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Nano Research 2024, 17(5): 3653-3659 https://doi.org/10.1007/s12274-023-6258-x
Research Article | Issue | Published: 24 November 2023

Dimensional reduction enhances photocatalytic carbon dioxide reduction performance of metal-organic frameworks

Show Author's Information Kaiyue Ma,  Jixin Li,  Jinlu Liu,  Chunguang Li,  Zhan Shi( ),  Shouhua Feng
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China
Keywords:
nanosheets, photocatalysis, CO2 reduction, light absorption, metal-organic frameworks (MOFs)
Topics:
Photocatalysis
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Ma K, Li J, Liu J, et al. Dimensional reduction enhances photocatalytic carbon dioxide reduction performance of metal-organic frameworks. Nano Research, 2024, 17(5): 3653-3659. https://doi.org/10.1007/s12274-023-6258-x
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Abstract Full text Electronic supplementary material About this article

Metal-organic frameworks (MOFs) have shown significant potential as photocatalysts. It has been widely assumed that all catalytic active sites within MOFs are functional in photocatalytic reactions but for a three-dimensional MOF, whether the internal catalytic active sites can effectively absorb light and actively contribute to photocatalytic reactions remains to be explored. In this context, we synthesized a two-dimensional nanosheet MOF (2D-MOF) and a three-dimensional bulk MOF (3D-MOF) composed of Zr6 clusters and tetracarboxylic porphyrin (TCPP) by the approach described in the literature. Re(bpy)(CO)3Cl (bpy = 2,2’-bipyridine), which has remarkable CO2 photoreduction ability, was introduced to the two MOFs to create two new photocatalysts 2D-MOF-Re and 3D-MOF-Re, respectively. Photocatalytic CO2 reduction experiments show that based on the equal number of catalytic active sites, the CO turnover number (TON) of 2D-MOF-Re reaches 27.8 in 6 h, which is 50 times that of 3D-MOF-Re. The result shows that certain catalytic active sites inside the bulk MOF are inactive due to the inability to absorb light. This study illuminates the potential of the dimensional reduction approach in the design of photocatalysts to exploit the capabilities fully.


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About this article

Dimensional reduction enhances photocatalytic carbon dioxide reduction performance of metal-organic frameworks

Show Author's information Kaiyue Ma, Jixin Li, Jinlu Liu, Chunguang Li, Zhan Shi( ), Shouhua Feng
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China

Abstract

Metal-organic frameworks (MOFs) have shown significant potential as photocatalysts. It has been widely assumed that all catalytic active sites within MOFs are functional in photocatalytic reactions but for a three-dimensional MOF, whether the internal catalytic active sites can effectively absorb light and actively contribute to photocatalytic reactions remains to be explored. In this context, we synthesized a two-dimensional nanosheet MOF (2D-MOF) and a three-dimensional bulk MOF (3D-MOF) composed of Zr6 clusters and tetracarboxylic porphyrin (TCPP) by the approach described in the literature. Re(bpy)(CO)3Cl (bpy = 2,2’-bipyridine), which has remarkable CO2 photoreduction ability, was introduced to the two MOFs to create two new photocatalysts 2D-MOF-Re and 3D-MOF-Re, respectively. Photocatalytic CO2 reduction experiments show that based on the equal number of catalytic active sites, the CO turnover number (TON) of 2D-MOF-Re reaches 27.8 in 6 h, which is 50 times that of 3D-MOF-Re. The result shows that certain catalytic active sites inside the bulk MOF are inactive due to the inability to absorb light. This study illuminates the potential of the dimensional reduction approach in the design of photocatalysts to exploit the capabilities fully.

Keywords: nanosheets, photocatalysis, CO2 reduction, light absorption, metal-organic frameworks (MOFs)

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Publication history
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Acknowledgements

Publication history

Received: 17 September 2023
Revised: 01 October 2023
Accepted: 09 October 2023
Published: 24 November 2023
Issue date: May 2024

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 22271114 and 21621001), the Foundation of Science and Technology Development of Jilin Province, China (No. 20200801004GH) and 111 Project (No. B17020). The authors also gratefully acknowledge the financial support by the program for JLU Science and Technology Innovative Research Team (JLUSTIRT).

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