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Nano Research 2021, 14(8): 2637-2643 https://doi.org/10.1007/s12274-020-3266-y
Research Article | Issue | Published: 27 February 2021

Jahn-Teller distortion assisted interstitial nitrogen engineering: Enhanced oxygen dehydrogenation activity of N-doped MnxCo3-xO4 hierarchical micro-nano particles

Show Author's Information Yangxin Jin1,2,  Fengfeng Li1,  Peixin Cui3,  Yun Yang2,  Qingping Ke1( ),  Minh Ngoc Ha1,4,  Wangcheng Zhan5,  Fei Ruan1,  Chao Wan1,  Zhao Lei1,  Van Noi Nguyen4,  Wei Chen2( ),  Jun Tang1( )
College of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan 243002, China
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China
Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008, China
VNU Key Laboratory of Advanced Material for Green Growth, VNU University of Science, Vietnam National University, Hanoi 100000, Vietnam
Key Laboratory for Advanced Materials and Research, Institute of Industrial Catalysis School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China
Keywords:
transition metal oxides, Jahn-Teller effect, interstitial nitrogen engineering, MnxCo3-xO4, dehydrogenation
Topics:
Oxidation
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Jin Y, Li F, Cui P, et al. Jahn-Teller distortion assisted interstitial nitrogen engineering: Enhanced oxygen dehydrogenation activity of N-doped MnxCo3-xO4 hierarchical micro-nano particles. Nano Research, 2021, 14(8): 2637-2643. https://doi.org/10.1007/s12274-020-3266-y
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Abstract Full text Electronic supplementary material About this article

Rational design of earth-abundant transition metal oxides catalysts is highly desirable for developing sustainable chemical processes. Herein, we demonstrate a prospective interstitial nitrogen engineering for fabricating oxygen vacancies (OVs)-rich nitrogen-doped-MnxCo3-xO4 (N-MnxCo3-xO4) oxide catalyst, in which the ratio of OVs concentration of N-MnxCo3-xO4 to Mn species is as high as 1:1, according to the characterizations of X-ray absorption (XAS) and X-ray photoelectron (XPS) spectroscopies. The promising strategy of interstitial nitrogen engineering through lattice distortion caused by the Jahn-Teller effect can significantly increase the amount of interstitial nitrogen. The resulting catalyst enables an additive-free aerobic dehydrogenation coupling of aromatic amine to afford azo compounds with > 99% yield and > 99% selectivity at 60 °C. We observed the superb catalytic activity is promoted by the enhanced oxygen mobility in OVs, which were created by the interstitial nitrogen in the catalyst matrix. The presence of interstitial nitrogen in transition metal oxides in this study shows how the manipulation of catalyst matrix can increase the OV sites to promote aerobic oxidation reaction.


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About this article

Jahn-Teller distortion assisted interstitial nitrogen engineering: Enhanced oxygen dehydrogenation activity of N-doped MnxCo3-xO4 hierarchical micro-nano particles

Show Author's information Yangxin Jin1,2, Fengfeng Li1, Peixin Cui3, Yun Yang2, Qingping Ke1( ), Minh Ngoc Ha1,4, Wangcheng Zhan5, Fei Ruan1, Chao Wan1, Zhao Lei1, Van Noi Nguyen4, Wei Chen2( ), Jun Tang1( )
College of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan 243002, China
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China
Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008, China
VNU Key Laboratory of Advanced Material for Green Growth, VNU University of Science, Vietnam National University, Hanoi 100000, Vietnam
Key Laboratory for Advanced Materials and Research, Institute of Industrial Catalysis School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

Abstract

Rational design of earth-abundant transition metal oxides catalysts is highly desirable for developing sustainable chemical processes. Herein, we demonstrate a prospective interstitial nitrogen engineering for fabricating oxygen vacancies (OVs)-rich nitrogen-doped-MnxCo3-xO4 (N-MnxCo3-xO4) oxide catalyst, in which the ratio of OVs concentration of N-MnxCo3-xO4 to Mn species is as high as 1:1, according to the characterizations of X-ray absorption (XAS) and X-ray photoelectron (XPS) spectroscopies. The promising strategy of interstitial nitrogen engineering through lattice distortion caused by the Jahn-Teller effect can significantly increase the amount of interstitial nitrogen. The resulting catalyst enables an additive-free aerobic dehydrogenation coupling of aromatic amine to afford azo compounds with > 99% yield and > 99% selectivity at 60 °C. We observed the superb catalytic activity is promoted by the enhanced oxygen mobility in OVs, which were created by the interstitial nitrogen in the catalyst matrix. The presence of interstitial nitrogen in transition metal oxides in this study shows how the manipulation of catalyst matrix can increase the OV sites to promote aerobic oxidation reaction.

Keywords: transition metal oxides, Jahn-Teller effect, interstitial nitrogen engineering, MnxCo3-xO4, dehydrogenation

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Publication history
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Acknowledgements

Publication history

Received: 11 August 2019
Revised: 16 October 2019
Accepted: 06 November 2020
Published: 27 February 2021
Issue date: August 2021

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020

Acknowledgements

This work was financially supported by the Anhui Provincial Natural Science Foundation of China (2008085M47), "Key Program for International S&T Cooperation Projects of China" (No. 2017YFE0124300) and Anhui Provincial Science Fund for Excellent Young Scholars (gxyqZD2018034).

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