CO Intermediate‐Assisted Dynamic Cu Sintering During Electrocatalytic CO2 Reduction on Cu−N−C Catalysts

• Published in: Angewandte Chemie International Edition Vol. 63; no. 23; pp. e202404763 - n/a
• Main Authors: Qin, Yanyang, Zhao, Wenshan, Xia, Chenfeng, Yu, Li‐Juan, Song, Fei, Zhang, Jianrui, Wu, Tiantian, Cao, Rui, Ding, Shujiang, Xia, Bao Yu, Su, Yaqiong
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 03.06.2024
• Edition: International ed. in English
• Subjects: Carbon dioxide; Catalyst stability; Catalysts; Chemical reduction; Clusters; CO2 reduction reaction; Density functional theory; Dynamic sintering; Electrocatalysts; Electrochemistry; Intermediates; Leaching; Molecular dynamics; Sintering
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202404763

The electrochemical CO2 reduction reaction (eCO2RR) to multicarbon products has been widely recognized for Cu‐based catalysts. However, the structural changes in Cu‐based catalysts during the eCO2RR pose challenges to achieving an in‐depth understanding of the structure–activity relationship, thereby limiting catalyst development. Herein, we employ constant‐potential density functional theory calculations to investigate the sintering process of Cu single atoms of Cu−N−C single‐atom catalysts into clusters under eCO2RR conditions. Systematic constant‐potential ab initio molecular dynamics simulations revealed that the leaching of Cu−(CO)x moieties and subsequent agglomeration into clusters can be facilitated by synergistic adsorption of H and eCO2RR intermediates (e.g., CO). Increasing the Cu2+ concentration or the applied potential can efficiently suppress Cu sintering. Both microkinetic simulations and experimental results further confirm that sintered Cu clusters play a crucial role in generating C2 products. These findings provide significant insights into the dynamic evolution of Cu‐based catalysts and the origin of their activity toward C2 products during the eCO2RR. A novel pathway involving the evolution of Cu−(CO)x moieties driven by the synergistic adsorption of CO and H was identified for dynamic Cu sintering in Cu−N−C catalysts under CO2 reduction conditions.