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Research Article

Mesoporous MnO2 nanosheets for efficient electrocatalytic nitrogen reduction via high spin polarization induced by oxygen vacancy

Yangyang Wen1,§, Jiahao Liu1,§, Feiran Zhang2, Zhenxing Li1( ), Ping Wang1, Zhao Fang1, Miao He1, Jingshuai Chen3, Weiyu Song2( ), Rui Si4( ), Lianzhou Wang5( )
State Key Laboratory of Heavy Oil Processing, College of New Energy and Materials, China University of Petroleum (Beijing), Beijing 102249, China
College of Science, China University of Petroleum (Beijing), Beijing 102249, China
School of Chemistry and Chemical Engineering, Anhui University, Hefei 230601, China
Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China
Nanomaterials Centre, School of Chemical Engineering and Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Brisbane, QLD 4072, Australia

§ Yangyang Wen and Jiahao Liu contributed equally to this work.

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Graphical Abstract

High spin state Mn3+-Mn3+ pairs induced by oxygen vacancy in MnO2 nanosheets greatly enhance the catalytic activities.

Abstract

The electrochemical N2 reduction reaction (NRR) represents a green and sustainable route for NH3 synthesis under ambient conditions. However, the mechanism of N2 activation in the electrocatalytic NRR remains unclear. Herein, we found that the high spin state Mn3+-Mn3+ pairs induced by oxygen vacancy in MnO2 nanosheets greatly enhance the catalytic activities. The strong electron transfer between d orbital of Mn and orbital of N2 forces the N2 to be of radical nature, which activates the hydrogenation process and weakens the N≡N bond. Based on the density functional theory (DFT) calculation results, we precisely designed mesoporous MnO2 nanosheets with rich oxygen vacancies via using methyltriphenylphosphonium bromide (MPB) to induce more Mn3+-Mn3+ pairs (Mn3-3-MnO2), which can achieve a fairly high ammonia yield of up to 147.2 µg·h−1·mgcat−1. at −0.75 V vs. reversible hydrogen electrode (RHE) and a high Faradaic efficiency (FE) of 11%. Furthermore, these mesoporous MnO2 nanosheets exhibit the superior durability with negligible changes in both NH3 yield and FE after a consecutive 6-recycle test and the current density electrolyzed over a 24-hour period. Our findings offer an approach to designing highly active transition metal catalysts for electrocatalytic nitrogen reduction.

Keywords

Mn3+-Mn3+ pairMnO2 nanosheetsmesoporesammonia synthesiselectrocatalytic nitrogen reduction.

Electronic Supplementary Material

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Nano Research
Volume 16 Issue 4,
April 2023
Pages 4664-4670
DOI: 10.1007/s12274-022-5117-5
Cite this article:
Wen Y, Liu J, Zhang F, et al. Mesoporous MnO2 nanosheets for efficient electrocatalytic nitrogen reduction via high spin polarization induced by oxygen vacancy. Nano Research, 2023, 16(4): 4664-4670. https://doi.org/10.1007/s12274-022-5117-5
Topics:
SynthesisElectrolytic reduction

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Received: 10 July 2022
Revised: 27 September 2022
Accepted: 29 September 2022
Published: 24 October 2022
© Tsinghua University Press 2022
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