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Nano Research 2020, 13(8): 2079-2084 https://doi.org/10.1007/s12274-020-2810-0
Research Article | Issue | Published: 05 August 2020

Synergy of Fe-N4 and non-coordinated boron atoms for highly selective oxidation of amine into nitrile

Show Author's Information Hong-Hui Wang1,  Li-Bing Lv1,  Shi-Nan Zhang1,  Hui Su1,  Guang-Yao Zhai1,  Wei-Wei Lei2,  Xin-Hao Li1( ),  Jie-Sheng Chen1
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Institute for Frontier Materials, Deakin University, Victoria 3216, Australia
Keywords:
selective oxidation, atomically dispersed catalyst, Fe-N4, non-coordinated boron, nitrile
Topics:
BoronCatalyst activityCatalyst selectivity CyanidesElectron density measurement
Cite this article:
Wang H-H, Lv L-B, Zhang S-N, et al. Synergy of Fe-N4 and non-coordinated boron atoms for highly selective oxidation of amine into nitrile. Nano Research, 2020, 13(8): 2079-2084. https://doi.org/10.1007/s12274-020-2810-0
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Abstract Full text Electronic supplementary material About this article

The rational design of highly active and stable atomically dispersed M-X4 (M = Fe, Co, Ni, etc., X = C, N) -based catalysts holds promises for wide application in almost all realms of catalysis. Despite great effort in the construction of specific M-X4 centers, the possible effect of non-coordinated heteroatoms on the catalytic activity of metal centers has been rarely explored. Herein, we develop a new type of M-X4 catalyst composed of Fe-N4 centers and non-coordinated B heteroatoms (FeNC+B) and find the key role of non-coordinated B adjacent to Fe-N4 centers in tailoring their electron density and final catalytic selectivity. The experimental and theoretical results demonstrated that non-coordinated boron atoms could decrease the electron density of Fe-N4 centers to a suitable level and thus boost the selective production of nitriles from amine oxidation by depressing the formation of imines due to the flattened energy barrier of the reversible conversion of imines back to amines. As a reusable heterocatalyst, the state-of-the-art FeNC+B catalyst provides a turn-over frequency (TOF) value of 21.6 molbenzonitrile·molFe-1·h-1 (100 °C), outpacing that of bench-marked nonnoble-metal-based homogeneous catalyst by a factor of 3.4.


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Electronic supplementary material
About this article

Synergy of Fe-N4 and non-coordinated boron atoms for highly selective oxidation of amine into nitrile

Show Author's information Hong-Hui Wang1, Li-Bing Lv1, Shi-Nan Zhang1, Hui Su1, Guang-Yao Zhai1, Wei-Wei Lei2, Xin-Hao Li1( ), Jie-Sheng Chen1
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Institute for Frontier Materials, Deakin University, Victoria 3216, Australia

Abstract

The rational design of highly active and stable atomically dispersed M-X4 (M = Fe, Co, Ni, etc., X = C, N) -based catalysts holds promises for wide application in almost all realms of catalysis. Despite great effort in the construction of specific M-X4 centers, the possible effect of non-coordinated heteroatoms on the catalytic activity of metal centers has been rarely explored. Herein, we develop a new type of M-X4 catalyst composed of Fe-N4 centers and non-coordinated B heteroatoms (FeNC+B) and find the key role of non-coordinated B adjacent to Fe-N4 centers in tailoring their electron density and final catalytic selectivity. The experimental and theoretical results demonstrated that non-coordinated boron atoms could decrease the electron density of Fe-N4 centers to a suitable level and thus boost the selective production of nitriles from amine oxidation by depressing the formation of imines due to the flattened energy barrier of the reversible conversion of imines back to amines. As a reusable heterocatalyst, the state-of-the-art FeNC+B catalyst provides a turn-over frequency (TOF) value of 21.6 molbenzonitrile·molFe-1·h-1 (100 °C), outpacing that of bench-marked nonnoble-metal-based homogeneous catalyst by a factor of 3.4.

Keywords: selective oxidation, atomically dispersed catalyst, Fe-N4, non-coordinated boron, nitrile

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Publication history
Copyright
Acknowledgements

Publication history

Received: 25 February 2020
Revised: 21 March 2020
Accepted: 12 April 2020
Published: 05 August 2020
Issue date: August 2020

Copyright

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 21722103, 21931005, 21720102002, and 21673140), Shanghai Science and Technology Committee (No. 19JC1412600) and the SJTU-MPI partner group. The authors thank Shanghai Synchrotron Radiation Facility for providing beam time (No. BL14W1).

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