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Nano Research 2023, 16(10): 12270-12280 https://doi.org/10.1007/s12274-023-5891-8
Research Article | Issue | Published: 31 July 2023

Core–shell Cu@SiO2/SiO2 catalyst for 1,6-hexanediol dehydrogenation to ε-caprolactone: High activity and stability from core–shell nanostructure

Show Author's Information Fengyang Jiang1,  Tian Lan1,  Jiaqiang Sun2( ),  Guofeng Zhao1,3,†( ),  Yong Lu1( )
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
Key Laboratory of Functional Molecular Solids, Ministry of Education, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, China
Present address: College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, China
Keywords:
dehydrogenation, Cu-based catalyst, core–shell nanostructure, 1,6-hexanediol, ε-caprolactone
Topics:
Catalysis
Cite this article:
Jiang F, Lan T, Sun J, et al. Core–shell Cu@SiO2/SiO2 catalyst for 1,6-hexanediol dehydrogenation to ε-caprolactone: High activity and stability from core–shell nanostructure. Nano Research, 2023, 16(10): 12270-12280. https://doi.org/10.1007/s12274-023-5891-8
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Abstract Full text Electronic supplementary material About this article

The gas-phase dehydrogenation of 1,6-hexanediol (1,6-HDO) to ε-caprolactone (ε-CL) over the high-performance Cu-based catalysts is highly desirable, but with grand challenges, because the Cu nanoparticles (NPs) are easy to be sintered with the low Hüttig temperature (< 150 °C vs. > 250 °C of reaction temperature). Herein, we report a highly efficient silica-encapsulated nano-Cu catalyst (Cu@SiO2/SiO2) prepared via a complexation–impregnation method for the dehydrogenation of 1,6-HDO, exhibiting a 1,6-HDO conversion of 95.3% and ε-CL selectivity of 80.0% at 270 °C. The catalyst also has the outstanding thermal stability (without sintering up to 270 °C for 100 h on stream), which can be attributed to the effective encapsulation of the SiO2 shell. In addition, the reaction network of 1,6-HDO dehydrogenation is proved. Finally, the pyridine-diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and in-situ X-ray photoelectron spectroscopy (XPS) reveal that the Cu0 species favor the conversion of 1,6-HDO to ε-CL. The synergistic effect of Cu+ and Cu0 benefits the conversion of ε-CL to 2-methylcyclopentanone (2-MCPN). This study is beneficial for designing the high-performance Cu-based catalysts for 1,6-HDO to ε-CL, understanding the reaction network of 1,6-HDO dehydrogenation over the Cu-based catalysts, and offering a strong foundation for the large-scale production of ε-CL.


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Electronic supplementary material
About this article

Core–shell Cu@SiO2/SiO2 catalyst for 1,6-hexanediol dehydrogenation to ε-caprolactone: High activity and stability from core–shell nanostructure

Show Author's information Fengyang Jiang1, Tian Lan1, Jiaqiang Sun2( ), Guofeng Zhao1,3,†( ), Yong Lu1( )
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
Key Laboratory of Functional Molecular Solids, Ministry of Education, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, China
Present address: College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, China

Abstract

The gas-phase dehydrogenation of 1,6-hexanediol (1,6-HDO) to ε-caprolactone (ε-CL) over the high-performance Cu-based catalysts is highly desirable, but with grand challenges, because the Cu nanoparticles (NPs) are easy to be sintered with the low Hüttig temperature (< 150 °C vs. > 250 °C of reaction temperature). Herein, we report a highly efficient silica-encapsulated nano-Cu catalyst (Cu@SiO2/SiO2) prepared via a complexation–impregnation method for the dehydrogenation of 1,6-HDO, exhibiting a 1,6-HDO conversion of 95.3% and ε-CL selectivity of 80.0% at 270 °C. The catalyst also has the outstanding thermal stability (without sintering up to 270 °C for 100 h on stream), which can be attributed to the effective encapsulation of the SiO2 shell. In addition, the reaction network of 1,6-HDO dehydrogenation is proved. Finally, the pyridine-diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and in-situ X-ray photoelectron spectroscopy (XPS) reveal that the Cu0 species favor the conversion of 1,6-HDO to ε-CL. The synergistic effect of Cu+ and Cu0 benefits the conversion of ε-CL to 2-methylcyclopentanone (2-MCPN). This study is beneficial for designing the high-performance Cu-based catalysts for 1,6-HDO to ε-CL, understanding the reaction network of 1,6-HDO dehydrogenation over the Cu-based catalysts, and offering a strong foundation for the large-scale production of ε-CL.

Keywords: dehydrogenation, Cu-based catalyst, core–shell nanostructure, 1,6-hexanediol, ε-caprolactone

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Publication history
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Acknowledgements

Publication history

Received: 30 April 2023
Revised: 01 June 2023
Accepted: 02 June 2023
Published: 31 July 2023
Issue date: October 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 22179038, 22272053, 22072043, 21773069, and 21703069), the Special Project for Peak Carbon Dioxide Emissions-Carbon Neutrality (No. 21DZ1206700) from the Shanghai Municipal Science and Technology Commission, and the Key Basic Research Project (No. 18JC1412100) from the Shanghai Municipal Science and Technology Commission.

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