Probing the Roles of Indium Oxides on Copper Catalysts for Enhanced Selectivity during CO2-to-CO Electrochemical Reduction

Yanyan Jia; Hua-Shan Hsu; Wan-Chun Huang; Da-Wei Lee; Sheng-Wei Lee; Tsan-Yao Chen; Lihui Zhou; Jeng-Han Wang; Kuan-Wen Wang; Sheng Dai

doi:10.1021/acs.nanolett.2c04925

Probing the Roles of Indium Oxides on Copper Catalysts for Enhanced Selectivity during CO₂-to-CO Electrochemical Reduction

Nano Lett. 2023 Mar 22;23(6):2262-2268. doi: 10.1021/acs.nanolett.2c04925. Epub 2023 Mar 13.

Authors

Yanyan Jia¹, Hua-Shan Hsu², Wan-Chun Huang³, Da-Wei Lee³, Sheng-Wei Lee³, Tsan-Yao Chen^{4

5}, Lihui Zhou¹, Jeng-Han Wang², Kuan-Wen Wang³, Sheng Dai¹

Affiliations

¹ Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China.
² Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan.
³ Institute of Materials Science and Engineering, National Central University, Taoyuan 320, Taiwan.
⁴ Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, Taiwan.
⁵ Hierarchical Green-Energy Materials (Hi-GEM) Research Center, National Cheng Kung University, Tainan 70101, Taiwan.

PMID: 36913488
DOI: 10.1021/acs.nanolett.2c04925

Abstract

The electrochemical CO₂ reduction reaction (CO₂RR) provides an alternative protocol to producing industrial chemicals with renewable electricity sources, and the highly selective, durable, and economic catalysts should expedite CO₂RR applications. Here, we demonstrate a composite Cu-In₂O₃ catalyst in which a trace amount of In₂O₃ decorated on Cu surface greatly improves the selectivity and stability for CO₂-to-CO reduction as compared to the counterparts (Cu or In₂O₃), realizing a CO faradaic efficiency (FE_CO) of 95% at -0.7 V (vs RHE) and no obvious degradation within 7 h. In situ X-ray absorption spectroscopy reveals that In₂O₃ undergoes the redox reaction and preserves the metallic state of Cu during the CO₂RR process. Strong electronic interaction and coupling occur at the Cu/In₂O₃ interface which serves as the active site for selective CO₂RR. Theoretical calculation confirms the roles of In₂O₃ in preventing oxidation and altering the electronic structure of Cu to assist COOH* formation and demote CO* adsorption at the Cu/In₂O₃ interface.

Keywords: CO2RR; copper; density functional theory; in situ X-ray absorption spectroscopy; indium oxide.