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Au-ZSM-5 catalyses the selective oxidation of CH4 to CH3OH and CH3COOH using O2

Nature Catalysis volume 5, pages 45–54 (2022)Cite this article

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Abstract

The oxidation of methane, the main component of natural gas, to selectively form oxygenated chemical feedstocks using molecular oxygen has been a long-standing grand challenge in catalysis. Here, using gold nanoparticles supported on the zeolite ZSM-5, we introduce a method to oxidize methane to methanol and acetic acid in water at temperatures between 120 and 240 °C using molecular oxygen in the absence of any added coreductant. Electron microscopy reveals that the catalyst does not contain gold atoms or clusters, but rather gold nanoparticles are the active component, while a mechanism involving surface adsorbed species is proposed in which methanol and acetic acid are formed via parallel pathways.

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Fig. 1: Catalytic performance of Au-ZSM-5 catalysts for methane oxidation.
Fig. 2: Oxygenate selectivity as a function of methane conversion.
Fig. 3: STEM high-angle annular dark-field images of 0.5 wt% Au-ZSM-5 catalysts.
Fig. 4: Calculated reaction pathways for methane activation by surface O atoms.
Fig. 5: Yield of products as a function of time.
Fig. 6: Schematic illustration of the proposed surface catalysed reactions.

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Data availability

All data used in this publication are available free of charge from Cardiff University via https://doi.org/10.17035/d.2021.0142278187 or available from the authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (grants U1932218, 21872170, 21733013 and 22061130202), as part of the Key projects of international partnership plan for foreign cooperation programme (112942KYSB20180009). J.X. thanks the Royal Society and the Newton Fund for Royal Society—Newton Advanced Fellowship. G.J.H. acknowledges the support from the Chinese Academy of Sciences President’s International Fellowship Initiative (grant no. 2019DM0015). Q.H. thanks the National Research Foundation Singapore for support under its NRF Fellowship (NRF-NRFF11-2019-0002). We thank Cardiff University and the Max Planck Centre for Fundamental Heterogeneous Catalysis (FUNCAT) for financial support. G.J.H., D.J.W. and C.R.A.C. thank the Engineering and Physical Sciences Research Council for funding this work (grant reference codes EP/P033695/1 and EP/L027240/1). Via our membership of the United Kingdom’s HEC Materials Chemistry Consortium, which is funded by the Engineering and Physical Sciences Research Council (EP/L000202 and EP/R029431), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) and the UK Materials and Molecular Modelling Hub, which is partially funded by the Engineering and Physical Sciences Research Council (EP/P020194), for computational resources.

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Authors and Affiliations

  1. National Centre for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan, China

    Guodong Qi, Xingling Zhao, Feng Deng & Jun Xu

  2. University of Chinese Academy of Sciences, Beijing, China

    Guodong Qi, Xingling Zhao & Jun Xu

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

    Thomas E. Davies, Ali Nasrallah, Mala A. Sainna, Richard J. Lewis, Matthew Quesne, C. Richard A. Catlow, David J. Willock, Donald Bethell, Mark J. Howard, Barry A. Murrer, Brian Harrison & Graham J. Hutchings

  4. National University of Singapore, Singapore, Singapore

    Alexander G. R. Howe & Qian He

  5. Department of Materials Science and Engineering, Lehigh University, Bethlehem, PA, USA

    Christopher J. Kiely

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Contributions

J.X. and G.J.H. conceived the research idea and organized the research programmes. G.Q. and R.J.L. prepared catalyst samples; G.Q., X.Z. and F.D. performed the catalytic experiments and NMR analysis; T.E.D., Q.H. and A.G.R.H. obtained electron microscopy data under the direction of C.J.K.; D.J.W., A.N., M.A.S. and M.Q. carried out most of the computational chemistry calculations. D.B. and M.J.H. provided mechanistic interpretation of results along with C.R.A.C. and D.J.W., who integrated experimental and computational insights. B.A.M. and B.H. provided advice on the industrial context of the work. J.X., G.J.H. and D.J.W. wrote the paper, and all authors discussed the results and the various revisions of the manuscript. J.X. and G.J.H. contributed equally to this work.

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Correspondence to Jun Xu or Graham J. Hutchings.

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Supplementary Figs. 1–25, Tables 1–15, Notes 1 and 2 and references.

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Qi, G., Davies, T.E., Nasrallah, A. et al. Au-ZSM-5 catalyses the selective oxidation of CH4 to CH3OH and CH3COOH using O2. Nat Catal 5, 45–54 (2022). https://doi.org/10.1038/s41929-021-00725-8

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