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Nano Research 2024, 17(4): 2444-2450 https://doi.org/10.1007/s12274-023-6117-9
Research Article | Issue | Published: 30 September 2023

Differentially-grown cobalt regulators cooperatively involved in the tandem catalysis for high-yield production of second amines

Show Author's Information Jinhui Xu1,2,  Xiao Wang1,2( ),  Ying Wang1,2,  Fei Wang1,2,  Lingling Zhang1,2,  Wenjie Cui1,2,  Shuyan Song1,2( ),  Hongjie Zhang1,2,3( )
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
Department of Chemistry, Tsinghua University, Beijing 100084, China
Keywords:
heterogeneous catalyst, CeO2, hierarchical structure, tandem catalysis, dual-site materials
Topics:
NanocatalystsNanoclusters
Cite this article:
Xu J, Wang X, Wang Y, et al. Differentially-grown cobalt regulators cooperatively involved in the tandem catalysis for high-yield production of second amines. Nano Research, 2024, 17(4): 2444-2450. https://doi.org/10.1007/s12274-023-6117-9
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Abstract Full text Electronic supplementary material About this article

One-pot tandem catalysis has been regarded as one of the most atomic economic ways to produce secondary amines, the important platform molecules for chemical synthesis and pharmaceutical manufacture, but it is facing serious issues in overall efficiency. New promotional effects are highly desired for boosting the activity and regulating the selectivity of conventional tandem catalysts. In this work, we report a high-performance tandem catalyst with maximized synergistic effect among each counterpart by preciously manipulating the spatial structure, which involves the active CeO2/Pt component as kernel, the densely-coated N-doped C (NC) layer as selectivity controller, and the differentially-grown Co species as catalytic performance regulators. Through comprehensive investigations, the unique growth mechanism and the promotion effect of Co regulators are clarified. Specifically, the surface-landed Co clusters (Cocs) are crucial to selectivity by altering the adsorption configuration of benzylideneaniline intermediates. Meanwhile, the inner Co particles (Cops) are essential for activity by denoting their electrons to neighboring Ptps. Benefiting from the unique promotion effect, a remarkably-improved catalytic efficiency (100% nitrobenzene conversion with 94% N-benzylaniline selectivity) is achieved at a relatively low temperature of 80 °C, which is much better than that of CeO2/Pt (100% nitrobenzene conversion with 12% N-benzylaniline selectivity) and CeO2/Pt/NC (35% nitrobenzene conversion with 94% benzylideneaniline selectivity).


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Electronic supplementary material
About this article

Differentially-grown cobalt regulators cooperatively involved in the tandem catalysis for high-yield production of second amines

Show Author's information Jinhui Xu1,2, Xiao Wang1,2( ), Ying Wang1,2, Fei Wang1,2, Lingling Zhang1,2, Wenjie Cui1,2, Shuyan Song1,2( ), Hongjie Zhang1,2,3( )
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
Department of Chemistry, Tsinghua University, Beijing 100084, China

Abstract

One-pot tandem catalysis has been regarded as one of the most atomic economic ways to produce secondary amines, the important platform molecules for chemical synthesis and pharmaceutical manufacture, but it is facing serious issues in overall efficiency. New promotional effects are highly desired for boosting the activity and regulating the selectivity of conventional tandem catalysts. In this work, we report a high-performance tandem catalyst with maximized synergistic effect among each counterpart by preciously manipulating the spatial structure, which involves the active CeO2/Pt component as kernel, the densely-coated N-doped C (NC) layer as selectivity controller, and the differentially-grown Co species as catalytic performance regulators. Through comprehensive investigations, the unique growth mechanism and the promotion effect of Co regulators are clarified. Specifically, the surface-landed Co clusters (Cocs) are crucial to selectivity by altering the adsorption configuration of benzylideneaniline intermediates. Meanwhile, the inner Co particles (Cops) are essential for activity by denoting their electrons to neighboring Ptps. Benefiting from the unique promotion effect, a remarkably-improved catalytic efficiency (100% nitrobenzene conversion with 94% N-benzylaniline selectivity) is achieved at a relatively low temperature of 80 °C, which is much better than that of CeO2/Pt (100% nitrobenzene conversion with 12% N-benzylaniline selectivity) and CeO2/Pt/NC (35% nitrobenzene conversion with 94% benzylideneaniline selectivity).

Keywords: heterogeneous catalyst, CeO2, hierarchical structure, tandem catalysis, dual-site materials

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Publication history
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Acknowledgements

Publication history

Received: 10 July 2023
Revised: 11 August 2023
Accepted: 20 August 2023
Published: 30 September 2023
Issue date: April 2024

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was supported by financial aid from the National Science and Technology Major Project of China (No. 2021YFB3500700), the National Natural Science Foundation of China (Nos. 22020102003, 22025506, and 22271274), and the Program of Science and Technology Development Plan of Jilin Province of China (Nos. 20230101035JC and 20230101022JC).

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