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H2-reduced phosphomolybdate promotes room-temperature aerobic oxidation of methane to methanol

Nature Catalysis volume 6, pages 895–905 (2023)Cite this article

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Abstract

The selective partial oxidation of methane to methanol using molecular oxygen (O2) represents a long-standing challenge, inspiring extensive study for many decades. However, considerable challenges still prevent low-temperature methane activation via the aerobic route. Here we report a precipitated Pd-containing phosphomolybdate, which, after activation by molecular hydrogen (H2), converts methane and O2 almost exclusively to methanol at room temperature. The highest activity reaches 67.4 μmol gcat−1 h−1. Pd enables rapid H2 activation and H spillover to phosphomolybdate for Mo reduction, while facile O2 activation and subsequent methane activation occur on the reduced phosphomolybdate sites. Continuous production of methanol from methane was also achieved by concurrently introducing H2, O2 and methane into the system, where H2 assists in maintaining a moderately reduced state of phosphomolybdate. This work reveals the underexplored potential of such a Mo-based catalyst for aerobic methane oxidation and highlights the importance of regulating the chemical valence state to construct methane active sites.

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Fig. 1: Structure and redox properties of Pd/CsPMA.
Fig. 2: Parameter–activity correlations and recycling tests for methane oxidation.
Fig. 3: Experimental insights into the methane oxidation mechanism over Pd/CsPMA-H.
Fig. 4: Proposed mechanism for methane activation and methanol formation from DFT calculations.

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All data are available from the authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

We thank the National Natural Science Foundation of China (92061109) for supporting the project. N.Y. and Q.H. sincerely acknowledge the support of the National Research Foundation (NRF) Singapore, under its NRF Investigatorship (NRF-NRFI07–2021–0006) and NRF Fellowship (NRF-NRFF11-2019-0002), respectively. R.J.L. and G.J.H. gratefully acknowledge Cardiff University and the Max Planck Centre for Fundamental Heterogeneous Catalysis (FUNCAT) for financial support. Z.Y. acknowledges support from the National Natural Science Foundation of China (52222102, 22272024 and 51871058) and the Eyas Program of Fujian Province. DFT simulations were conducted at the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory.

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Authors and Affiliations

  1. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou, China

    Sikai Wang, Jinquan Chang & Ning Yan

  2. Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Singapore

    Sikai Wang, Max J. Hülsey, Jinquan Chang & Ning Yan

  3. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Victor Fung

  4. School of Computational Science and Engineering, Georgia Institute of Technology, Atlanta, GA, USA

    Victor Fung

  5. State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, China

    Xiaocong Liang & Zhiyang Yu

  6. Net Zero Innovation Institute, Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, UK

    Andrea Folli

  7. Max Planck Centre on the Fundamentals of Heterogeneous Catalysis FUNCAT, Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, UK

    Richard J. Lewis & Graham J. Hutchings

  8. Department of Materials Science and Engineering, National University of Singapore, Singapore, Singapore

    Qian He

  9. Centre for Hydrogen Innovations, National University of Singapore, Singapore, Singapore

    Ning Yan

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  1. Sikai Wang
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Contributions

N.Y. conceived and supervised the project. Q.H. and G.J.H. co-supervised the project. S.W. conducted most experiments including synthesis, characterization and testing, as well as data analysis. V.F. carried out DFT calculations and wrote the related section. M.J.H. and J.C. carried out the catalyst synthesis and characterization. X.L. and Z.Y. conducted TEM analysis. A.F. and R.J.L. contributed to data analysis of the EPR spectra and H2O2 detection. S.W., Q.H. and N.Y. wrote the paper. G.J.H., A.F. and R.J.L. revised the paper. All authors discussed the paper.

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Correspondence to Graham J. Hutchings, Qian He or Ning Yan.

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Nature Catalysis thanks Lars Grabow, Gunnar Jeschke and Liang Wang for their contribution to the peer review of this work.

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Supplementary Figs. 1–32, Notes 1 and 2, Tables 1–7 and Refs. 1–11.

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INCAR and POSCAR files for the structures shown in Fig. 4 for DFT calculations.

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Wang, S., Fung, V., Hülsey, M.J. et al. H2-reduced phosphomolybdate promotes room-temperature aerobic oxidation of methane to methanol. Nat Catal 6, 895–905 (2023). https://doi.org/10.1038/s41929-023-01011-5

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