Operando evidence of Cu+ stabilization via a single-atom modifier for CO2 electroreduction

• Published in: Journal of materials chemistry. A, Materials for energy and sustainability Vol. 8; no. 48; pp. 25970 - 25977
• Main Authors: Zhang, Wei, He, Peng, Wang, Chao, Ding, Tao, Chen, Tao, Liu, Xiaokang, Cao, Linlin, Huang, Tianming, Shen, Xinyi, Usoltsev, Oleg A, Bugaev, Aram L, Lin, Yue, Yao, Tao
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 01.01.2020
• Subjects: Absorption spectroscopy; adsorption; Carbon dioxide; Carbon monoxide; Catalysts; Charge transfer; Chemical reduction; Copper; Copper oxides; Electrocatalysts; Electrowinning; Infrared spectroscopy; nanosheets; oxygen; Selectivity; Species; Spectrum analysis; Statistical analysis; statistics; Synchrotron radiation; Synchrotrons; Tin; X ray absorption; X-ray absorption spectroscopy
• ISSN: 2050-7488; 2050-7496; 2050-7496
• DOI: 10.1039/d0ta08369k

Oxide-derived Cu materials are most commonly used as electrocatalysts for the carbon dioxide reduction reaction (CO2RR). Previous studies have proved that Cu+ and residual subsurface oxygen species can enhance the CO2RR activity; however the stable presence of Cu+ remains a subject of debate. Here, we design a strategy of single-atom Sn anchored on Cu2O nanosheets to stabilize the key Cu+ species for electroreduction of CO2. Operando synchrotron X-ray absorption spectroscopy and statistics analysis distinguish the active Cu+ and reduced Cu+ species, and reveal that the constructed Sn–O–Cu sites with charge transfer can significantly enhance the resistance of copper oxides to reduction. Operando infrared spectroscopy suggests that the survival of Cu+ species on the catalyst surface promotes the adsorption of *CO during the CO2RR, leading to the obvious improvement of CO2-to-CO conversion. Our results demonstrate the role of a single-atom-modifier in both stabilizing Cu+ species and enhancing the CO2RR selectivity of oxide-derived Cu catalysts.