Wang Shifu, Li Fuhua, Zhao Jian, Zeng Yaqiong, Li Yifan, Lin Zih-Yi, Lee Tsung-Ju, Liu Shuhui, Ren Xinyi, Wang Weijue, Chen Yusen, Hung Sung-Fu, Lu Ying-Rui, Cui Yi, Yang Xiaofeng, Li Xuning, Huang Yanqiang, Liu Bin
Department of Chemical Physics, University of Science and Technology of China, Hefei, 230026, P. R. China.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, P. R. China.
Nat Commun. 2024 Nov 26;15(1):10247. doi: 10.1038/s41467-024-54636-w.
Manipulation C-C coupling pathway is of great importance for selective CO electroreduction but remain challenging. Herein, two model Cu-based catalysts, by modifying Cu nanowires with Ag nanoparticles (AgCu NW) and Ag single atoms (AgCu NW), respectively, are rationally designed for exploring the C-C coupling mechanisms in electrochemical CO reduction reaction (CORR). Compared to AgCu NW, the AgCu NW exhibits a more than 10-fold increase of C selectivity in CO reduction to ethanol, with ethanol-to-ethylene ratio increased from 0.41 over AgCu NW to 4.26 over AgCu NW. Via a variety of operando/in-situ techniques and theoretical calculation, the enhanced ethanol selectivity over AgCu NW is attributed to the promoted HO dissociation over the atomically dispersed Ag sites, which effectively accelerated *CO hydrogenation to form *CHO intermediate and facilitated asymmetric *CO-*CHO coupling over paired Cu atoms adjacent to single Ag atoms. Results of this work provide deep insight into the C-C coupling pathways towards target C product and shed light on the rational design of efficient CORR catalysts with paired active sites.
操纵C-C偶联途径对于选择性CO电还原非常重要，但仍然具有挑战性。在此，通过分别用Ag纳米颗粒（AgCu NW）和Ag单原子（AgCu NW）修饰Cu纳米线，合理设计了两种基于Cu的模型催化剂，用于探索电化学CO还原反应（CORR）中的C-C偶联机制。与AgCu NW相比，AgCu NW在CO还原为乙醇的过程中C选择性提高了10倍以上，乙醇与乙烯的比例从AgCu NW上的0.41增加到AgCu NW上的4.26。通过各种原位/非原位技术和理论计算，AgCu NW上乙醇选择性的提高归因于原子分散的Ag位点上HO解离的促进，这有效地加速了CO氢化形成CHO中间体，并促进了与单个Ag原子相邻的成对Cu原子上的不对称*CO-*CHO偶联。这项工作的结果为通向目标C产物的C-C偶联途径提供了深入的见解，并为具有成对活性位点的高效CORR催化剂的合理设计提供了启示。
