Tuning Structural and Electronic Configuration of FeN₄ via External S for Enhanced Oxygen Reduction Reaction

Shidong Li^¹, Lixue Xia^¹, Jiantao Li^⁴, Zhuo Chen^¹, Wei Zhang^¹, Jiexin Zhu^¹, Ruohan Yu^⁵, Fang Liu^⁵, Sungsik Lee^⁶, Yan Zhao^{⁷^,⁸}

(), Liang Zhou^{¹^,²^,³}

(), Liqiang Mai^{¹^,²^,³}()

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China

Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory, Foshan 528200, China

Hubei Longzhong Laboratory, Xiangyang 441000, China

Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, IL 60439, USA

NRC (Nanostructure Research Centre), Wuhan University of Technology, Wuhan 430070, China

X-ray Science Division, Advanced Photon Sources, Argonne National Laboratory, 9700 South Cass, Avenue, Lemont, IL 60439, USA

State Key Laboratory of Silicate Materials for Architectures, International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China

The Institute of Technological Sciences, Wuhan University, Wuhan 430072, China

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Abstract

The Fe–N–C material represents an attractive oxygen reduction reaction electrocatalyst, and the FeN₄ moiety has been identified as a very competitive catalytic active site. Fine tuning of the coordination structure of FeN₄ has an essential impact on the catalytic performance. Herein, we construct a sulfur-modified Fe–N–C catalyst with controllable local coordination environment, where the Fe is coordinated with four in-plane N and an axial external S. The external S atom affects not only the electron distribution but also the spin state of Fe in the FeN₄ active site. The appearance of higher valence states and spin states for Fe demonstrates the increase in unpaired electrons. With the above characteristics, the adsorption and desorption of the reactants at FeN₄ active sites are optimized, thus promoting the oxygen reduction reaction activity. This work explores the key point in electronic configuration and coordination environment tuning of FeN₄ through S doping and provides new insight into the construction of M–N–C-based oxygen reduction reaction catalysts.

Keywords

coordination structure electronic configuration FeN₄ moiety oxygen reduction reaction sulfur doping

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References

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M. Escudero-Escribano, P. Malacrida, M. H. Hansen, U. G. Vej-Hansen, A. Velázquez-Palenzuela, V. Tripkovic, J. Schiøtz, J. Rossmeisl, I. E. L. Stephens, I. Chorkendorff, Science 2016, 352, 73.

Tuning Structural and Electronic Configuration of FeN4 via External S for Enhanced Oxygen Reduction Reaction

Abstract

Keywords

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References

Tuning Structural and Electronic Configuration of FeN₄ via External S for Enhanced Oxygen Reduction Reaction