catalyst and preparation method therefor |
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