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TiO2 nanofiber-supported copper nanoparticle catalysts for highly efficient methane conversion to C1 oxygenates under mild conditions

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Abstract

The selective oxidation of methane under mild conditions remains the “Holy Grail of Catalysis”. The key to activating methane and inhibiting over-oxidation of target oxygenates lies in designing active centers. Copper nanoparticles were loaded onto TiO2 nanofibers using the photo-deposition method. The resulting catalysts were found to effectively convert methane into C1 oxygenated products under mild conditions. Compared with previously reported catalysts, it delivers a superior performance of up to 2510.7 mmol·gCu−1·hr−1 productivity with a selectivity of around 100% at 80 °C for 5 min. Microstructure characterizations and density functional theory (DFT) calculations indicate that TiO2 in the mixed phase of anatase and rutile significantly increases the Cu+/Cu0 ratio of the supported Cu species, and this ratio is linearly related to the formation rate of oxygen-containing species. The Cu1 site promotes the generation of active O species from H2O2 dissociation on Cu2O (111). These active O species reduce the energy barrier for breaking the C–H bond of CH4, thus boosting the catalytic activity. The methane conversion mechanism was proposed as a methyl radical pathway to form CH3OH and CH3OOH, and then the generated CH3OH is further oxidized to HOCH2OOH.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 92145301, 91845201, 22002094, 22102106, and 22309061) and the Natural Science Foundation of Jilin Province (No. YDZJ202201ZYTS360).

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Author notes

  1. Wencui Li, Yu Ren, and Zean Xie contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing, 102249, China

    Wencui Li, Hengfang Shen, Jiaxin Cai & Zhen Zhao

  2. Institute of Catalysis for Energy and Environment, College of Chemistry & Chemical Engineering, Shenyang Normal University, Shenyang, 110034, China

    Wencui Li, Yu Ren, Zean Xie, Yipeng Wang, Hang Zhang, Peng Wang, Tongxin Zhang & Zhen Zhao

  3. Institute of Petrochemical Technology, Jilin Institute of Chemical Technology, Jilin, 132022, China

    Dianxiang Peng & Hongfei Shi

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  1. Wencui Li
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Correspondence to Hang Zhang, Hongfei Shi or Zhen Zhao.

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TiO2 nanofiber-supported copper nanoparticle catalysts for highly efficient methane conversion to C1 oxygenates under mild conditions

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Li, W., Ren, Y., Xie, Z. et al. TiO2 nanofiber-supported copper nanoparticle catalysts for highly efficient methane conversion to C1 oxygenates under mild conditions. Nano Res. 17, 3844–3852 (2024). https://doi.org/10.1007/s12274-023-6356-9

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