CN-122013249-A - Copper metal complex for electrocatalytic water oxidation reaction and preparation method thereof

CN122013249ACN 122013249 ACN122013249 ACN 122013249ACN-122013249-A

Abstract

Copper metal complex for electrocatalytic water oxidation and a preparation method and application thereof, which belong to the technical field of new materials. The catalyst shows good catalytic performance in the electrocatalytic water oxidation reaction, and in electrochemical test, the catalyst shows good catalytic activity, can be electrolyzed for 2 hours under the voltage of 0.2 mA cm ‑2 of current density, the water oxidation initiation potential is 1.048V vs. NHE (vs. NHE relative to a reversible hydrogen electrode), and the voltage reaching 1 mA cm ‑2 is 1.586V vs. NHE, and the overpotential is 359.7 mV. The method provided by the invention has the advantages of simple operation, high safety, mild reaction conditions and environment-friendly process.

Inventors

WU XIUJUAN
WANG CHUNLAI
ZHAO JIE
ZHENG YE

Assignees

大连理工大学

Dates

Publication Date: 20260512
Application Date: 20260320

Claims (6)

1. The copper metal complex for electrocatalytic water oxidation reaction is characterized in that the structural formula of the complex is as follows: 。
2. the method for preparing a copper metal complex for electrocatalytic water oxidation reaction according to claim 1, comprising the steps of: s1, adding copper perchlorate hexahydrate into anhydrous methanol of diethylenetriamine ligand, stirring at room temperature, and filtering to obtain blue solid; the molar ratio of the copper perchlorate hexahydrate to the diethylenetriamine ligand is 1:2; s2, dissolving with acetonitrile solvent to obtain blue solution, adding diethyl ether to precipitate solid, and drying the obtained solid in an oven to obtain the copper metal complex.
3. Use of a copper metal complex for electrocatalytic water oxidation reactions according to claim 1, characterized in that: the copper metal complex is applied to electrocatalytic water oxidation reaction.
4. Use according to claim 3, wherein the electrolyte in the electrocatalytic water oxidation reaction is 0.1M potassium nitrate in water.
5. The use according to claim 3, wherein the electrolytic potential applied during the reaction is 1.56V vs. NHE.
6. Use according to claim 3, characterized in that the concentration of catalyst added to the homogeneous system is 0.4-0.8 mmol/L.

Description

Copper metal complex for electrocatalytic water oxidation reaction and preparation method thereof Technical Field The invention belongs to the technical field of new materials, and particularly discloses a metal-organic complex catalyst which is concise, efficient and green at a lower temperature and is constructed based on diethylenetriamine organic ligands, a preparation method and application thereof in electrocatalytic water oxidation. Background The two problems of environmental pollution and energy crisis are particularly serious nowadays, and finding clean energy has been an important task for economic and social development. Among the many known green clean energy sources, hydrogen is a good choice, mainly because hydrogen has the characteristics of high energy density, easy storage and only water generation after combustion, and also because of the characteristics, hydrogen is the first choice to replace the traditional energy source. The current method for obtaining hydrogen is a technology which is developed and mature at present and has a great development prospect, but the reaction rate is slow due to the high thermodynamic energy required in the process of oxygen evolution reaction of the anode, and the method is the biggest problem in the water electrolysis reaction, so that the development of a catalyst with good catalytic effect and stable catalysis is particularly important, and is also the key for improving the water electrolysis efficiency. Disclosure of Invention In order to solve the problems in the prior art, the invention provides a copper metal complex, a preparation method and application thereof in electrocatalytic water oxidation reaction. The technical scheme adopted by the invention is that the copper metal complex for electrocatalytic water oxidation reaction has the structural formula: 。 The preparation method of the copper metal complex for electrocatalytic water oxidation reaction comprises the following steps: s1, adding copper perchlorate hexahydrate into anhydrous methanol of diethylenetriamine ligand, stirring at room temperature, and filtering to obtain blue solid; the molar ratio of the copper perchlorate hexahydrate to the diethylenetriamine ligand is 1:2; s2, dissolving with acetonitrile solvent to obtain blue solution, adding diethyl ether to precipitate solid, and drying the obtained solid in an oven to obtain the copper metal complex. Further, the copper metal complex is applied to electrocatalytic water oxidation reaction. Further, the electrolyte in the electrocatalytic water oxidation reaction was 0.1M potassium nitrate aqueous solution. Further, the electrolytic potential applied during the reaction was 1.56V vs. NHE. Further, the concentration of the catalyst added into the homogeneous system is The raw materials selected by the invention are diethylenetriamine as a ligand and copper perchlorate hexahydrate, and the obtained copper metal complex catalyst shows good catalytic performance in the reaction of electrocatalytic water oxidation, can be electrolyzed for 2 hours under the voltage of 0.2 mA cm -2 of current density, has the water oxidation initiation potential of 1.048V vs. NHE (vs. NHE relative to a reversible hydrogen electrode), and has the voltage of 1.586. 1.586V vs of mA cm -2 and the overpotential of 359.7 mV. Meanwhile, the method provided by the invention is simple to operate, high in safety, mild in reaction condition and environment-friendly in process, and the defects and problems that the use of a strong oxidant in the traditional chemical oxidation process, the generation of waste which is difficult to treat, the emission of a large amount of greenhouse gases and the like do not accord with the environment-friendly chemical production concept can be effectively avoided. The molecular formula of the copper metal complex is [ Cu (DETA) 2 ], wherein Cu is a divalent ion, DETA is a diethylenetriamine organic ligand, and the chemical structural formula is as follows: The preparation method of the copper metal complex comprises the following steps: Copper perchlorate hexahydrate (0.371 g,1.0 mm) was slowly added to 3 mL anhydrous methanol in which 0.206 g (2.0 mmol) DETA ligand was dissolved, stirred at room temperature for 20 h, filtered to give a blue solid, then the blue solid was dissolved with 5mL acetonitrile solvent to form a blue solution, followed by filtration in 20 mL diethyl ether solution, and the obtained solid was dried in an oven for 10 h, followed by 0.430 g blue metal complex Cu (DETA) 2 in 90% yield. The conditions during the catalytic synthesis are that the pH is neutral, and the reaction is carried out under stirring, ultrasonic or vibration state at room temperature. The copper metal complex catalyst prepared by the invention has good catalytic performance in the electrocatalytic water oxidation reaction, can be electrolyzed for 2 hours under the voltage with the current density of 0.2 mA cm -2 , has the water oxidation