Si Doping-Induced Electronic Structure Regulation of Single-Atom Fe Sites for Boosted CO2 Electroreduction at Low Overpotentials

Cao，Changsheng1; Zhou，Shenghua1,2; Zuo，Shouwei3; Zhang，Huabin3; Chen，Bo4; Huang，Junheng5; Wu，Xin Tao1,2,6; Xu，Qiang7,8; Zhu，Qi Long1,2,6

2023

10.34133/research.0079

Research   Impact Factor & Quartile

2096-5168

2639-5274

Transition metal-based single-atom catalysts (TM-SACs) are promising alternatives to Au- and Ag-based electrocatalysts for CO production through CO 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 CO-to-CO conversion with exceptional current density (>350.0mAcm) and~100% Faradaic efficiency (FE) at the overpotential of <400 mV, far superior to the reported Fe-based SACs. Further assembling Fe-N-C-Si as the cathode in a rechargeable Zn-CO battery delivers an outstanding performance with a maximal power density of 2.44 mW cm at an output voltage of 0.30 V, as well as high cycling stability and FE (>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 CORR performance. This work provides an efficient strategy to tune the adsorption/desorption behaviors of intermediates on single-atom sites to improve their electrocatalytic performance.

SCI

English

Others

Natural Science Foundation of Fujian Province[2020J01116];Natural Science Foundation of Fujian Province[2021J06033];China Postdoctoral Science Foundation[2021M703215];China Postdoctoral Science Foundation[2021TQ0332];National Key Research and Development Program of China[2021YFA1500402];National Natural Science Foundation of China[22105203];National Natural Science Foundation of China[22175174];

WOS:000928828300001

2-s2.0-85152122939

Scopus

1.State Key Laboratory of Structural Chemistry,Fujian Institute of Research,the Structure of Matter,Chinese Academy of Sciences,Fuzhou,350002,China
2.University of Chinese Academy of Science,Beijing,100049,China
3.KAUST Catalysis Center (KCC),King Abdullah University of Science and Technology (KAUST),Thuwal,23955-6900,Saudi Arabia
4.Department of Chemistry,City University of Hong Kong,Hong Kong,999077,Hong Kong
5.CAS Key Laboratory of Design and Assembly of Functional Nanostructures,Fujian Provincial Key Laboratory of Nanomaterials,FujianInstitute of Research,The Structure of Matter,Chinese Academy of Sciences,Fuzhou,350002,China
6.Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou,350108,China
7.Institute for Integrated Cell-Material Sciences (iCeMS),Kyoto University,Kyoto,606-8501,Japan
8.Shenzhen Key Laboratory of Micro/ Nano-Porous Functional Materials (SKLPM),SUSTech-Kyoto University Advanced Energy Materials Joint Innovation Laboratory (SKAEM-JIL),Department of Materials Science and Engineering,Southern University of Science and Technology (SUSTech),Shenzhen,518055,China

Cao，Changsheng,Zhou，Shenghua,Zuo，Shouwei,et al. Si Doping-Induced Electronic Structure Regulation of Single-Atom Fe Sites for Boosted CO2 Electroreduction at Low Overpotentials[J]. Research,2023,6.

Cao，Changsheng.,Zhou，Shenghua.,Zuo，Shouwei.,Zhang，Huabin.,Chen，Bo.,...&Zhu，Qi Long.(2023).Si Doping-Induced Electronic Structure Regulation of Single-Atom Fe Sites for Boosted CO2 Electroreduction at Low Overpotentials.Research,6.

Cao，Changsheng,et al."Si Doping-Induced Electronic Structure Regulation of Single-Atom Fe Sites for Boosted CO2 Electroreduction at Low Overpotentials".Research 6(2023).