Search

CN-121976224-A - High-entropy perovskite supported catalyst and preparation method and application thereof

CN121976224ACN 121976224 ACN121976224 ACN 121976224ACN-121976224-A

Abstract

The invention discloses a high-entropy perovskite supported catalyst and a preparation method and application thereof, wherein the catalyst comprises a perovskite carrier and iridium nanoclusters dispersed on the perovskite carrier, the perovskite carrier is a high-entropy perovskite carrier with B sites occupied by five different transition metal elements, the five different transition metal elements comprise Ir, ti, ni, co and Mo, the mass ratio of the iridium nanoclusters to the perovskite carrier is 0.6-1:1, and the catalyst has a rooting structure with active component iridium elements distributed in a perovskite mineral phase and the iridium nanoclusters. The prepared rooting type high-entropy perovskite carrier supported iridium catalyst has good catalytic activity and catalytic stability in proton exchange membrane water electrolysis equipment, and effectively solves the problem that iridium active species in the proton exchange membrane electrolysis water anode supported catalyst are easy to agglomerate and fall off under the reaction condition.

Inventors

  • XING WEI
  • NI JING
  • LIU CHANGPENG
  • XIAO MEILING
  • JIN ZHAO
  • LI CHENYANG
  • LIANG LIANG
  • WANG CHEN

Assignees

  • 中国科学院长春应用化学研究所

Dates

Publication Date
20260505
Application Date
20251216

Claims (10)

  1. 1. The high-entropy perovskite supported catalyst is characterized by comprising a perovskite carrier and iridium nanoclusters dispersed on the perovskite carrier; The perovskite carrier is a high-entropy perovskite carrier with B sites occupied by five different transition metal elements, wherein the five different transition metal elements comprise Ir, ti, ni, co and Mo, the mass ratio of the iridium nanocluster to the perovskite carrier is 0.6-1:1, and the catalyst has a rooting structure in which iridium elements serving as active components are simultaneously distributed in a perovskite body phase and the iridium nanocluster.
  2. 2. The method for preparing a high-entropy perovskite supported catalyst according to claim 1, comprising, Mixing soluble metal salt solutions of Ir, ti, ni, co and Mo with nitrate and citric acid, and carrying out water bath treatment and drying by a sol-gel method to obtain a high-entropy perovskite precursor; Roasting the high-entropy perovskite precursor in an air atmosphere to obtain a high-entropy perovskite carrier; and (3) carrying out heat treatment on the high-entropy perovskite carrier to enable iridium element to segregate, and sequentially carrying out acid washing, water washing and drying to obtain the high-entropy perovskite supported catalyst.
  3. 3. The preparation method according to claim 2, wherein the soluble metal salt solution of Ir, ti, ni, co and Mo is mixed with nitrate and citric acid, wherein the soluble metal salt of Ir is potassium hexachloroiridium, the soluble metal salt of Ti is isopropyl titanate, the soluble metal salt of Ni is nickel nitrate hexahydrate, the soluble metal salt of Co is cobalt nitrate hexahydrate, the soluble metal salt of Mo is ammonium molybdate, and the nitrate comprises one of strontium nitrate and barium nitrate.
  4. 4. The method according to claim 3, wherein the molar ratio of the soluble metal salt of Ir, ti, ni, co, mo is 0.9-1.1:0.9-1.1, and the molar ratio of the soluble metal salt, nitrate, and citric acid is 0.9-1.1:3-5:1-2.
  5. 5. The method of claim 2, wherein the sol-gel process is performed by water bath treatment and drying, wherein the water bath temperature is 60-80 ℃, the water bath time is 3-5 hours, the drying temperature is 160-200 ℃, and the drying time is 6-18 hours.
  6. 6. The method of claim 2, wherein the calcining of the high entropy perovskite precursor in an air atmosphere is performed at a stepwise elevated temperature comprising a first to a fourth stage, The roasting temperature in the first stage is 190-210 ℃ and the roasting time is 3-6 h; the roasting temperature of the second stage is 290-310 ℃ and the roasting time is 3-6 h; The roasting temperature in the third stage is 490-510 ℃ and the roasting time is 3-6 h; The roasting temperature in the fourth stage is 600-800 ℃ and the roasting time is 3-6 h; the temperature rising rate is 0.5-10 ℃ min -1 .
  7. 7. The method of claim 2, wherein the high-entropy perovskite support is subjected to heat treatment, wherein the heat treatment is performed in a flowing atmosphere, and the flowing atmosphere is a mixed gas comprising a mixed gas of hydrogen and argon and a mixed gas of hydrogen and nitrogen.
  8. 8. The method of claim 7, wherein the hydrogen content of the mixed gas is 5-10% by volume.
  9. 9. The method of claim 7, wherein the heat treatment temperature is 500-700 ℃, the heat treatment time is 1.5-3 hours, and the heating rate is 0.5-10 ℃ min -1 .
  10. 10. Use of the high entropy perovskite supported catalyst according to claim 1 in proton exchange membrane electrolysis of water.

