CN-122013229-A - Nickel-vanadium-based composite catalyst and preparation method and application thereof

Abstract

The invention discloses a nickel-vanadium-based composite catalyst, and a preparation method and application thereof. The nickel vanadium-based composite catalyst comprises a Ni-S compound and Ni 3 V. According to the invention, through sulfuration doping, catalytic sites with high activity can be generated in situ, and the conductivity of the catalytic material is obviously improved. The nickel-vanadium-based composite catalyst provided by the invention has good oxygen evolution performance.

Inventors

• ZHAO QINGRUI
• FENG YINGJIE
• FU XIAOYUE
• FENG JING
• ZHOU YUE
• LI YIFENG

Assignees

• 中国石油化工股份有限公司
• 中石化(北京)化工研究院有限公司

Dates

Publication Date

20260512

Application Date

20241112

Claims (10)

1. 1. A nickel-vanadium based composite catalyst comprises Ni-S compound and Ni 3 V.
2. 2. The nickel vanadium based composite catalyst according to claim 1, wherein: The molar ratio of Ni 3 V to Ni-S compound is (2-10): 1, preferably (2-5): 1.
3. 3. The nickel vanadium based composite catalyst according to claim 1, wherein: The size of the nickel-vanadium-based composite catalyst is 20-100 nm, preferably 20-60 nm.
4. 4. A method for preparing a nickel-vanadium based composite catalyst, preferably for preparing the nickel-vanadium based composite catalyst according to any one of claims 1-3, comprising mixing a sulfur-containing nickel source and a sulfur-containing vanadium source with water, adding an alkali solution, performing hydrothermal crystallization to obtain a nickel-vanadium based precursor, and finally calcining in an inert gas/H 2 atmosphere.
5. 5. The method of manufacturing according to claim 4, wherein: the sulfur-containing nickel source is selected from nickel sulfate, and/or, The sulfur-containing vanadium source is selected from vanadyl sulfate, and/or, The alkali liquor is at least one selected from potassium hydroxide solution, sodium hydroxide solution and ammonia water.
6. 6. The method of manufacturing according to claim 4, wherein: The mole ratio of the nickel source to the vanadium source is (4-8): 1, and/or, The molar ratio of the alkali liquor to the vanadium source is (4-10): 1, and/or, The concentration of the alkali liquor is 1-2.5M.
7. 7. The method of manufacturing according to claim 4, wherein: The hydrothermal crystallization temperature is 100-180 ℃ and the time is 20-28 h, preferably 100-160 ℃ and the time is 23-26 h.
8. 8. The method of manufacturing according to claim 4, wherein: The temperature rising rate of calcination is 4-8 ℃ per minute, preferably 4-6 ℃ per minute, and/or, The calcination temperature is 360-580 ℃ for 2-4 h, preferably 370-550 ℃ for 2-3 h.
9. 9. Use of the nickel vanadium based composite catalyst according to any one of claims 1 to 3 or the nickel vanadium based composite catalyst obtained by the preparation method according to any one of claims 2 to 8 in electrocatalytic oxygen evolution.
10. 10. The method according to claim 9, wherein the nickel-vanadium-based composite catalyst is used in an alkaline membrane electrolysis process.

Description

Nickel-vanadium-based composite catalyst and preparation method and application thereof Technical Field The invention relates to the field of hydrogen production by water electrolysis, in particular to a nickel-vanadium-based composite catalyst, a preparation method thereof and application thereof in the aspect of electrocatalytic oxygen evolution. Background With the world energy crisis becoming more and more severe and with the drastic changes in climate, the earth is experiencing serious environmental problems. In order to solve the environmental problems of global warming, resource shortage and the like, the development of green renewable clean energy to replace petrochemical energy is a research hotspot of the current energy industry. And hydrogen energy is taken as a clean energy source and can be hopeful to replace the traditional fossil energy source. With the progress of technology, various methods for preparing hydrogen have been developed. The method for producing hydrogen by electrolyzing water takes water as a raw material, no pollutant is produced in the electrolysis process, and meanwhile, the technology has a simple production process, so the method is considered as an efficient, environment-friendly and sustainable hydrogen production technology, and has wide application prospect. Anionic membrane electrolyzed water uses an Anionic Exchange Membrane (AEM) as a membrane and a low noble or non-noble metal as a catalyst. Compared with the traditional alkaline water electrolysis technology, the low-concentration alkaline solution or water can be used as the electrolyte, so that the electrolyte has the advantages of low cost, high efficiency and the like, and is also an electrolysis water technology which is paid attention in the future. The research and development of hydrogen evolution catalyst and oxygen evolution catalyst with high activity is an effective method for reducing the energy consumption in the water electrolysis process. In the catalytic oxygen evolution process, the noble metal catalyst has high activity, but is difficult to popularize and use in the commercial field due to low noble metal content and high price. Therefore, the research and development of the oxygen evolution catalytic electrode with low price, simple preparation process and high activity is very important. Although many studies on OER electrocatalysts in alkaline media have been reported in the literature, their use in AEMs has been less studied. Materials such as oxides and hydroxides have been widely paid attention to because of low cost and good oxygen evolution reactivity, but have a great gap from practical application requirements, and further improvement of performance and stability is required. Disclosure of Invention In order to solve the problems in the prior art, the invention develops the electrocatalytic oxygen evolution catalyst with low cost and high performance. One of the purposes of the invention is to provide a nickel-vanadium-based composite catalyst, which comprises a Ni-S compound and Ni 3 V. The nickel-vanadium-based composite catalyst material is a composite structure of an external sulfide (Ni-S compound) and an internal metal alloy (Ni 3 V). In the nickel-vanadium-based composite catalyst, the molar ratio of Ni 3 V to Ni-S compound is (2-10): 1, preferably (2-5): 1, and may be, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc. The size of the nickel-vanadium-based composite catalyst is 20-100 nm, preferably 20-60 nm. The Ni-S/Ni 3 V composite catalyst improves the oxygen vacancy density of the material based on Ni-S doping, thereby improving the charge transfer capability and oxygen evolution performance of the material. The second purpose of the invention is to provide a preparation method of the nickel-vanadium-based composite catalyst, which is one of the purposes of the invention: Mixing a sulfur-containing nickel source and a sulfur-containing vanadium source with water, adding alkali liquor, performing hydrothermal crystallization to obtain a nickel-vanadium-based precursor, and finally calcining in an inert gas/H 2 atmosphere. According to the invention, the sulfur-containing nickel source is selected from nickel sulfate. According to the invention, the sulfur-containing vanadium source is selected from vanadyl sulfate. According to the invention, the alkaline solution is at least one selected from potassium hydroxide solution, sodium hydroxide solution and ammonia water. According to the invention, the molar ratio of the nickel source to the vanadium source is (4-8): 1, for example, 4:1, 5:1, 6:1, 7:1, 8:1, etc. According to the present invention, the concentration of the alkali solution is 1 to 2.5M, for example, 1M, 1.5M, 2M, 2.5M, etc. According to the invention, the molar ratio of alkali liquor to vanadium source is (4-10): 1, for example, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc. According to the invention, the temperature of hydrothermal crystallization is 10