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Nano Research 2023, 16(4): 5601-5609 https://doi.org/10.1007/s12274-021-4013-8
Research Article | Issue | Published: 20 December 2021

Design of mesoporous ZnCoSiOx hollow nanoreactors with specific spatial distribution of metal species for selective CO2 hydrogenation

Show Author's Information Xinyao Wang1,2,  Runping Ye1,  Melis S. Duyar3,  Cameron Alexander Hurd Price4,  Hao Tian1,5,  Yanping Chen1,  Na Ta1,  Hao Liu5,  Jian Liu1,3,6( )
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
University of Chinese Academy of Sciences, Beijing 100049, China
Department of Chemical and Process Engineering, University of Surrey, Guildford, Surrey GU2 7XH, UK
Department of Chemical Engineering and Analytical Science, University of Manchester, Manchester, UK
Centre for Clean Energy Technology, University of Technology Sydney, Sydney, Broadway NSW 2007, Australia
DICP-Surrey Joint Centre for Future Materials, Advanced Technology Institute, University of Surrey, Guildford, Surrey GU2 7XH, UK
Keywords:
nanostructures, mesoporous materials, metal–organic frameworks, supported catalysts, structure-activity relationships
Cite this article:
Wang X, Ye R, Duyar MS, et al. Design of mesoporous ZnCoSiOx hollow nanoreactors with specific spatial distribution of metal species for selective CO2 hydrogenation. Nano Research, 2023, 16(4): 5601-5609. https://doi.org/10.1007/s12274-021-4013-8
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Abstract Full text Electronic supplementary material About this article

In heterogeneous catalysis, the precise placement of active components to perform unique functions in cooperation with each other is a tremendous challenge. The migration of matter on micro/nano-scale caused by diffusion is a promising pathway for design of catalytic nanoreactors with precise active sites location and controllable microenvironment through compartmentalization and confinement effects. Herein, we report two categories of mesoporous ZnCoSiOx hollow nanoreactors with different metal distributions and microenvironment engineered by the diffusion behavior of metal species in confined nanospace. Double-shelled hollow structures with well-distributed metal species were obtained by adopting core@shell structured ZnCo-zeolitic imidazolate framework (ZIF)@SiO2 as a template and employing three stages of hydrothermal treatment including the decomposition of ZIF, diffusion of metal species into the silica shell, and Ostwald ripening. Additionally, the formation of yolk@shell structure with a collective (Zn-Co) metal oxide as the yolk was achieved by direct pyrolysis of ZnCo-ZIF@SiO2. In CO2 hydrogenation, ZnCoSiOx with double-shelled hollow structures and yolk@shell structures respectively afford CO and CH4 as main product, which is related with different dispersion and location of active sites in the two catalysts. This study provides an efficient method for the synthesis of catalytic nanoreactors on the basis of insights of the atomic diffusion in confined space at the mesoscale.


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Electronic supplementary material
About this article

Design of mesoporous ZnCoSiOx hollow nanoreactors with specific spatial distribution of metal species for selective CO2 hydrogenation

Show Author's information Xinyao Wang1,2, Runping Ye1, Melis S. Duyar3, Cameron Alexander Hurd Price4, Hao Tian1,5, Yanping Chen1, Na Ta1, Hao Liu5, Jian Liu1,3,6( )
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
University of Chinese Academy of Sciences, Beijing 100049, China
Department of Chemical and Process Engineering, University of Surrey, Guildford, Surrey GU2 7XH, UK
Department of Chemical Engineering and Analytical Science, University of Manchester, Manchester, UK
Centre for Clean Energy Technology, University of Technology Sydney, Sydney, Broadway NSW 2007, Australia
DICP-Surrey Joint Centre for Future Materials, Advanced Technology Institute, University of Surrey, Guildford, Surrey GU2 7XH, UK

Abstract

In heterogeneous catalysis, the precise placement of active components to perform unique functions in cooperation with each other is a tremendous challenge. The migration of matter on micro/nano-scale caused by diffusion is a promising pathway for design of catalytic nanoreactors with precise active sites location and controllable microenvironment through compartmentalization and confinement effects. Herein, we report two categories of mesoporous ZnCoSiOx hollow nanoreactors with different metal distributions and microenvironment engineered by the diffusion behavior of metal species in confined nanospace. Double-shelled hollow structures with well-distributed metal species were obtained by adopting core@shell structured ZnCo-zeolitic imidazolate framework (ZIF)@SiO2 as a template and employing three stages of hydrothermal treatment including the decomposition of ZIF, diffusion of metal species into the silica shell, and Ostwald ripening. Additionally, the formation of yolk@shell structure with a collective (Zn-Co) metal oxide as the yolk was achieved by direct pyrolysis of ZnCo-ZIF@SiO2. In CO2 hydrogenation, ZnCoSiOx with double-shelled hollow structures and yolk@shell structures respectively afford CO and CH4 as main product, which is related with different dispersion and location of active sites in the two catalysts. This study provides an efficient method for the synthesis of catalytic nanoreactors on the basis of insights of the atomic diffusion in confined space at the mesoscale.

Keywords: nanostructures, mesoporous materials, metal–organic frameworks, supported catalysts, structure-activity relationships

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Publication history
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Acknowledgements

Publication history

Received: 04 September 2011
Revised: 09 November 2021
Accepted: 22 November 2021
Published: 20 December 2021
Issue date: April 2023

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

Acknowledgements

The authors are grateful to Prof. Qihua Yang for fruitful discussions. This work was financially supported by the National Natural Science Foundation of China (No. 22005296), the Natural Science Foundation of Liaoning Province, China (No. 2020-YQ-01), and the LiaoNing Revitalization Talents Program, China (No. XLYC1807077).

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