CN-122013241-A - Doping regulation type ruthenium iridium-based electrocatalytic oxygen evolution catalyst and preparation method thereof

CN122013241ACN 122013241 ACN122013241 ACN 122013241ACN-122013241-A

Abstract

The invention belongs to the technical field of preparation of electrocatalytic oxygen evolution catalysts, and particularly discloses a doping regulation type ruthenium-iridium-based electrocatalytic oxygen evolution catalyst and a preparation method thereof, wherein the preparation method comprises the following steps of S1, dispersing ruthenium salt, iridium salt and doping metal salt in a solvent, wherein the doping metal salt is one or more selected from yttrium salt, strontium salt, potassium salt, calcium salt, magnesium salt, scandium salt, gallium salt and aluminum salt; S2, preparing a precursor mixture, S3, performing heat treatment to obtain a solid product, and S4, washing and drying to obtain the metal element doped ruthenium iridium-based electrocatalytic oxygen evolution catalyst. The doping regulation type ruthenium iridium-based electrocatalysis oxygen evolution catalyst and the preparation method thereof are simple in process and strong in universality, doping of various elements can be realized by replacing doping metal salt, and the obtained catalyst has excellent oxygen evolution activity of acidic electrolyzed water and long-cycle stability, and can avoid excessive phase splitting of Y element and excessive lattice distortion of other elements.

Inventors

HU CHUANGANG
Kou Ruitian
YU ZEQIANG
HU YINGJIE
ZHAO LINJIE
Mao Baoguang

Assignees

北京化工大学

Dates

Publication Date: 20260512
Application Date: 20260209

Claims (10)

1. The preparation method of the doped regulation type ruthenium iridium-based electrocatalytic oxygen evolution catalyst is characterized by comprising the following steps of: S1, preparing a metal salt mixed solution, namely dispersing ruthenium salt, iridium salt and doped metal salt in a solvent according to a molar ratio, and stirring to obtain the metal salt mixed solution, wherein the doped metal salt is one or more of yttrium salt, strontium salt, potassium salt, calcium salt, magnesium salt, scandium salt, gallium salt and aluminum salt; S2, preparing a precursor mixture, namely adding the metal salt mixed solution obtained in the step S1 into a carrier precursor, and grinding and homogenizing to obtain the precursor mixture; S3, placing the precursor mixture obtained in the step S2 in heat treatment equipment, performing heat treatment in an oxygen-containing atmosphere, and cooling to room temperature to obtain a solid product; And S4, washing and drying, namely firstly carrying out acid washing on the solid product obtained in the step S3, then washing with deionized water until the washing liquid is neutral, and carrying out drying treatment to obtain the metal element doped ruthenium iridium-based electrocatalytic oxygen evolution catalyst.
2. The preparation method of the doping-controlled ruthenium iridium-based electrocatalytic oxygen evolution catalyst according to claim 1, wherein in S1, the ruthenium salt is one or two selected from ruthenium trichloride and ruthenium trichloride hydrate, the iridium salt is one or two selected from iridium trichloride and iridium trichloride hydrate, and the yttrium salt is one or two selected from yttrium chloride hexahydrate and yttrium nitrate.
3. The method for preparing a doping-controlled ruthenium-iridium-based electrocatalytic oxygen evolution catalyst according to claim 2, wherein in S1, the solvent is ethanol.
4. The preparation method of the doped-control ruthenium-iridium-based electrocatalytic oxygen evolution catalyst according to claim 2, wherein in S1, the molar ratio of the ruthenium salt to the iridium salt to the yttrium salt is 0.6-0.8:0.1-0.3:0.05-0.15.
5. The preparation method of the doping-regulated ruthenium-iridium-based electrocatalytic oxygen evolution catalyst according to claim 1, wherein in S1, the concentration of ruthenium element in the metal salt mixed solution is 10-50 g/L, the concentration of iridium element is 5-20 g/L, and the concentration of doping element corresponding to the doping metal salt is 2-10 g/L.
6. The preparation method of the doped-control ruthenium iridium-based electrocatalytic oxygen evolution catalyst according to claim 1, wherein in S2, the carrier precursor is a mixture of NH 4 NO 3 and D-glucose, and the mass ratio of NH 4 NO 3 to D-glucose is 0.6-1.0:1.
7. The method for preparing a doping-controlled ruthenium iridium-based electrocatalytic oxygen evolution catalyst according to claim 1, wherein in S3, the heat treatment is specifically: Heating to 400-600 ℃, wherein the heating rate is 5-10 ℃ per minute, and the heat preservation time is 60-120 min; The oxygen-containing atmosphere is specifically an air atmosphere.
8. The method for preparing a doped-control ruthenium iridium-based electrocatalytic oxygen evolution catalyst according to claim 1, wherein in S4, the washing is specifically: washing the solid product for 2-3 times by using 0.5-2.0 mol/L hydrochloric acid or sulfuric acid, filtering the solid product, washing with deionized water, and repeatedly washing until the pH value of the washing liquid is=6.5-7.5.
9. The method for preparing a doped-control ruthenium iridium-based electrocatalytic oxygen evolution catalyst according to claim 1, wherein in S4, the drying is specifically: Freeze drying is adopted, the drying temperature is-100 to-25 ℃, the drying air pressure is 10-40 pa, and the drying time is 1-5 days.
10. The doping regulation type ruthenium-iridium-based electrocatalytic oxygen evolution catalyst prepared by the preparation method of the doping regulation type ruthenium-iridium-based electrocatalytic oxygen evolution catalyst according to any one of claims 1-9, which is characterized by comprising active components of Y doped Ru-Ir composite oxide, wherein the purity of the Y doped Ru-Ir composite oxide is more than or equal to 99.9wt%.

