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Research Article

Atomic manganese coordinated to nitrogen and sulfur for oxygen evolution

Xue Bai1,§, Liming Wang3,4,§, Bing Nan5,§, Tianmi Tang1, Xiaodi Niu2( ), Jingqi Guan1( )
Institute of Physical Chemistry, College of Chemistry, Jilin University, 2519 Jiefang Road, Changchun 130021, China
College of Food Science and Engineering, Jilin University, Changchun 130062, China
CAS Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety & CAS-HKU Joint Laboratory of Metallomics on Health and Environment, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Beijing 100191, China
Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Science, Shanghai 201210, China

§ Xue Bai, Liming Wang, and Bing Nan contributed equally to this work.

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Graphical Abstract

Single-atom Mn-NSG (NSG means N- and S- codoped graphene) with Mn-N3S sites shows a low oxygen evolution reaction (OER) overpotential of 296 mV at 10 mA·cm−2 and a small Tafel slope of 38 mV·dec–1 in alkaline media, over which the O–O formation step is the rate-determining step.

Abstract

Lack of high-efficiency, cost-efficient, and well-stocked oxygen evolution reaction (OER) electrocatalysts is a main challenge in large-scale implementation of electrolytic water. By regulating the electronic structure of isolated single-atom metal sites, high-performance transition-metal-based catalysts can be fabricated to greatly improve the OER performance. Herein, we demonstrate single-atom manganese coordinated to nitrogen and sulfur species in two-dimensional graphene nanosheets Mn-NSG (NSG means N- and S- codoped graphene) as an active and durable OER catalyst with a low overpotential of 296 mV in alkaline media, compared to that of the benchmark IrO2 catalyst. Theoretical calculations and experimental measurements reveal that the Mn-N3S sites in the graphene matrix are the most active sites for the OER due to modified electronic structure of the Mn site by three nitrogen and one sulfur atoms coordination, which show lower theoretical overpotential than the Mn-N4 sites and over which the O–O formation step is the rate-determining step.

Keywords

single-atom catalystoxygen evolution reactiontheoretical calculationsMn-N-CN/S co-coordination

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Nano Research
Volume 15 Issue 7,
July 2022
Pages 6019-6025
DOI: 10.1007/s12274-022-4293-7
Cite this article:
Bai X, Wang L, Nan B, et al. Atomic manganese coordinated to nitrogen and sulfur for oxygen evolution. Nano Research, 2022, 15(7): 6019-6025. https://doi.org/10.1007/s12274-022-4293-7
Topics:
Oxygen evolution reaction

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Received: 25 January 2022
Revised: 01 March 2022
Accepted: 04 March 2022
Published: 25 April 2022
© Tsinghua University Press 2022
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