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CN-121976243-A - Amorphous high-entropy solid solution oxide catalyst and preparation method and application thereof

CN121976243ACN 121976243 ACN121976243 ACN 121976243ACN-121976243-A

Abstract

The invention relates to the technical field of electrolytic water oxygen evolution, in particular to an amorphous high-entropy solid solution oxide catalyst, a preparation method and application thereof. Mixing the metal salt 1, the metal salt 2, the C 3 N 4 carrier and water, stirring and steaming in turn to obtain a spin-steamed material, and roasting the spin-steamed material to obtain the amorphous high-entropy solid solution oxide catalyst. The preparation method of the iridium-based amorphous solid solution oxide catalyst provided by the invention is simple to operate and has controllable metal components and loading capacity. The prepared amorphous high-entropy solid solution oxide catalyst has the advantages of high bulk density, high oxygen evolution activity and good stability, and has great potential for practical application in proton exchange membrane water electrolysis.

Inventors

  • ZHOU KEBIN
  • YANG XIAOXIN
  • WANG ZHE
  • HU MINGZHEN

Assignees

  • 中国科学院大学
  • 滨州魏桥国科高等技术研究院

Dates

Publication Date
20260505
Application Date
20260203

Claims (10)

  1. 1. The preparation method of the amorphous high-entropy solid solution oxide catalyst is characterized by comprising the following steps of: 1) Mixing the metal salt 1, the metal salt 2, the C 3 N 4 carrier and water, and then sequentially stirring and rotary steaming to obtain a rotary steamed material; The metal salt 1 is iridium trichloride hydrate; the number of the metal salt 2 is any 4 of RuCl 3 ·3H 2 O、(NH 4 ) 6 Mo 7 O 24 ·4H 2 O、Zr(SO 4 ) 2 ·4H 2 O、Ti(SO 4 ) 2 、C 4 H 4 NNbO 9 ·nH 2 O、La(NO 3 ) 3 ·6H 2 O、Sm(NO 3 ) 3 ·6H 2 O; 2) Roasting the rotary steaming material in the step 1) to obtain the amorphous high-entropy solid solution oxide catalyst.
  2. 2. The preparation method according to claim 1, wherein the mass ratio of the metal salt 1, the metal salt 2, the C 3 N 4 carrier and the water in the step 1) is 15.6 mg:7.1-27.2 mg:40mg:30mL.
  3. 3. The production method according to claim 2, wherein when the metal salt 2 is (NH 4 ) 6 Mo 7 O 24 ·4H 2 O、C 4 H 4 NNbO 9 ·nH 2 O、La(NO 3 ) 3 ·6H 2 O and Sm (NO 3 ) 3 ·6H 2 O), the mass ratio of (NH 4 ) 6 Mo 7 O 24 ·4H 2 O、C 4 H 4 NNbO 9 ·nH 2 O、La(NO 3 ) 3 ·6H 2 O and Sm (NO 3 ) 3 ·6H 2 O is 0.9:1.6:2.3:2.3).
  4. 4. The preparation method according to claim 2, wherein when the metal salt 2 is RuCl 3 ·3H 2 O、(NH 4 ) 6 Mo 7 O 24 ·4H 2 O、Zr(SO 4 ) 2 ·4H 2 O and Ti (SO 4 ) 2 ), the mass ratio of RuCl 3 ·3H 2 O、(NH 4 ) 6 Mo 7 O 24 ·4H 2 O、Zr(SO 4 ) 2 ·4H 2 O to Ti (SO 4 ) 2 is 4.6-13.7:2.3-3.1:4.6-6.2:3.1-4.2.
  5. 5. The method according to claim 1, wherein the stirring conditions in step 1) include a rotation speed of 500 to 1000rpm for 8 to 12 hours.
  6. 6. The preparation method according to claim 1, wherein the spin-steaming condition in step 1) comprises a rotation speed of 175-215 rpm and a temperature of 50-60 ℃.
  7. 7. The method of claim 1, wherein the method of preparing the C 3 N 4 support of step 1) comprises the step of calcining the urea at 550 ℃ for 3 hours.
  8. 8. The method according to claim 1, wherein the conditions for the firing in step 2) include a temperature of 400℃for a period of 2 hours.
  9. 9. An amorphous high entropy solid solution oxide catalyst prepared by the preparation method of any one of claims 1 to 8.
  10. 10. Use of the amorphous high entropy solid solution oxide catalyst according to claim 9 for the electrolytic water oxygen evolution.

