CN-122013243-A - Doped ruthenium-based catalyst, and preparation method and application thereof

CN122013243ACN 122013243 ACN122013243 ACN 122013243ACN-122013243-A

Abstract

The invention belongs to the technical field of electrocatalysis, and particularly relates to a doped ruthenium-based catalyst, and a preparation method and application thereof. The transition metal doping element can stabilize crystal lattice, inhibit structural change and active component loss of the catalyst in the reaction process, and carbon optimizes electron cloud distribution and enhances adsorption and activation capability of reaction intermediates. In addition, the transition metal and carbon form a metal carbide network structure with high corrosion resistance and conductivity in ruthenium dioxide crystal lattice, so that the transition metal and carbon can not only be used as a network skeleton to strengthen the mechanical strength of a carrier, but also construct a high-speed electron transmission channel and optimize the interfacial charge transfer efficiency, thereby improving the catalytic activity of the ruthenium-based catalyst, and effectively inhibiting migration agglomeration and dissolution loss of ruthenium dioxide particles in a high-potential environment, so that the chemical stability and thermal stability of the catalyst are improved in a breakthrough manner, and meanwhile, the loading amount of noble metal ruthenium is obviously reduced, and the raw material cost is greatly saved.

Inventors

YU YONGZHI
WU YURU
SUN HONGJIANG
CHEN YUNXIA
CHENG SI
SHI WEI
WU YUANFA
LUO TING

Assignees

景德镇陶瓷大学

Dates

Publication Date: 20260512
Application Date: 20260323

Claims (10)

1. A doped ruthenium-based catalyst comprising ruthenium dioxide and a transition metal and carbon doped in the ruthenium dioxide lattice; the transition metal includes a transition metal other than ruthenium; The transition metal and carbon form a transition metal carbide network.
2. A doped ruthenium-based catalyst according to claim 1 wherein the transition metal comprises at least one of molybdenum, chromium, tungsten, zirconium, titanium, and vanadium; The mol ratio of the transition metal to the ruthenium is 1:9-4:1; The molar ratio of the carbon to the ruthenium is 1:4-2:1.
3. A doped ruthenium-based catalyst according to claim 1, wherein the doped ruthenium-based catalyst is of rutile crystalline structure; the particle size of the doped ruthenium-based catalyst is less than 10nm.
4. A method for preparing a doped ruthenium-based catalyst according to any one of claims 1 to 3, comprising the steps of: The method comprises the steps of firstly mixing a ruthenium source, a transition metal source, glucose, urea and water, and drying an obtained foaming system to obtain a porous foam material, wherein the transition metal source is a transition metal source except the ruthenium source; Performing first calcination on the porous foam material to obtain transition metal doped ruthenium dioxide; And (3) carrying out a second mixing of the transition metal doped ruthenium dioxide, glucose and water, carrying out a hydrothermal reaction, and then carrying out a second calcination on the obtained product to obtain the doped ruthenium-based catalyst.
5. The method of preparing according to claim 4, wherein the ruthenium source comprises one of ruthenium chloride, ruthenium acetate, and ammonium chlororuthenate; the transition metal source comprises at least one of a molybdenum source, a chromium source, a tungsten source, a zirconium source, a titanium source and a vanadium source; The molybdenum source comprises at least one of ammonium molybdate and molybdenum nitrate; the chromium source comprises at least one of chromium chloride, chromium nitrate, chromium acetate, chromium sulfate, and ammonium chromate; The tungsten source comprises at least one of ammonium metatungstate, sodium tungstate and tungsten chloride; the zirconium source comprises at least one of zirconium oxychloride, zirconium chloride, zirconium nitrate and zirconium acetylacetonate; The titanium source comprises at least one of titanium sulfate and titanium acetylacetonate; the vanadium source comprises at least one of vanadium chloride and ammonium metavanadate; In the first mixing, the mass ratio of the glucose to the urea is 4-8:1; the mass ratio of the total mass of glucose and urea to the ruthenium source is 100-300:1; And the molar ratio of the transition metal source to the ruthenium source is 1:9-4:1 based on the molar ratio of the transition metal to the ruthenium.
6. The preparation method according to claim 4, wherein the drying temperature is 120-160 ℃ and the heat preservation time is 12-36 h; The temperature of the first calcination is 500-600 ℃, the heat preservation time is 3-10 h, and the temperature rising rate is 5-10 ℃ per minute.
7. The method according to claim 4, wherein the molar ratio of the transition metal to ruthenium in the transition metal doped ruthenium dioxide is 1:9 to 4:1 based on the molar ratio of the transition metal to ruthenium.
8. The method according to claim 4, wherein in the second mixture, the mass ratio of the glucose to the transition metal-doped ruthenium dioxide is 1-2:1.
9. The preparation method according to claim 4, wherein the hydrothermal reaction is carried out at a temperature of 140-220 ℃ and a heat preservation time of 8-24 hours; The temperature of the second calcination is 400-500 ℃, the heat preservation time is 1-5 h, and the temperature rising rate is 5-20 ℃ per minute.
10. Use of the doped ruthenium-based catalyst according to any one of claims 1 to 3 or the doped ruthenium-based catalyst prepared by the preparation method according to any one of claims 4 to 9 in electrolysis of water.

