Si Doping-Induced Electronic Structure Regulation of Single-Atom Fe Sites for Boosted CO2 Electroreduction at Low Overpotentials
Changsheng Cao,
Shenghua Zhou,
Shouwei Zuo,
Huabin Zhang,
Bo Chen,
Junheng Huang,
Xin-Tao Wu,
Qiang Xu,
Qi-Long Zhu
Affiliations
Changsheng Cao
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
Shenghua Zhou
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
Shouwei Zuo
KAUST Catalysis Center (KCC),
King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.
Huabin Zhang
KAUST Catalysis Center (KCC),
King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.
Bo Chen
Department of Chemistry,
City University of Hong Kong, Hong Kong, 999077, China.
Junheng Huang
CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Provincial Key Laboratory of Nanomaterials, FujianInstitute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
Xin-Tao Wu
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
Qiang Xu
Institute for Integrated Cell-Material Sciences (iCeMS),
Kyoto University, Kyoto 606-8501, Japan.
Qi-Long Zhu
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
Transition metal-based single-atom catalysts (TM-SACs) are promising alternatives to Au- and Ag-based electrocatalysts for CO production through CO2 reduction reaction. However, developing TM-SACs with high activity and selectivity at low overpotentials is challenging. Herein, a novel Fe-based SAC with Si doping (Fe-N-C-Si) was prepared, which shows a record-high electrocatalytic performance toward the CO2-to-CO conversion with exceptional current density (>350.0 mA cm−2) and ~100% Faradaic efficiency (FE) at the overpotential of 90%) for CO production. Experimental combined with theoretical analysis unraveled that the nearby Si dopants in the form of Si-C/N bonds modulate the electronic structure of the atomic Fe sites in Fe-N-C-Si to markedly accelerate the key pathway involving *CO intermediate desorption, inhibiting the poisoning of the Fe sites under high CO coverage and thus boosting the CO2RR performance. This work provides an efficient strategy to tune the adsorption/desorption behaviors of intermediates on single-atom sites to improve their electrocatalytic performance.
