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CN-122013227-A - Cobalt-iron bimetallic hydrogen evolution catalyst and preparation method and application thereof

CN122013227ACN 122013227 ACN122013227 ACN 122013227ACN-122013227-A

Abstract

The invention discloses a cobalt-iron bimetallic hydrogen evolution catalyst, a preparation method and application thereof, and relates to the technical field of hydrogen production by water electrolysis; based on the total weight of the catalyst as 100%, the weight percentage of Co element in the catalyst is 32% -50%, and the weight percentage of Fe element in the catalyst is 1% -12%. The synergistic effect of the bimetallic active sites of the catalyst can improve the hydrogen evolution activity of the material in the electrolytic water, promote the transfer and transfer of electrons in a system, and has excellent hydrogen evolution performance. Under the condition of 1MKOH, when the current density can reach 10mA/cm 2 , the hydrogen evolution overpotential of the working electrode can reach 177mV, the attenuation rate in 12 hours can reach 1.58%, and the Tafel slope can reach 98mV/dec.

Inventors

  • ZHOU YUE
  • FENG YINGJIE
  • ZHAO QINGRUI
  • FU XIAOYUE
  • FENG JING
  • LIU DONGBING
  • LI WEI
  • BAI JIE

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
20241111

Claims (13)

  1. 1. A cobalt-iron bimetallic hydrogen evolution catalyst, characterized in that the catalyst comprises: the Co-ZIF material and Fe element freely dispersed in the cavity of the Co-ZIF material; Based on 100% of the total weight of the catalyst, The weight percentage of Co element in the catalyst is 32% -50%; the weight percentage of Fe element in the catalyst is 1% -12%.
  2. 2. The catalyst of claim 1, wherein: The weight percentage of Co element in the catalyst is 37% -45%, and/or, The weight percentage of Fe element in the catalyst is 3% -7%.
  3. 3. The catalyst of claim 1, wherein: The Co-ZIF material is a nitrogen doped Co-ZIF material, preferably, The weight percentage of nitrogen element in the nitrogen-doped Co-ZIF material is 3.8% -4.8%, and more preferably 4.1% -4.6%.
  4. 4. A catalyst according to any one of claims 1 to 3, characterized in that: the particle size of the catalyst ranges from 100 to 500nm, preferably from 180 to 350nm.
  5. 5. A method for preparing the cobalt-iron bimetallic hydrogen evolution catalyst according to any one of claims 1-4, wherein the method comprises: Mixing cobalt-containing compound and ferric trichloride dissolved in the solvent A with 2-methylimidazole dissolved in the solvent B, stirring for reaction, centrifuging, and washing to obtain the catalyst.
  6. 6. The method according to claim 5, characterized in that the method further comprises: and mixing the catalyst with a nitrogen-containing compound, and then annealing at a high temperature in a protective gas atmosphere.
  7. 7. The method according to claim 5, wherein: The weight ratio of the cobalt-containing compound, the ferric trichloride and the 2-methylimidazole is 1 (0.01-0.5): 1-10, preferably 1 (0.05-0.3): 2-5, and/or, The concentration of the cobalt-containing compound after dissolution in the A solvent is 0.01 to 0.2mol/L, preferably 0.02 to 0.06mol/L, and/or, The concentration of the 2-methylimidazole after being dissolved in the solvent B is 0.1-1.6mol/L, preferably 0.2-0.8mol/L.
  8. 8. The method according to claim 6, wherein: the weight ratio of the catalyst to the nitrogen-containing compound is 1 (0.1-2), preferably 1 (0.3-1).
  9. 9. The method according to claim 5, wherein: The solvent A is methanol and/or ethanol, preferably methanol, and/or, The cobalt-containing compound is cobalt nitrate hexahydrate and/or cobalt chloride hexahydrate, and/or, The solvent B is methanol and/or ethanol, preferably methanol.
  10. 10. The method according to claim 6, wherein: the nitrogen-containing compound is melamine and/or urea, preferably melamine, and/or, The protective gas is argon and/or nitrogen, preferably argon.
  11. 11. The method according to claim 5, wherein: The reaction temperature of the stirring reaction is 10 ℃ to 35 ℃, preferably 20 ℃ to 30 ℃, and/or the reaction time is 8 to 72 hours, preferably 16 to 36 hours, and/or the stirring rotation speed is 6000 to 2000rpm, preferably 1000 to 1600rpm.
  12. 12. The method according to claim 6, wherein: the high temperature anneal is performed at an anneal temperature of 700 ℃ to 900 ℃, preferably 760 ℃ to 840 ℃, and/or at a ramp rate of 1 ℃ to 10 ℃ per minute, preferably 3 ℃ to 5 ℃ per minute, and/or for an anneal time of 1 to 8 hours, preferably 3 to 5 hours.
  13. 13. Use of the cobalt-iron bimetallic hydrogen evolution catalyst according to any one of claims 1-4 or the cobalt-iron bimetallic hydrogen evolution catalyst prepared by the method according to any one of claims 5-12 in the field of hydrogen production by water electrolysis.