Description

Amorphous high-entropy solid solution oxide catalyst and preparation method and application thereof Technical Field The invention relates to the technical field of electrolytic water oxygen evolution, in particular to an amorphous high-entropy solid solution oxide catalyst, a preparation method and application thereof. Background Hydrogen gas is used as a clean renewable energy source and plays an important role in restoring environmental pollution and relieving energy crisis. In various hydrogen production technologies, proton exchange membrane water electrolysis stands out due to the advantages of high energy efficiency, current density, hydrogen purity and the like. However, the anodic oxygen evolution reaction in proton exchange membrane water electrolysis is a multi-step mass electrotransfer reaction with slow kinetics, and the acidic and strong oxidation environment also causes the problem of poor stability of the electrocatalyst. Therefore, the need for an efficient and stable oxygen evolution electrocatalyst has become an leading topic of proton exchange membrane water electrolysis research. The electrolytic water oxygen evolution catalyst used in industry at present is iridium-based catalyst, and the intrinsic activity of the catalyst is low. The solid solution oxide formed by other non-noble metals and iridium can regulate and control the electronic structure of iridium species, and optimize the adsorption energy of an oxygen-containing intermediate on iridium active center atoms in the oxygen evolution process, so that the catalytic performance is optimized. In particular, the solid solution component is added into five obtained high-entropy solid solution oxides, which can further regulate and control the electronic structure of active metal, and meanwhile, the high-entropy system increases the energy barrier of atomic diffusion and migration, so that the excellent durability under severe conditions is realized. However, it is still difficult for the conventional crystalline high entropy solid solution oxide catalyst to break through the linear relationship between the binding energies of the reaction intermediates OH and OOH, severely limiting the oxygen evolution reaction rate. The metal active site in the amorphous oxide catalyst has dynamic movement characteristic, and can realize direct coupling of the O intermediate, thereby providing possibility for further improving oxygen evolution efficiency. In recent years, some progress has been made in the preparation of amorphous oxide catalysts. For example, the preparation of amorphous oxide catalysts can be easily achieved by the molten salt method, but the composition of amorphous catalysts synthesized by this method is limited to binary, ternary, etc. minor solid solutions. In view of the great difficulty in mixing multiple elements on the nanometer scale, the research on the preparation method of the amorphous high-entropy solid solution oxide is very deficient. Therefore, a preparation method of the amorphous high-entropy solid solution oxide catalyst with simple operation, controllable metal components and loading capacity, high activity and high stability is needed to be invented at present. Disclosure of Invention In order to solve the problems, the invention provides an amorphous high-entropy solid solution oxide catalyst, a preparation method and application thereof. In order to achieve the above object, the present invention provides the following technical solutions: The invention provides a preparation method of an amorphous high-entropy solid solution oxide catalyst, which comprises the following steps: 1) Mixing the metal salt 1, the metal salt 2, the C 3N4 carrier and water, and then sequentially stirring and rotary steaming to obtain a rotary steamed material; The metal salt 1 is iridium trichloride hydrate; the number of the metal salt 2 is any 4 of RuCl3·3H2O、(NH4)6Mo7O24·4H2O、Zr(SO4)2·4H2O、Ti(SO4)2、C4H4NNbO9·nH2O、La(NO3)3·6H2O、Sm(NO3)3·6H2O; 2) Roasting the rotary steaming material in the step 1) to obtain the amorphous high-entropy solid solution oxide catalyst. Preferably, the mass of the metal salt 1, the mass of the metal salt 2, the mass of the C 3N4 carrier and the volume ratio of water in the step 1) are 15.6mg to 7.1-27.2 mg to 40mg to 30mL. Preferably, when the metal salt 2 is (NH4)6Mo7O24·4H2O、C4H4NNbO9·nH2O、La(NO3)3·6H2O and Sm (NO 3)3·6H2 O), the mass ratio of (NH4)6Mo7O24·4H2O、C4H4NNbO9·nH2O、La(NO3)3·6H2O to Sm (NO 3)3·6H2 O is 0.9:1.6:2.3:2.3). Preferably, when the metal salt 2 is RuCl3·3H2O、(NH4)6Mo7O24·4H2O、Zr(SO4)2·4H2O and Ti (SO 4)2), the mass ratio of RuCl3·3H2O、(NH4)6Mo7O24·4H2O、Zr(SO4)2·4H2O to Ti (SO 4)2 is 4.6-13.7:2.3-3.1:4.6-6.2:3.1-4.2). Preferably, the stirring condition in the step 1) comprises the rotation speed of 500-1000 rpm and the time of 8-12 h. Preferably, the spin-steaming condition in the step 1) comprises the rotation speed of 175-215 rpm and the temperature of 50-60 ℃. Preferably, the