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Co3O4 as full-solar-spectrum photocatalyst for selective methane conversion through reactive oxygen species control

Nature Catalysis volume 9, pages 73–86 (2026) Cite this article

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Abstract

Methane, a potent greenhouse gas and a chemically inert molecule, presents a major challenge for catalytic conversion. Existing methods are energy-intensive, while photocatalysis offers a promising solar-driven alternative; yet, its efficiency and selectivity are often hampered by uncontrolled radical reactivity and inefficient charge separation. Here we have developed a full-solar-spectrum photocatalyst by constructing a Schottky heterojunction with Pd deposited on Co3O4 derived from a metal–organic framework. The narrow bandgap and black colouration of Co3O4 enable broad solar absorption, while its tailored band structure minimizes overoxidation and undesired by-products by suppressing reactive species, including O2•−, ·OH and ·OOH. The work function difference between Pd and Co3O4 establishes an interfacial electric field that promotes directional carrier migration and reduces recombination. This design achieves efficient solar utilization, precise radical regulation and robust charge separation, delivering a C2H6 production rate from CH4 of 16.1 mmol per gram catalyst per hour with ~96.2% selectivity under mild conditions.

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Fig. 1: Bandgaps and light absorption of photocatalysts.
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Fig. 2: Synthesis and characterization of Pd/Co3O4 photocatalysts.
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Fig. 3: Charge transfer mechanism at the Pd/Co3O4 interface revealed by in situ and spectroscopic analyses.
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Fig. 4: Ultrafast charge transfer dynamics in pure Co3O4 and the Pd/Co3O4 heterojunction.
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Fig. 5: Photocatalytic OCM performance.
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Fig. 6: Investigation of the reaction mechanism.
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Data availability

All of the data supporting the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper. These data are also available via figshare at https://doi.org/10.6084/m9.figshare.28091891 (ref. 69).

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2022YFE0115900 (J.Y.)), the National Natural Science Foundation of China (22378371 (F.X.), 52003213 (F.X.), 22238009 (J.Y.), U24A2071 (J.Y.), 22361142704 (J.Y.) and 22261142666 (J.Y.)) and the Natural Science Foundation of Hubei Province of China (2025AFD020 (F.X.) and 2022CFA001 (F.X.)). Partial support from the Iran National Science Foundation (grant number 4021464 (J.Y.)) is also acknowledged. We thank the Faculty of Materials Science and Chemistry, China University of Geosciences (CUG), Wuhan, for its TEM facilities and the data analysis by M. Gong. We also thank L. Zhang (Specreation Instruments) and H. Cao for their assistance with in situ XAFS characterization and related data analysis.

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Authors and Affiliations

  1. Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan, People’s Republic of China

    Feiyan Xu, Luoxuan Zheng, Jianjun Zhang, Ying He & Jiaguo Yu

  2. Instituto Universitario de Tecnología Química, CSIC-UPV, Universitat Politècnica de València, Valencia, Spain

    Feiyan Xu & Hermenegildo García

  3. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, People’s Republic of China

    Heng Cao & Xusheng Zheng

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  1. Feiyan Xu
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Contributions

F.X., H.G. and J.Y. conceived and designed the experiments. L.Z. synthesized the materials, carried out the photocatalytic test and characterized the materials. L.Z. and J.Z. performed the ultrafast TA measurements. L.Z., H.C. and X.Z. conducted the XAFS measurements. F.X., L.Z. and Y.H. analysed all the results. L.Z. wrote the paper. F.X. conducted the DFT calculations, contributed to the data analysis and revised the papert. F.X., X.Z., H.G. and J.Y. supervised the project. All authors discussed the results and commented on the paper.

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Correspondence to Xusheng Zheng, Hermenegildo García or Jiaguo Yu.

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Xu, F., Zheng, L., Zhang, J. et al. Co3O4 as full-solar-spectrum photocatalyst for selective methane conversion through reactive oxygen species control. Nat Catal 9, 73–86 (2026). https://doi.org/10.1038/s41929-025-01471-x

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