Description

High-entropy perovskite supported catalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of catalysts, and particularly relates to a high-entropy perovskite supported catalyst, and a preparation method and application thereof. Background Proton Exchange Membrane Water Electrolysis (PEMWE) is an energy conversion technology with great application prospect, and can convert renewable electric power into clean and high-purity hydrogen, thereby being beneficial to solving energy problems and environmental challenges. However, since the kinetics of the anode side Oxygen Evolution Reaction (OER) are relatively slow, the energy conversion efficiency and the application scalability of this technology are still severely limited by the OER catalyst performance. Currently, iridium (Ir) based materials, which are subject to the severe environment of strong acidity and high potential on the anode side, with relatively synergistic activity and stability, are considered to be the most promising PEMWE anode catalysts. However, due to its scarcity and high cost, reducing the anode side Ir content becomes a significant challenge for the technological development. The supported catalyst can realize high dispersion of active sites, is considered as one of effective ways to reduce Ir content, and has been studied more recently. However, the single metal oxide supported catalyst has limited anchoring ability to the Ir catalytic layer, and particularly when the Ir content is reduced, the active sites face frequent structural transformations, so that the Ir is liable to undergo severe dissolution and agglomeration at a sustained anode potential. Therefore, improvement of durability in use of the low Ir catalyst has become an important research direction for development of PEMWE. At present, more work has been done to develop an anchoring strategy for low Ir catalysts from the point of physical structure regulation, for example, new teaching team of Jilin university Xiao has developed a TaB 2 -supported IrO 2 catalyst, which utilizes the defects of the TaOx amorphous layer generated under electrochemical conditions to achieve effective anchoring of active sites. The university of lanzhou Xi Pinxian teaches that an efficient oxygen evolution process is achieved by anchoring the monoatomic Ir through oxygen vacancies. The vinca-religion institute Xing Wei researchers realize the local strong anchoring of the Ir catalytic layer through the homogeneous heterogeneous interface carrier, and finally realize the good application of the developed catalyst in the PEMWE monocell. However, the active site anchoring strategies developed at present are mainly focused on the regulation and control of the physical structure of the catalyst under non-reaction conditions, and are difficult to meet the stability requirement of the dynamic structural change of the catalyst under actual working conditions. Disclosure of Invention This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the invention and in the title of the invention, which may not be used to limit the scope of the invention. The present invention has been made in view of the above and/or problems occurring in the prior art. Therefore, the invention aims to overcome the defects in the prior art and provide a high-entropy perovskite supported catalyst. In order to solve the technical problems, the invention provides the following technical scheme: the catalyst comprises a perovskite carrier and iridium nanoclusters dispersed on the perovskite carrier; The perovskite carrier is a high-entropy perovskite carrier with B sites occupied by five different transition metal elements, wherein the five different transition metal elements comprise Ir, ti, ni, co and Mo, the mass ratio of the iridium nanocluster to the perovskite carrier is 0.6-1:1, and the catalyst has a rooting structure in which iridium elements serving as active components are simultaneously distributed in a perovskite body phase and the iridium nanocluster. The invention further aims to overcome the defects in the prior art and provide a preparation method of the high-entropy perovskite supported catalyst. In order to solve the technical problems, the invention provides the following technical scheme: Mixing soluble metal salt solutions of Ir, ti, ni, co and Mo with nitrate and citric acid, and carrying out water bath treatment and drying by a sol-gel method to obtain a high-entropy perovskite precursor; Roasting the high-entropy perovskite precursor in an air atmosphere to obtain a high-entropy perovskite carrier; and (3) carrying out heat treatment on the high-entropy perovskite carrier to enable iridium element to segregate, and sequentially carrying out acid washing, water washing and drying to