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Identification of the active sites and mechanism for partial methane oxidation to methanol over copper-exchanged CHA zeolites

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Abstract

To make methane a suitable energy carrier and transport less costly, it is an urgent and challenging task for us to convert methane to liquid under mild conditions efficiently. In this study, we explored partial methane oxidation to methanol by density functional theory (DFT) calculations using a hybrid functional (HSE06) with van der Waals (vdW) interactions. The stabilities of different active sites over SSZ-13 and SAPO-34, two CHA type zeolites, are thoroughly investigated by ab initio molecular dynamics (AIMD) simulations and ab initio thermodynamics analyses. Four possible active sites, namely [CuOHCu]2+, [Cu(OH)2Cu]2+, [CuOCu]2+ and [CuOH]+, are identified stable. Methane-to-methanol reaction mechanisms are further studied upon these most stable active sites, among which [CuOCu]2+ and [CuOH]+ are proved to be reactive. The migration of species among zeolite pores are also discussed, which accounts for the activity on [CuOH]+ sites. This concept may represent a more complete picture of catalytic reactions over zeolites in general.

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Acknowledgements

This work was supported by the Queen’s University of Belfast and Chinese Scholarship Council for a Joint Scholarship. The authors gratefully acknowledged the U.K.’s National High-Performance Computing Service ARCHER (for which access was obtained via the UKCP consortium) and High-Performance Computing (HPC) System at the Queen’s University of Belfast for computing time.

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, The Queen’s University of Belfast, Belfast, UK

    Yu Mao & P. Hu

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  1. Yu Mao
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  2. P. Hu
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Correspondence to P. Hu.

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The authors declare that they have no conflict of interest.

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The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Mao, Y., Hu, P. Identification of the active sites and mechanism for partial methane oxidation to methanol over copper-exchanged CHA zeolites. Sci. China Chem. 63, 850–859 (2020). https://doi.org/10.1007/s11426-019-9695-9

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  • DOI: https://doi.org/10.1007/s11426-019-9695-9

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