Tuning C1 /C2 Selectivity of CO2 Electrochemical Reduction over in-Situ Evolved CuO/SnO2 Heterostructure

Min Wang; Huimin Chen; Min Wang; Jinxiu Wang; Yongxiao Tuo; Wenzhen Li; Shanshan Zhou; Linghui Kong; Guangbo Liu; Luhua Jiang; Guoxiong Wang

doi:10.1002/anie.202306456

Tuning C₁ /C₂ Selectivity of CO₂ Electrochemical Reduction over in-Situ Evolved CuO/SnO₂ Heterostructure

Angew Chem Int Ed Engl. 2023 Oct 2;62(40):e202306456. doi: 10.1002/anie.202306456. Epub 2023 Aug 25.

Authors

Min Wang¹, Huimin Chen¹, Min Wang², Jinxiu Wang¹, Yongxiao Tuo³, Wenzhen Li⁴, Shanshan Zhou¹, Linghui Kong¹, Guangbo Liu¹, Luhua Jiang¹, Guoxiong Wang⁵

Affiliations

¹ Nanomaterials and Electrocatalysis Laboratory, College of Materials Science and Engineering, Qingdao University of Science and Technology, 53 Zhengzhou Road, Qingdao, 266042, P. R. China.
² 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.
³ State Key Laboratory of Heavy Oil Processing, College of New Energy, China University of Petroleum (East China), Qingdao, Shandong, 266580, P. R. China.
⁴ Department of Chemical & Biological Engineering, Iowa State University, Ames, IA 50011-1098, USA.
⁵ 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.

PMID: 37485764
DOI: 10.1002/anie.202306456

Abstract

Heterostructured oxides with versatile active sites, as a class of efficient catalysts for CO₂ electrochemical reduction (CO₂ ER), 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 CO₂ ER product selectivity and the in situ evolved heterostructures. At -0.85 V_RHE , the CuO/SnO₂ evolves to Cu₂ O/SnO₂ with high selectivity to HCOOH (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.

Keywords: CO2 Electrochemical Reduction; DFT Calculations; Heterostructure; Selectivity to Ethanol; in-Situ Characterization.

Abstract

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