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How the microenvironment dominated by the distance effect to regulate the FeN4 site ORR activity and selectivity?

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Abstract

The distance effect of the doped heteroatoms away from the catalytic centers has rarely been reported. In this work, we conducted density functional theory calculations to thoroughly investigate the influence of heteroatom (N, P, B, and S atoms) doping distance on the oxygen reduction reaction (ORR) activity of graphene-based FeN4 sites. We uncovered a Sabatier-like relationship between heteroatom doping distance and ORR activity of FeN4 sites. The nearest doping does not significantly improve and even block the ORR activity of FeN4 sites. Optimal ORR activity is achieved when the heteroatoms are 4–5 Å (N, P, and S atoms) or 6–7 Å (B atoms) away from the Fe atoms. Analysis of electronic structure indicates that distance effect can modulate the local chemical environment of Fe atoms, thereby account for the changes in ORR activity along with the doping distance and doping atoms. This study provides insights into the influence of heteroatom doping on the chemical environment of reaction active centers, and provides the theoretical guidance for controlling the doping distance of heteroatoms to achieve optimal catalytic activity and selectivity.

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Acknowledgements

Y. Q. S. acknowledges the “Young Talent Support Plan” of Xi’an Jiaotong University. Supercomputing facilities were provided by Hefei Advanced Computing Center.

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Authors and Affiliations

  1. School of Chemistry, Engineering Research Center of Energy Storage Materials and Devices of Ministry of Education, National Innovation Platform (Center) for Industry-Education Integration of Energy Storage Technology, Xi’an Jiaotong University, Xi’an, 710049, China

    Peng Li, Jianrui Zhang, Shujiang Ding & Yaqiong Su

  2. Huanghe Science and Technology College, Zhengzhou, 450063, China

    Qingfeng Guo

  3. General Research Institute of Engineering of Gotion High-Tech, Hefei, 230041, China

    Ruilin Chen

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  1. Peng Li
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  2. Qingfeng Guo
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  3. Jianrui Zhang
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Correspondence to Jianrui Zhang, Ruilin Chen or Yaqiong Su.

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Li, P., Guo, Q., Zhang, J. et al. How the microenvironment dominated by the distance effect to regulate the FeN4 site ORR activity and selectivity?. Nano Res. (2024). https://doi.org/10.1007/s12274-024-6414-y

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