CN-122013242-A - Preparation method and application of entropy metal oxide catalyst in zinc-doped ruthenium titanium tin zinc

Abstract

The invention belongs to the technical field of electrochemical catalysis, and particularly discloses a zinc-doped ruthenium-titanium-tin-zinc entropy metal oxide catalyst, wherein the catalyst is RuTiSnZnO x obtained by doping RuTiSnO x with Zn, and the doping mole ratio of Zn relative to the total amount of Ru, ti and Sn is 1.4-62.5%. The Zn doped catalyst has the advantages that the Zn doped catalyst is utilized to induce the surface of the catalyst to generate lattice defects and enable Ru atoms to form a charge-lacking state, and then the intermediate adsorption species of the electrochemical chlorine evolution reaction are regulated and controlled from Ru-O-Cl to Ru-Cl, so that the occurrence of the competition reaction of preparing oxygen by electrolyzed water is effectively inhibited, the chlorine evolution selectivity and the catalytic activity of the catalyst are obviously improved, the excellent stability is maintained under the industrial severe working condition, and compared with the unmodified RuTiSnO x catalyst, the Zn doped catalyst has more favorable initial potential and larger electrochemical activity area of the electrochemical Chlorine Evolution Reaction (CER), and the catalytic activity is obviously improved in the thermodynamic aspect.

Inventors

• LI JIANFENG
• PENG ZEYU
• WANG YAOHUI

Assignees

• 厦门大学

Dates

Publication Date

20260512

Application Date

20260210

Claims (10)

1. 1. The zinc-doped ruthenium-titanium-tin-zinc entropy metal oxide catalyst is RuTiSnZnO x obtained by doping RuTiSnO x with Zn, wherein the doping mole ratio of Zn relative to the total mole amount of Ru, ti and Sn is 1.4% -62.5%.
2. 2. The zinc-doped ruthenium titanium tin zinc intermediate entropy metal oxide catalyst according to claim 1, wherein the doping of Zn induces oxygen vacancy defects on the catalyst surface and places Ru atoms in electron-deficient state, causing the intermediate adsorbed species of CER reaction to be converted from Ru-O-Cl to Ru-Cl.
3. 3. The zinc-doped ruthenium titanium tin zinc intermediate entropy metal oxide catalyst of claim 1, wherein the catalyst is supported on a three-dimensional conductive substrate that is a chemically inert substrate material including, but not limited to, titanium plate, titanium felt, titanium foam.
4. 4. Use of a zinc-doped ruthenium titanium tin zinc entropy metal oxide catalyst according to any one of claims 1 to 3 in electrochemical chlorine evolution.
5. 5. A catalytic system for electrochemical chlorine evolution, characterized by comprising a zinc-doped ruthenium titanium tin zinc isentropic metal oxide catalyst according to any one of claims 1 to 3.
6. 6. A method for preparing the zinc-doped ruthenium titanium tin zinc entropy metal oxide catalyst according to any one of claims 1 to 3, comprising the following steps: (1) The substrate pretreatment, namely cleaning the three-dimensional conductive substrate in an organic solvent and an acid solution in sequence to remove the surface Organic and oxide compounds; (2) Preparing a precursor solution, namely dispersing metal salts containing Ru, sn and Zn in an organic solvent respectively, adding tetrabutyl titanate, and uniformly mixing to obtain the precursor solution; (3) And (3) loading and calcining, namely spraying the precursor solution obtained in the step (2) on the surface of the three-dimensional conductive substrate treated in the step (1) for a plurality of times, and drying and calcining after each spraying to obtain the catalyst RuTiSnZnO x .
7. 7. The method for preparing the entropy metal oxide catalyst in zinc-doped ruthenium-titanium-tin-zinc according to claim 6, wherein the acid solution in the step (1) is hydrochloric acid solution with the concentration of 3-9M, the cleaning temperature is 80-95 ℃, and the cleaning time is 20-40 min.
8. 8. The method for preparing the entropy metal oxide catalyst in zinc-doped ruthenium-titanium-tin-zinc according to claim 6, wherein the Ru-containing metal salt in the step (2) is RuCl 3 , the Sn-containing metal salt is SnCl 2 ·2H 2 O, and the Zn-containing metal salt is ZnCl 2 .
9. 9. The method for preparing an entropy metal oxide catalyst in zinc-doped ruthenium-titanium-tin-zinc according to claim 6, wherein in the precursor solution in the step (2), the content of Ru is 0.1-0.3 mmol, the content of Sn is 0.05-0.25: 0.25 mmol, the content of Zn is 0.01-0.15: 0.15 mmol, and the content of Ti is 0.09-0.18: 0.18 mmol in terms of metal elements.
10. 10. The method for preparing the zinc-doped ruthenium-titanium-tin-zinc entropy metal oxide catalyst according to claim 6, wherein the step (3) is performed by spraying for 2-6 times at a drying temperature of 80-120 ℃ for 5-15 min hours, the calcination is performed in an air atmosphere at 400-600 ℃ and each of the other calcination times is 10-20 min except for the last calcination time of 2-4 h.

