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

Liqun Kang; Bolun Wang; Andreas T Güntner; Siyuan Xu; Xuhao Wan; Yiyun Liu; Sushila Marlow; Yifei Ren; Diego Gianolio; Chiu C Tang; Vadim Murzin; Hiroyuki Asakura; Qian He; Shaoliang Guan; Juan J Velasco-Vélez; Sotiris E Pratsinis; Yuzheng Guo; Feng Ryan Wang

doi:10.1002/anie.202102570

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

Angew Chem Int Ed Engl. 2021 Jun 21;60(26):14420-14428. doi: 10.1002/anie.202102570. Epub 2021 Apr 8.

Authors

Liqun Kang¹, Bolun Wang¹, Andreas T Güntner², Siyuan Xu³, Xuhao Wan³, Yiyun Liu¹, Sushila Marlow¹, Yifei Ren¹, Diego Gianolio⁴, Chiu C Tang⁴, Vadim Murzin⁵, Hiroyuki Asakura⁶, Qian He⁷, Shaoliang Guan⁸, Juan J Velasco-Vélez⁹, Sotiris E Pratsinis², Yuzheng Guo³, Feng Ryan Wang¹

Affiliations

¹ Department of Chemical Engineering, University College London, London, WC1E 7JE, UK.
² Particle Technology Laboratory, Institute of Process Engineering, Department of Mechanical and Process Engineering, ETH Zürich, 8092, Zürich, Switzerland.
³ School of Electrical Engineering and Automation, Wuhan University, Wuhan, China.
⁴ Diamond Light Source Ltd, Harwell Science and Innovation Campus, Didcot, Oxfordshire, OX11 0DE, UK.
⁵ Deutsches Elektronen Synchrotron DESY, 22607, Hamburg, Germany.
⁶ Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyotodaigaku Katsura, Nishikyo-ku, Kyoto 6158510, Japan.
⁷ Department of Materials Science and Engineering, National University of Singapore, Singapore, 117575, Singapore.
⁸ HarwellXPS-The EPSRC National Facility for Photoelectron Spectroscopy, Research Complex at Harwell (RCaH), Didcot, OX11 0FA, UK.
⁹ Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195, Berlin, Germany.

Abstract

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.

Keywords: CO oxidation; EMSI; copper-ceria; electrophilicity; surface chemistry.

Abstract

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