Min Wang^a#, Huimin Chen^a#, Min Wang^b,  Jinxiu Wang^a, Yongxiao Tuo*^c, Wenzhen Li^d, Shanshan Zhou^a, Linghui Kong^a, Guangbo Liu^a, Luhua Jiang*^a, Guoxiong Wang*^e

^a Nanomaterials and Electrocatalysis Laboratory, College of Materials and Engineering, Qingdao University of Science and Technology, 53 Zhengzhou Road, Qingdao 266042, P. R. China

^b State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, P. R. China

^c State Key Laboratory of Heavy Oil Processing, College of New Energy, China University of Petroleum (East China), Qingdao, Shandong 266580, P. R. China

^d Department of Chemical & Biological Engineering, Iowa State University, Ames, IA 50011-1098, Unites States.

^e State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 P. R. China

* Corresponding author. E-mail addresses: yxtuo@upc.edu.cn (Y. Tuo); luhuajiang@qust.edu.cn (L. Jiang); wanggx@dicp.ac.cn (G. Wang)

^# These authors contribute equally to this work.

Abstract:

Heterostructured oxides with versatile active sites, as a class of efficient catalysts for CO₂ electrochemical reduction (CO₂ER), are prone to undergo structure reconstruction under working conditions, thus bringing challenges to understanding the reaction mechanism and rationally designing catalysts. Herein, we for the first time elucidate the structural reconstruction of CuO/SnO₂ under electrochemical potentials and reveal the intrinsic relationship between CO₂ER product selectivity and the in-situ evolved heterostructures. At -0.85 V_RHE, the CuO/SnO₂ evolves to Cu₂O/SnO₂ with high selectivity to formate (Faradaic efficiency of 54.81%). Mostly interestingly, it is reconstructed to Cu/SnO_2-x at -1.05 V_RHE with significantly improved Faradaic efficiency to ethanol of 39.8%. In-situ Raman spectra and density functional theory (DFT) calculations reveal that the synergetic absorption of *COOH and *CHOCO intermediates at the interface of Cu/SnO_2-x favors the formation of *CO and decreases the energy barrier of C-C coupling, leading to high selectivity to ethanol.

全文链接：https://doi.org/10.1002/anie.202306456