Nature of the Active Sites of Copper Zinc Catalysts for Carbon Dioxide Electroreduction

• Published in: Angewandte Chemie International Edition Vol. 61; no. 22; pp. e202201913 - n/a
• Main Authors: Zhen, Shiyu, Zhang, Gong, Cheng, Dongfang, Gao, Hui, Li, Lulu, Lin, Xiaoyun, Ding, Zheyuan, Zhao, Zhi‐Jian, Gong, Jinlong
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 23-05-2022
• Edition: International ed. in English
• Subjects: Carbon dioxide; Catalysts; Copper; CuZn Catalysts; Density Functional Theory; Electrochemical CO2 Reduction; Electrochemistry; Global Optimization; High-Throughput Calculations; Nanoparticles; Neural networks; Zinc; Global Optimization; High-Throughput Calculations; CuZn Catalysts; Electrochemical CO2 Reduction; Density Functional Theory
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202201913

The electrochemical CO2 reduction (CO2ER) to multi‐carbon chemical feedstocks over Cu‐based catalysts is of considerable attraction but suffers with the ambiguous nature of active sites, which hinder the rational design of catalysts and large‐scale industrialization. This paper describes a large‐scale simulation to obtain realistic CuZn nanoparticle models and the atom‐level structure of active sites for C2+ products on CuZn catalysts in CO2ER, combining neural network based global optimization and density functional theory calculations. Upon analyzing over 2000 surface sites through high throughput tests based on NN potential, two kinds of active sites are identified, balanced Cu−Zn sites and Zn‐heavy Cu−Zn sites, both facilitating C−C coupling, which are verified by subsequent calculational and experimental investigations. This work provides a paradigm for the design of high‐performance Cu‐based catalysts and may offer a general strategy to identify accurately the atomic structures of active sites in complex catalytic systems.
The synergistic effect between Cu and Zn enabling optimal adsorption of CO is reported. Through high throughput screening for optimal CO adsorption, two types of active sites were identified that effectively facilitated the C−C coupling, thus boosting the electroreduction of CO2 to C2+ products.