Description

Doped ruthenium-based catalyst, and preparation method and application thereof Technical Field The invention belongs to the technical field of electrocatalysis, and particularly relates to a doped ruthenium-based catalyst, and a preparation method and application thereof. Background The hydrogen energy is taken as a secondary energy source which has various acquisition ways, is clean and environment-friendly and has multiple purposes, and is widely regarded as an ideal energy source selection in the century in the field of global energy. Hydrogen energy is becoming an increasingly interesting and growing source of clean energy. The conversion of renewable energy sources such as unstable wind energy, solar energy and the like into environmentally friendly green hydrogen through the electrolysis of water is considered as an important green technology for coping with energy sources and environmental challenges. Ruthenium catalysts, particularly ruthenium dioxide having a rutile structure, which has excellent intrinsic catalytic activity, high natural reserves and low price, are considered as a promising material for hydrogen evolution reactions instead of iridium. However, ruthenium-based catalysts present serious challenges in acidic oxygen evolution reactions, such as structural collapse induced by the participation of lattice oxygen in the reaction, and the formation of high-valence soluble ruthenium species with surface ruthenium dioxide clusters falling off during the reaction. To solve the above problems, many researchers have significantly improved their catalytic performance through doping strategies in recent years. In the prior art, a colloid method is adopted to synthesize the phosphorus-doped ruthenium nano particles, and the phosphorus content is regulated and controlled by optimizing pyrolysis conditions, so that partial electron deficiency of ruthenium atoms is realized, thereby weakening hydrogen adsorption energy, promoting hydrogen desorption and remarkably improving hydrogen evolution reaction performance. However, the limitations of single element doping and the poor intrinsic conductivity of oxides limit further increases in their catalytic activity, and therefore, exploration of new strategies capable of simultaneously modulating electronic structures and enhancing conductivity is imperative. To break through the bottleneck of single doping, researchers also direct their eyes to a "dual element collaboration" strategy. By introducing two different doping elements, the electronic structure, the crystal structure and the surface property of the catalyst are expected to be cooperatively regulated and controlled, and the limitation of single element doping is overcome. For example, in the prior art, strontium and tantalum elements are simultaneously introduced into ruthenium dioxide, the electron environment around ruthenium is adjusted by the introduction of strontium, the adsorption of reactants is promoted, and the lattice stability is enhanced by tantalum, so that the catalyst shows excellent activity and stability in an acidic oxygen evolution reaction. In addition, bi-element doping may induce new active sites or active centers, alter reaction pathways, and lower the reaction energy barrier. The carrier with good conductivity is reasonably selected to be compounded with the double-element doped ruthenium-based catalyst, so that the overall electron transmission performance can be effectively improved. However, the catalytic activity of the existing ruthenium-based catalyst needs to be improved so as to meet the requirement of high performance. Disclosure of Invention The invention aims to provide a doped ruthenium-based catalyst, and 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 doped ruthenium-based catalyst, which comprises ruthenium dioxide, transition metal and carbon doped in ruthenium dioxide crystal lattice; the transition metal includes a transition metal other than ruthenium; The transition metal and carbon form a transition metal carbide network. Preferably, the transition metal comprises at least one of molybdenum, chromium, tungsten, zirconium, titanium, and vanadium; The mol ratio of the transition metal to the ruthenium is 1:9-4:1; The molar ratio of the carbon to the ruthenium is 1:4-2:1. Preferably, the doped ruthenium-based catalyst has a rutile crystal structure; the particle size of the doped ruthenium-based catalyst is less than 10nm. The invention also provides a preparation method of the doped ruthenium-based catalyst, which comprises the following steps: The method comprises the steps of firstly mixing a ruthenium source, a transition metal source, glucose, urea and water, and drying an obtained foaming system to obtain a porous foam material, wherein the transition metal source is a transition metal source except the ruthenium source; P