Description

Cobalt-iron bimetallic hydrogen evolution catalyst and preparation method and application thereof Technical Field The invention relates to the technical field of hydrogen production by water electrolysis, in particular to a cobalt-iron bimetallic hydrogen evolution catalyst and a preparation method and application thereof. Background Development of new clean energy sources is a powerful solution to achieve the above objectives effectively. The hydrogen energy has the characteristics of light weight, high energy density, large combustion heat value, environmental friendliness and the like, and becomes a green energy carrier with great potential in a new energy revolution. 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. Noble metal materials such as Pt/C, ruO 2, irO 2 and the like show excellent performance in the field of water electrolysis hydrogen production, but the industrialization of the water electrolysis hydrogen production technology is limited due to high price. Therefore, development of a non-noble metal catalyst having high activity and high stability is necessary for development in this field. The bimetallic active sites can perform electron transfer and transmission through the synergistic effect of the bimetallic active sites, so that the catalytic performance of the catalyst is improved. In addition, the content, particle size and structure of the active component all influence the intrinsic activity of the catalyst. At present, the synthesis process of the Co and Fe bimetallic catalyst based on ZIF is complex, and Fe components are mostly coated on the surface of the Co-ZIF material by granular substances, so that the actions of bimetallic sites are limited. Disclosure of Invention In order to solve the problems in the prior art, at present, most of the electrolyzed water hydrogen evolution catalysts have higher production cost and complex preparation process, and limit the development and application of the electrolyzed water hydrogen evolution catalysts. The invention provides a cobalt-iron bimetallic hydrogen evolution catalyst and a preparation method and application thereof. According to the invention, the Fe@Co-ZIF precursor material is synthesized by a one-step method under normal temperature, so that the preparation conditions that the synthesis process of the material is complex and high-temperature heating is required are improved, and the mass production is facilitated. The non-noble bimetallic catalyst is prepared through a simple and feasible synthesis process, so that the production cost is effectively reduced. Meanwhile, the catalyst shows good catalytic activity and cycle stability. The invention aims to provide a cobalt-iron bimetallic hydrogen evolution catalyst. The cobalt-iron bimetallic hydrogen evolution catalyst provided by the invention comprises the following components: A Co-ZIF material and Fe element freely dispersed in a cavity of the Co-ZIF material; Based on 100% of the total weight of the catalyst, The weight percentage of Co element in the catalyst is 32% -50%; the weight percentage of Fe element in the catalyst is 1% -12%. The type, number, morphology and size of the active sites of the catalyst determine the catalytic performance of the catalyst. In the Co and Fe bimetallic catalyst, fe element exists in a free state, and the Co and Fe bimetallic catalyst can promote the dynamic process of the electrolytic water hydrogen evolution reaction through synergistic effect, so that the hydrogen evolution performance of the catalyst is improved. In a preferred embodiment of the invention: The weight percentage of Co element in the catalyst is 37% -45%, and/or, The weight percentage of Fe element in the catalyst is 3% -7%. In a preferred embodiment of the invention: The Co-ZIF material is a nitrogen doped Co-ZIF material, preferably, The weight percentage of nitrogen element in the nitrogen-doped Co-ZIF material is 3.8% -4.8%, and more preferably 4.1% -4.6%. In a preferred embodiment of the invention: the particle size of the catalyst ranges from 100 to 500nm, preferably from 180 to 350nm. The second purpose of the invention is to provide a preparation method of the cobalt-iron bimetallic hydrogen evolution catalyst. The invention relates to a preparation method of a cobalt-iron bimetallic hydrogen evolution catalyst, which comprises the following steps: Mixing cobalt-containing compound and ferric trichloride dissolved in the solvent A with 2-methylimidazole dissolved in the solvent B, stirring for reaction, centrifuging, and washing to obtain the catalyst. In a preferred e