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Nano Research 2023, 16(5): 6642-6651 https://doi.org/10.1007/s12274-023-5421-0
Research Article | Issue | Published: 28 February 2023

Identifying the key N species for electrocatalytic oxygen reduction reaction on N-doped graphene

Show Author's Information Yiyin Peng1,  Zhaoyong Bian1( ),  Wenhai Zhang1,  Hui Wang2
College of Water Sciences, Beijing Normal University, Beijing 100875, China
College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, China
Keywords:
nitrogen-doped graphene, oxygen reduction, electrocatalysis, environmental remediation
Topics:
Electrolytic reduction Oxygen reduction reaction Selective catalytic reduction
Cite this article:
Peng Y, Bian Z, Zhang W, et al. Identifying the key N species for electrocatalytic oxygen reduction reaction on N-doped graphene. Nano Research, 2023, 16(5): 6642-6651. https://doi.org/10.1007/s12274-023-5421-0
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Abstract Full text Electronic supplementary material About this article

The state of nitrogen in nitrogen-doped graphene (NG) promoting the conversion of molecular oxygen to hydrogen peroxide was investigated. The oxygen reduction reaction (ORR) reactivity of graphitic-N, pyrrolic-N, and pyridinic-N in NG was predicted by density functional theory (DFT). A series of NG samples with different contents of these doped nitrogen types were prepared by the low-temperature thermal reduction method and used for the ORR evaluation. The H2O2 yield, 2e− ORR current efficiency, H2O2 selectivity, and electron transfer number (n) were systematically studied. The 2e− ORR selectivity was positively correlated with the N content, approaching 100% with increasing N content (0.40 V vs. reversible hydrogen electrode (RHE)), whereas the comparative energy efficiency showed a volcano-type trend related to N content, reaching a maximum of 94%. In addition, N species validation experiments proved the key role of pyrrolic-N in the synthesis of H2O2. Compared with a pure graphene catalyst, further contaminant degradation studies on NG electrodes with different pyrrolic-N contents revealed that the lower pyrrolic-N the higher removal of p-nitrophenol (PNP). This work provides insight into the mechanism of ORR on metal-free catalysts and a facile approach to optimize this important environmental catalytic strategy.


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About this article

Identifying the key N species for electrocatalytic oxygen reduction reaction on N-doped graphene

Show Author's information Yiyin Peng1, Zhaoyong Bian1( ), Wenhai Zhang1, Hui Wang2
College of Water Sciences, Beijing Normal University, Beijing 100875, China
College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, China

Abstract

The state of nitrogen in nitrogen-doped graphene (NG) promoting the conversion of molecular oxygen to hydrogen peroxide was investigated. The oxygen reduction reaction (ORR) reactivity of graphitic-N, pyrrolic-N, and pyridinic-N in NG was predicted by density functional theory (DFT). A series of NG samples with different contents of these doped nitrogen types were prepared by the low-temperature thermal reduction method and used for the ORR evaluation. The H2O2 yield, 2e− ORR current efficiency, H2O2 selectivity, and electron transfer number (n) were systematically studied. The 2e− ORR selectivity was positively correlated with the N content, approaching 100% with increasing N content (0.40 V vs. reversible hydrogen electrode (RHE)), whereas the comparative energy efficiency showed a volcano-type trend related to N content, reaching a maximum of 94%. In addition, N species validation experiments proved the key role of pyrrolic-N in the synthesis of H2O2. Compared with a pure graphene catalyst, further contaminant degradation studies on NG electrodes with different pyrrolic-N contents revealed that the lower pyrrolic-N the higher removal of p-nitrophenol (PNP). This work provides insight into the mechanism of ORR on metal-free catalysts and a facile approach to optimize this important environmental catalytic strategy.

Keywords: nitrogen-doped graphene, oxygen reduction, electrocatalysis, environmental remediation

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Publication history
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Acknowledgements

Publication history

Received: 16 October 2022
Revised: 20 November 2022
Accepted: 18 December 2022
Published: 28 February 2023
Issue date: May 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

The present work is financially supported by the Beijing Natural Science Foundation of China (No. 8222061), the National Natural Science Foundation of China (Nos. 21872009 and 52070015), and the National Key Research and Development Program of China (No. 2018YFC1802500).

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