Boosting the activity of Fe-Nx moieties in Fe-N-C electrocatalysts via phosphorus doping for oxygen reduction reaction

P掺杂提高Fe–N–C催化剂中Fe–Nx活性基团的氧还原催化活性

Abstract

The Fe-N-C material is a promising non-noble-metal electrocatalyst for oxygen reduction reaction (ORR). Further improvement on the ORR activity is highly desired in order to replace Pt/C in acidic media. Herein, we developed a new-type of single-atom Fe-N-C electrocatalyst, in which Fe-Nx active sites were modified by P atoms. The half-wave potential of the optimized material reached 0.858 V, which is 23 mV higher than that of the pristine one in a 0.1 mol L−1 HClO4 solution. Density functional theory (DFT) calculations revealed that P doping can reduce the thermodynamic over potential of the rate determining step and consequently improve the ORR activity.

摘要

Fe–N–C材料是一类有前景的非贵金属氧还原催化剂. 为了在酸性介质中取代Pt/C催化剂, 需要大幅度地改善其氧还原催化活性. 本文提出一种通过P原子掺杂的方法来调节单原子Fe–N–C材料中Fe–Nx活性位点的活性. 优化得到的材料在0.1 mol L−1 HClO4溶液中表现出优异的氧还原性能, 其半波电位为0.858 V(比没有P掺杂的Fe–N–C材料高23 mV). 密度泛函理论计算表明, P掺杂能降低限制步骤的热力学过电位, 从而提高其氧还原催化活性.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2017YFB0102900), the Research Grant Council (N_HKUST610117) of Hong Kong Special Administrative Region. It used resources of the Advanced Photon Source, Office of Science user facilities, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (DE-AC02-06CH11357). Lin Y would like to acknowledge the WSU start-up fund. Li T is thankful for the NIU start-up fund.

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Contributions

Author contributions Li JC, Shao M, and Lin Y designed the experiments; Li JC, Zhong H, Xu M, Li T, Wang L, Shi Q, Feng S, Lyu Z, Liu D, Du D, Beckman SP, and Pan X performed the experiments and data analysis; Li JC, Shao M, and Lin Y wrote the manuscript. All authors contributed to the general discussion, reviewed and revised the manuscript.

Corresponding authors

Correspondence to Yuehe Lin 林跃河 or Minhua Shao 邵敏华.

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The authors declare that they have no conflict of interest.

Jin-Cheng Li received his PhD degree in materials science in 2017 from the Institute of Metal Research, Chinese Academy of Sciences. He is now a postdoctoral researcher in the Hong Kong University of Science and Technology. His research mainly focuses on electrocatalysis, fuel cells, and metal-air batteries.

Yuehe Lin is a professor at Washington State University, a Laboratory Fellow of Pacific Northwest National Laboratory, and a fellow of the American Association for the Advancement of Science, Royal Society of Chemistry and American Institute of Medical and Biological Engineering. He has been actively working in the nano-technology area, particularly in the synthesis of functional nanomaterials for energy and environmental applications and new bioelectronic devices for biomedical diagnosis and drug delivery.

Minhua Shao earned his PhD degree in materials science and engineering from the State University of New York at Stony Brook (2006). He is now an Associate Professor in the Department of Chemical and Biological Engineering and Associate Director of Energy Institute of the Hong Kong University of Science and Technology. His research mainly focuses on electrocatalysis, fuel cells, and advanced batteries.

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Li, J., Zhong, H., Xu, M. et al. Boosting the activity of Fe-Nx moieties in Fe-N-C electrocatalysts via phosphorus doping for oxygen reduction reaction. Sci. China Mater. 63, 965–971 (2020). https://doi.org/10.1007/s40843-019-1207-y

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Keywords

  • P-doping
  • single-atom catalysts
  • oxygen reduction