Crystal Facet‐Dependent Metal‐Support Interaction for Stabilizing Cu <sup>δ+</sup> Species Toward Efficient CO <sub>2</sub> Electroreduction
Abstract
ABSTRACT Cu δ+ species are recognized as optimal active sites for the electrocatalytic CO 2 reduction reaction. While metal‐support interactions (MSIs) modulate the local microenvironment of Cu δ+ , the intrinsic contribution of support crystallographic facets to these interactions remains obscured by interfering oxygen vacancies. In this work, we present a definitive study decoupling the facet effect from vacancy‐related variables by utilizing CeO 2 supports with comparable oxygen vacancy concentrations. Our findings reveal that Cu single atoms supported on various CeO 2 facets follow a pronounced facet‐dependent stability order of Cu/CeO 2 ‐(110) > Cu/CeO 2 ‐(100) > Cu/CeO 2 ‐(111), yet exhibit facet‐independent methane Faraday efficiency (∼80% at −200 mA/cm 2 ). Mechanistic studies unravel this dichotomy, revealing that identical Cu coordination environments drive the uniform initial activity, whereas distinct surface electronic structures dictate long‐term stability by modulating facet‐dependent MSIs. Specifically, the (110) facet exhibits the strongest MSI, acting as a robust “electron buffer” that securely anchors high‐valent Cu δ+ species and effectively retards their irreversible reductive agglomeration into clusters. By establishing an unambiguous structure–performance relationship under single‐variable conditions, this study provides a rational geometric descriptor for designing long‐lasting CO 2 conversion catalysts.
Article Details
Authors (13)
Airong Xu
School of Nuclear Science and Technology Key Laboratory of Precision and Intelligent Chemistry Hefei National Research Center for Physical Sciences at the Microscale National Synchrotron Radiation Laboratory University of Science and Technology of China Hefei P.R. China
Lanyue Zhang
Yuanhua Sun
School of Nuclear Science and Technology Key Laboratory of Precision and Intelligent Chemistry Hefei National Research Center for Physical Sciences at the Microscale National Synchrotron Radiation Laboratory University of Science and Technology of China Hefei P.R. China
Hui Huang
Center of Basic Molecular Science (CBMS), Department of Chemistry
Wenzhi Li
Mengyuan Liu
Shuaiwei Jiang
School of Nuclear Science and Technology Key Laboratory of Precision and Intelligent Chemistry Hefei National Research Center for Physical Sciences at the Microscale National Synchrotron Radiation Laboratory University of Science and Technology of China Hefei P.R. China
Longfei Hu
Xiaokang Liu
State Key Laboratory of Geomicrobiology and Environmental Changes, School of Earth Sciences, China University of Geosciences
Mei Sun
Dong Liu
Hefei National Research Center for Physical Sciences at the Microscale, School of Chemistry and Materials Science, National Synchrotron Radiation Laboratory
Tao Ding
Tao Yao
National Synchrotron Radiation Laboratory, State Key Laboratory of Precision and Intelligent Chemistry, School of Nuclear Science and Technology