Regulating the d-band electrons of the Fe-N-C single-atom catalyst for high-efficiency CO2 electroreduction by electron-donating S-doping

Yiqun Chen; Qinghua Gong; Xuefeng Sun; Guochang Li; Guowei Zhou

doi:10.1039/d3dt00394a

Regulating the d-band electrons of the Fe-N-C single-atom catalyst for high-efficiency CO₂ electroreduction by electron-donating S-doping

Dalton Trans. 2023 Apr 11;52(15):4819-4825. doi: 10.1039/d3dt00394a.

Authors

Yiqun Chen^{1

2}, Qinghua Gong^{2

3}, Xuefeng Sun³, Guochang Li¹, Guowei Zhou³

Affiliations

¹ School of Materials Science and Chemical Engineering, Ningbo University, Ningbo, 315211, P.R. China. liguochang@nbu.edu.cn.
² School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, P.R. China.
³ Key Laboratory of Fine Chemicals in Universities of Shandong, Jinan Engineering Laboratory for Multi-scale Functional Materials, School of Chemistry and Chemical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250353, P. R. China. gwzhou@qlu.edu.cn.

PMID: 36939161
DOI: 10.1039/d3dt00394a

Abstract

Developing highly efficient electrocatalysts is crucially significant for the application of advanced energy conversion. The Fe-N-C single-atom catalyst is promising for CO₂ electroreduction reaction (CO₂RR) but suffers from insufficient intrinsic activity and inferior conductivity, which could be addressed by redistributing the electron density via heteroatom doping. Herein, we synthesized S-doped Fe-N-C (Fe-SN-C) as an advanced electrocatalyst for CO₂RR using a simple trapping-pyrolysis strategy. Density functional theory calculations and experimental results indicate that S doping increases the d-band electrons and conductivity of Fe-SN-C by electron donating, and thus boosts *CO desorption during the CO₂RR process and suppresses the competing hydrogen evolution reaction. Consequently, Fe-SN-C exhibits the maximum CO faradaic efficiency of 93% at -0.5 V and the highest partial current density of 10.1 mA cm^-2 at -0.8 V for 2e^- CO₂RR. This finding provides a feasible and controllable method to achieve advanced electrocatalysts for efficient energy conversion.