Description

Preparation method and application of entropy metal oxide catalyst in zinc-doped ruthenium titanium tin zinc Technical Field The invention belongs to the technical field of electrochemical catalysis, and particularly relates to a zinc-doped enhanced electrochemical chlorine evolution catalyst, and a preparation method and application thereof. Background Chlorine (Cl 2) is used as a key basic chemical raw material, is widely applied to various industrial fields of organic synthesis, water treatment, metallurgy, polymer production and the like, has global annual demand of about 9000 ten thousand tons, has over 15000 derived chlorine-based chemicals, and has an irreplaceable supporting effect on the development of chemical industry. Industrial chlorine is mainly prepared by electrolyzing sodium chloride solution, chlorine molecules are generated by the oxidation reaction of chlorine ions generated at the anode in the process, and hydrogen and sodium hydroxide are generated at the cathode, so that a core process of the chlor-alkali industry is formed. However, the chlor-alkali electrolysis industry has the problem of high energy consumption, the annual power consumption is about 180TWh, and the total power consumption accounts for 0.8 percent of the total power consumption worldwide, so that the performance optimization of the electrolysis process has important significance for reducing the industrial cost and improving the economic benefit. The current commercial electrochemical Chlorine Evolution (CER) catalyst is mainly a Dimensionally Stable Anode (DSA), the core structure of the catalyst is a RuO 2-IrO2-TiO2 composite coating supported by a titanium plate, but the catalyst has the remarkable defects that the RuO 2 and the IrO 2 have high catalytic activity in competition reaction on CER, namely electrolytic water oxygen production (OER), so that the DSA has low chlorine selectivity in the CER process, and the improvement of the electrolytic efficiency is restricted. The prior study proves that the reaction of the intermediate adsorption species is a key factor for determining CER selectivity, and the adjustment of the intermediate adsorption species from Ru-O-Cl to Ru-Cl can effectively inhibit OER from occurring, thereby improving chlorine selectivity. However, the current technical system for realizing the regulation and control of the intermediate species is mainly concentrated on a single-atom catalyst, and the catalyst only stays in a laboratory research stage, cannot adapt to severe working conditions such as high current density, high-concentration electrolyte, strong acid environment and the like required by chlor-alkali industrial production, is difficult to realize long-term stable operation, and cannot meet the industrial application requirements. In summary, the existing CER catalyst has the inherent defect of low selectivity, and the targeted improvement scheme is limited by the technical bottleneck of insufficient industrial applicability. Therefore, development of a novel catalyst system with high CER selectivity, high catalytic activity and strong industrial adaptability is needed to break through the double bottleneck of the existing DSA material in terms of selectivity and stability. Disclosure of Invention The invention aims to overcome the defects of the prior art, and provides a zinc-doped enhanced electrochemical chlorine evolution catalyst, a preparation method and application thereof, wherein a RuTiSnZnO x catalyst is formed by doping RuTiSnO x of zinc element, the surface of the catalyst is induced to generate lattice defects by doping Zn, ru atoms form a charge-deficient state, and then the intermediate adsorption species of the electrochemical chlorine evolution reaction are regulated and controlled from Ru-O-Cl to Ru-Cl, so that the occurrence of the competition reaction of oxygen production by electrolysis water is effectively inhibited, the chlorine evolution selectivity and catalytic activity of the catalyst are obviously improved, and excellent stability is maintained under the severe industrial working condition. In order to achieve the aim, one of the technical schemes of the invention is that the zinc-doped ruthenium-titanium-tin-zinc entropy metal oxide catalyst is RuTiSnZnO x obtained by doping RuTiSnO x with Zn, and the doping mole ratio of Zn relative to the total mole amount of Ru, ti and Sn is 1.4-62.5%. Wherein x is the number of oxygen atoms satisfying charge balance. In a preferred embodiment of the invention, the doping of Zn causes oxygen vacancy defects to be formed on the surface of the catalyst, increases the electrochemical active area of the material, and causes Ru atoms to be in an electron-deficient state, so that an intermediate adsorption species of the electrochemical Chlorine Evolution (CER) reaction is converted from Ru-O-Cl to Ru-Cl, and the selectivity and activity of the chlorine evolution reaction are improved. The catalyst realizes the optimiza