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A selective Au-ZnO/TiO2 hybrid photocatalyst for oxidative coupling of methane to ethane with dioxygen

Nature Catalysis volume 4, pages 1032–1042 (2021)Cite this article

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A Publisher Correction to this article was published on 07 January 2022

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Abstract

Direct oxidation of methane to valuable chemicals is a great challenge as catalysts with both high activity and selectivity for the activation of inert C–H bonds are required. Here, we report the highly efficient and selective photo-oxidation of methane to ethane with dioxygen in a flow reactor using a Au nanoparticle (NP) loaded ZnO/TiO2 hybrid. An ethane production rate of over 5,000 μmol g−1 h−1 with 90% selectivity is achieved, which is more than one order of magnitude higher than the state-of-the-art photocatalytic systems. Detailed characterizations and theoretical studies show that the formation of heterojunctions between ZnO and TiO2 leads to enhanced photocatalytic activity, while maintaining high selectivity owing to the weak overoxidation ability of the main component ZnO. Moreover, the Au cocatalyst enables the facile desorption of methyl (CH3) species as •CH3 radicals in the gas phase, thereby facilitating C2H6 formation and inhibiting overoxidation of CH4 to CO2.

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Fig. 1: Structural characterizations of catalysts.
Fig. 2: Photocatalytic OCM performance.
Fig. 3: Photocatalytic OCM performance under different conditions.
Fig. 4: Mechanistic studies of O2 activation.
Fig. 5: In situ DRIFT spectroscopy characterization.
Fig. 6: DFT calculations and proposed reaction mechanism for photocatalytic oxidation of CH4 with O2.

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Data availability

The data that support the plots within this paper and other findings of this study are available from the article and Supplementary Information or from the corresponding authors on reasonable request. Source data are provided with this paper.

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Acknowledgements

This work received partial financial support from JSPS KAKENHI grant number JP18H02065, Photo-excitonix Project in Hokkaido University, National Natural Science Foundation of China (grant nos. 21633004, 51872091, 21633015 and 11721404), Ministry of Science and Technology (grant no. 2018YFA0208700), Hundred Talents Program of Hebei Province (grant no. E2018050013) and State Scholarship Fund by China Scholarship Council (grant no. 201806240195).

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  1. These authors contributed equally to this work: Shuang Song, Hui Song.

Authors and Affiliations

  1. College of Architecture and Environment, Sichuan University, Chengdu, China

    Shuang Song & Wei Chu

  2. International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, Japan

    Shuang Song, Hui Song, Shengyao Wang, Kang Peng, Xianguang Meng, Qi Wang, Bowen Deng, Huiwen Lin, Tetsuya Kako & Jinhua Ye

  3. Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Japan

    Hui Song, Qi Wang, Bowen Deng & Jinhua Ye

  4. Institute for Advanced Study, Chengdu University, Chengdu, China

    Luming Li

  5. State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an, China

    Kang Peng

  6. Beijing National Laboratory for Condensed Matter Physics, Laboratory of Soft Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Qianxia Liu, Zhuan Wang & Yuxiang Weng

  7. School of Physical Sciences, University of Chinese Academy of Sciences, Beijing, China

    Qianxia Liu & Yuxiang Weng

  8. TJU-NIMS International Collaboration Laboratory, School of Materials Science and Engineering, Tianjin University, Tianjin, China

    Huilin Hu & Jinhua Ye

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Contributions

J.Y. supervised the research. H.S. conceived the ideas and wrote the paper. S.S. and H.S. performed catalyst synthesis, characterization and photocatalytic tests. L.L. conducted O2-TPD measurement. S.W. and H.H. conducted ESR measurement. K.P. conducted TEM measurement. Q.W. participated in DFT calculations. B.D. carried out DRIFT measurements. H.L. performed ATR-IR measurements. S.S., H.S. and J.Y. analysed the data. W.C., X.M., Q.L., Z.W., Y.W. and T.K. participated in the analysis of some results. All authors contribute to the discussion and revision of the paper.

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Correspondence to Hui Song or Jinhua Ye.

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Peer review information Nature Catalysis thanks Jinlin Long, Ana Belén Muñoz-García and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Song, S., Song, H., Li, L. et al. A selective Au-ZnO/TiO2 hybrid photocatalyst for oxidative coupling of methane to ethane with dioxygen. Nat Catal 4, 1032–1042 (2021). https://doi.org/10.1038/s41929-021-00708-9

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