Description

Doping regulation type ruthenium iridium-based electrocatalytic oxygen evolution catalyst and preparation method thereof Technical Field The invention relates to the technical field of preparation of electrocatalytic oxygen evolution catalysts, in particular to a doping regulation type ruthenium iridium-based electrocatalytic oxygen evolution catalyst and a preparation method thereof. Background Along with the increasing severity of global energy crisis and environmental pollution problems, the development of clean and sustainable new energy conversion technology becomes a current research hotspot. Electrolytic water hydrogen production is considered as one of the most potential energy storage and conversion approaches because of the ability to convert renewable energy sources (e.g., solar energy, wind energy) into high energy density hydrogen energy. Oxygen Evolution Reaction (OER) is used as an anode core reaction in the water electrolysis process, and the slow dynamic process severely restricts the overall efficiency of an water electrolysis system, so that the development of an efficient and stable OER electrocatalytic material is a key for promoting the large-scale application of the water electrolysis hydrogen production technology. In acidic electrolyzed water systems, the choice of electrocatalyst is severely limited due to harsh operating conditions such as strong acid media, high operating potential, etc. Commercial acid OER catalysts mainly depend on rare noble metal oxides of ruthenium (Ru) and iridium (Ir), wherein ruthenium-iridium composite oxides are one of the optimal systems for balanced activity and stability by virtue of high catalytic activity of Ru and excellent structural stability of Ir. However, the pure ruthenium iridium composite oxide still has the problems of insufficient electronic structure regulation, easy loss of active sites in long-term reaction and the like, so that the catalytic performance is difficult to meet the requirement of large-scale application. Doping of heterogeneous elements has proved to be an effective strategy for optimizing the electronic structure of ruthenium iridium composite oxide, stabilizing the lattice structure and synchronously improving the catalytic activity and the cycling stability. In the prior art, the preparation method of the doped ruthenium iridium-based catalyst has obvious limitations: (1) Most preparation processes are strong in pertinence, only doping of specific single elements can be realized, doping elements are difficult to flexibly replace to adapt to performance requirements of different application scenes, and universality is poor; (2) The content control precision of the doped element is insufficient, the dosage of the carrier and the element characteristics are not cooperatively considered, when the doped element is Y, excessive doping is easy to cause phase separation, and other elements are excessive to possibly cause lattice distortion, and meanwhile, the improper dosage of the carrier can cause metal ion agglomeration or residue to further influence the catalytic performance; (3) The carrier used in part of the preparation method is difficult to completely remove, and the residual carrier component can influence the exposure of the active site of the catalyst, thereby restricting the synergistic catalysis performance of the ruthenium-iridium composite system. Therefore, the three materials of doping element selection, doping content control and carrier dosage proportion cooperate to meet the performance requirement of the ruthenium iridium-based catalyst, and the research and development of the preparation method of the doped ruthenium iridium-based electro-catalytic oxygen evolution catalyst with strong universality (flexible substitution of doping elements and accurate regulation and control of key parameters), simple preparation process and high catalyst purity has important significance for promoting the development of the hydrogen production technology of acidic electrolyzed water. Disclosure of Invention The invention aims to provide a doping regulation type ruthenium iridium-based electrocatalysis oxygen evolution catalyst and a preparation method thereof, which have simple process and strong universality, and can realize doping of various elements by replacing doped metal salt, and the obtained catalyst has excellent oxygen evolution activity of acidic electrolyzed water and long-cycle stability, and can avoid excessive phase splitting of Y element and excessive lattice distortion of other elements. In order to achieve the above purpose, the invention provides a preparation method of a doped regulation type ruthenium iridium-based electrocatalytic oxygen evolution catalyst, which comprises the following steps: S1, preparing a metal salt mixed solution, namely dispersing ruthenium salt, iridium salt and doped metal salt in a solvent according to a molar ratio, and stirring to obtain the metal salt mixed solution,