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Nano Research 2023, 16(2): 1810-1819 https://doi.org/10.1007/s12274-022-4939-5
Research Article | Issue | Published: 12 September 2022

Phosphorus-doped iron-nitrogen-carbon catalyst with penta-coordinated single atom sites for efficient oxygen reduction

Show Author's Information Lili Fan1,§( ),  Xiaofei Wei1,§,  Xuting Li1,  Zhanning Liu1,  Mengfei Li2,  Shuo Liu1,  Zixi Kang1,  Fangna Dai1,  Xiaoqing Lu1,  Daofeng Sun1( )
School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, China
College of Science, China University of Petroleum (East China), Qingdao 266580, China

§ Lili Fan and Xiaofei Wei contributed equally to this work.

Keywords:
oxygen reduction reaction, Fe-N-C, Fe-N4, penta-coordination, P-doping
Topics:
Carbon
Cite this article:
Fan L, Wei X, Li X, et al. Phosphorus-doped iron-nitrogen-carbon catalyst with penta-coordinated single atom sites for efficient oxygen reduction. Nano Research, 2023, 16(2): 1810-1819. https://doi.org/10.1007/s12274-022-4939-5
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Abstract Full text Electronic supplementary material About this article

Single-atomic Fe-N4 is the well-acknowledged active site in iron-nitrogen-carbon (Fe-N-C) material for oxygen reduction reaction (ORR). The adjusting of the electronic distribution of Fe-N4 is promising for further enhancing the performance of the Fe-N-C catalyst. Herein, a phosphorus (P)-doped Fe-N-C catalyst with penta-coordinated single atom sites (FeNPC) is reported for efficient oxygen reduction. Fe K-edge X-ray absorption spectroscopy (XAS) verifies the coordination environment of single Fe atom, while density functional theory (DFT) calculations reveal that the penta-coordination and neighboring doped P atoms can simultaneously change the electronic distribution of Fe-N4 and its adsorption strength of key intermediates, reducing the reaction-free energy of the potential-limiting step. Electrochemical tests validate the remarkable intrinsic ORR activity of FeNPC in alkaline media (a half-wave potential (E1/2) of 0.904 V vs. reversible hydrogen electrode (RHE) and limited current density (JL) of 6.23 mA·cm−2) and an enhanced ORR performance in neutral (E1/2 = 0.751 V, JL = 5.27 mA·cm−2) and acidic media (E1/2 = 0.735 V, JL = 5.82 mA·cm−2) with excellent stability, highlighting the benefits of optimizing the local environment of single-atomic Fe-N4.


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About this article

Phosphorus-doped iron-nitrogen-carbon catalyst with penta-coordinated single atom sites for efficient oxygen reduction

Show Author's information Lili Fan1,§( ), Xiaofei Wei1,§, Xuting Li1, Zhanning Liu1, Mengfei Li2, Shuo Liu1, Zixi Kang1, Fangna Dai1, Xiaoqing Lu1, Daofeng Sun1( )
School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, China
College of Science, China University of Petroleum (East China), Qingdao 266580, China

§ Lili Fan and Xiaofei Wei contributed equally to this work.

Abstract

Single-atomic Fe-N4 is the well-acknowledged active site in iron-nitrogen-carbon (Fe-N-C) material for oxygen reduction reaction (ORR). The adjusting of the electronic distribution of Fe-N4 is promising for further enhancing the performance of the Fe-N-C catalyst. Herein, a phosphorus (P)-doped Fe-N-C catalyst with penta-coordinated single atom sites (FeNPC) is reported for efficient oxygen reduction. Fe K-edge X-ray absorption spectroscopy (XAS) verifies the coordination environment of single Fe atom, while density functional theory (DFT) calculations reveal that the penta-coordination and neighboring doped P atoms can simultaneously change the electronic distribution of Fe-N4 and its adsorption strength of key intermediates, reducing the reaction-free energy of the potential-limiting step. Electrochemical tests validate the remarkable intrinsic ORR activity of FeNPC in alkaline media (a half-wave potential (E1/2) of 0.904 V vs. reversible hydrogen electrode (RHE) and limited current density (JL) of 6.23 mA·cm−2) and an enhanced ORR performance in neutral (E1/2 = 0.751 V, JL = 5.27 mA·cm−2) and acidic media (E1/2 = 0.735 V, JL = 5.82 mA·cm−2) with excellent stability, highlighting the benefits of optimizing the local environment of single-atomic Fe-N4.

Keywords: oxygen reduction reaction, Fe-N-C, Fe-N4, penta-coordination, P-doping

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Publication history
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Acknowledgements

Publication history

Received: 07 July 2022
Revised: 18 August 2022
Accepted: 19 August 2022
Published: 12 September 2022
Issue date: February 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 21875285, 22171288, and 22005340), the Key Research and Development Projects of Shandong Province (No. 2019JZZY010331), and the Natural Science Foundation of Shandong Province (No. ZR2020MB017).

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