The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO‐CeO2 Catalysts

• Published in: Angewandte Chemie International Edition Vol. 60; no. 26; pp. 14420 - 14428
• Main Authors: Kang, Liqun, Wang, Bolun, Güntner, Andreas T., Xu, Siyuan, Wan, Xuhao, Liu, Yiyun, Marlow, Sushila, Ren, Yifei, Gianolio, Diego, Tang, Chiu C., Murzin, Vadim, Asakura, Hiroyuki, He, Qian, Guan, Shaoliang, Velasco‐Vélez, Juan J., Pratsinis, Sotiris E., Guo, Yuzheng, Wang, Feng Ryan
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 21.06.2021; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: Absorption spectroscopy; Carbon; Carbon dioxide; Carbonyl compounds; Carbonyls; Catalysts; Cerium oxides; CO oxidation; Copper; Copper oxides; copper-ceria; electrophilicity; EMSI; Fine structure; Fourier transforms; Infrared spectroscopy; Metal oxides; Metals; Oxidation; Pressure; Redox reactions; Species; Surface chemistry; Synchrotrons; Ultrastructure
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202102570

Electronic metal–support interactions (EMSI) describe the electron flow between metal sites and a metal oxide support. It is generally used to follow the mechanism of redox reactions. In this study of CuO‐CeO2 redox, an additional flow of electrons from metallic Cu to surface carbon species is observed via a combination of operando X‐ray absorption spectroscopy, synchrotron X‐ray powder diffraction, near ambient pressure near edge X‐ray absorption fine structure spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy. An electronic metal–support–carbon interaction (EMSCI) is proposed to explain the reaction pathway of CO oxidation. The EMSCI provides a complete picture of the mass and electron flow, which will help predict and improve the catalytic performance in the selective activation of CO2, carbonate, or carbonyl species in C1 chemistry. During the oxidation of CO over the surface of a CuO‐CeO2 catalyst, electrons are simultaneously transferred from Cu0 to lattice Ce4+ and surface carbon species deposited from CO. These “electronic metal–support–carbon interactions” (EMSCI) are thought to play an important role in the reactions involving the support and surface carbon species in C1 chemistry.