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Nano Research 2023, 16(12): 12942-12948 https://doi.org/10.1007/s12274-023-6345-z
Research Article | Issue | Published: 05 December 2023

Tandem photo-oxidation of methane to methanol at room temperature and pressure over Pt/TiO2

Show Author's Information Yingxue Sun1,§,  Chunling Bo2,3,§,  Zhijjie Cheng2,4,  Xinyi Zhang2,3,  Jianjun Liu1( ),  Lingyu Piao2,5( )
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
National Center for Nanoscience and Technology, Beijing 100190, China
University of Chinese Academy of Sciences, Beijing 100049, China
Key Laboratory of Marine Chemistry Theory and Technology (Ministry of Education), College of Chemistry & Chemical Engineering, OceanUniversity of China, Qingdao 266100, China
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

§ Yingxue Sun and Chunling Bo contributed equally to this work.

Keywords:
TiO2, methanol, tandem reaction, photocatalytic oxidation of methane
Topics:
Photocatalytic activity
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Sun Y, Bo C, Cheng Z, et al. Tandem photo-oxidation of methane to methanol at room temperature and pressure over Pt/TiO2. Nano Research, 2023, 16(12): 12942-12948. https://doi.org/10.1007/s12274-023-6345-z
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Abstract Full text Electronic supplementary material About this article

In the process of methane (CH4) oxidation to methanol (CH3OH), CH3OH is more easily oxidized than CH4, resulting in inevitable peroxide phenomenon. In this work, we innovatively proposed a tandem reaction pathway to obtain a photocatalytic oxidation process of CH4 with high activity and selectivity. This work confirms that the methyl hydrogen peroxide (CH3OOH), the first product of CH4 oxidation by H2O2, is then completely reduced to CH3OH in an electron-rich environment. Under irradiation, H2O2 was excited into hydroxyl radicals (·OH) and hydroperoxyl radicals (·OOH) on brookite TiO2 photocatalyst. The ·OH oxidized CH4 to form methyl radicals (·CH3), which then reacted with ·OOH to form CH3OOH. CH3OOH gained electrons on Pt nanoparticles (NPs) and was reduced to CH3OH. At this point, low concentration of ·OH was difficult to further oxidize CH3OH, so that it can exist stably. Under the conditions of room temperature (25 °C) and atmospheric pressure, the productivity of CH3OH was 883 μmol/(g·h), which was 4 times more than the reported photocatalytic CH4 oxidation system with the same reaction conditions, and the selectivity was 100% in liquid products (98.77% for all products). The photocatalyst showed excellent stability and maintained ＞ 85% product activity after 9 catalytic cycles. This work contributed to the development of highly efficient and selective CH4 photooxidation system under mild conditions.


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About this article

Tandem photo-oxidation of methane to methanol at room temperature and pressure over Pt/TiO2

Show Author's information Yingxue Sun1,§, Chunling Bo2,3,§, Zhijjie Cheng2,4, Xinyi Zhang2,3, Jianjun Liu1( ), Lingyu Piao2,5( )
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
National Center for Nanoscience and Technology, Beijing 100190, China
University of Chinese Academy of Sciences, Beijing 100049, China
Key Laboratory of Marine Chemistry Theory and Technology (Ministry of Education), College of Chemistry & Chemical Engineering, OceanUniversity of China, Qingdao 266100, China
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

§ Yingxue Sun and Chunling Bo contributed equally to this work.

Abstract

In the process of methane (CH4) oxidation to methanol (CH3OH), CH3OH is more easily oxidized than CH4, resulting in inevitable peroxide phenomenon. In this work, we innovatively proposed a tandem reaction pathway to obtain a photocatalytic oxidation process of CH4 with high activity and selectivity. This work confirms that the methyl hydrogen peroxide (CH3OOH), the first product of CH4 oxidation by H2O2, is then completely reduced to CH3OH in an electron-rich environment. Under irradiation, H2O2 was excited into hydroxyl radicals (·OH) and hydroperoxyl radicals (·OOH) on brookite TiO2 photocatalyst. The ·OH oxidized CH4 to form methyl radicals (·CH3), which then reacted with ·OOH to form CH3OOH. CH3OOH gained electrons on Pt nanoparticles (NPs) and was reduced to CH3OH. At this point, low concentration of ·OH was difficult to further oxidize CH3OH, so that it can exist stably. Under the conditions of room temperature (25 °C) and atmospheric pressure, the productivity of CH3OH was 883 μmol/(g·h), which was 4 times more than the reported photocatalytic CH4 oxidation system with the same reaction conditions, and the selectivity was 100% in liquid products (98.77% for all products). The photocatalyst showed excellent stability and maintained ＞ 85% product activity after 9 catalytic cycles. This work contributed to the development of highly efficient and selective CH4 photooxidation system under mild conditions.

Keywords: TiO2, methanol, tandem reaction, photocatalytic oxidation of methane

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Publication history
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Acknowledgements

Publication history

Received: 08 October 2023
Revised: 05 November 2023
Accepted: 17 November 2023
Published: 05 December 2023
Issue date: December 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

We acknowledge the financial support by the National Natural Science Foundation of China (No. 21972028) and the Strategic Priority Research Program of Chinese Academy of Sciences (No. XDB36000000).

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