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Methane activation by [LnO]+: the 4f orbital matters

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Abstract

Gas-phase reactions of [LnO]+ with methane have been studied by using inductively coupled plasma-mass spectrometer (ICPMS) combined with quantum chemical calculations. Experiments indicate that the [LnO]+ (Ln=Sm-Lu) ions are able to activate methane to generate methyl radicals. In particular, [EuO]+ and [YbO]+ exhibit the highest reactivity. Interestingly, ab initio computations reveal a novel HAT process operating in the absence of a terminal oxygen radical, as mediated by [EuO]+ and [YbO]+. Such a process diverges from previous findings on the methane activation by metal oxide clusters, not only on the electronic pattern during the course of hydrogen transfer, but also on the important role that 4f electrons play. The associated electronic origins have been discussed, and the well-designed 4f electron occupation may turn to be a promising approach in constructing lanthanide involved catalysts.

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Acknowledgments

This work is supported by the “Pioneer” and “Leading Goose” R&D Program of Zhejiang (2023C01102, 2023C01208) and the “AI for Electrochemistry Program” of Xiamen University (RD2023100101).

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Authors and Affiliations

  1. College of Chemical and Biological Engineering, Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, Zhejiang University, Hangzhou, 310027, China

    Bowei Yuan & Shaodong Zhou

  2. Zhejiang Provincial Innovation Center of Advanced Chemicals Technology, Institute of Zhejiang University-Quzhou, Quzhou, 324000, China

    Bowei Yuan, Mincheng Yu & Shaodong Zhou

  3. Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen, 361005, China

    Jingxiang Zou

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  1. Bowei Yuan
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  2. Jingxiang Zou
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Correspondence to Jingxiang Zou, Mincheng Yu or Shaodong Zhou.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://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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Yuan, B., Zou, J., Yu, M. et al. Methane activation by [LnO]+: the 4f orbital matters. Sci. China Chem. 67, 330–335 (2024). https://doi.org/10.1007/s11426-023-1801-4

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  • DOI: https://doi.org/10.1007/s11426-023-1801-4

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