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Research Article

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

Wencui Li1,2,§, Yu Ren2,§, Zean Xie2,§, Yipeng Wang2, Hang Zhang2(), Dianxiang Peng3, Hengfang Shen1, Hongfei Shi3(), Jiaxin Cai1, Peng Wang2, Tongxin Zhang2, Zhen Zhao1,2()
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China
Institute of Catalysis for Energy and Environment, College of Chemistry & Chemical Engineering, Shenyang Normal University, Shenyang 110034, China
Institute of Petrochemical Technology, Jilin Institute of Chemical Technology, Jilin 132022, China

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

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The intrinsic inertness of the C–H bond in methane poses a significant challenge for the direct conversion of methane into high-value-added chemicals. This study is focused on the design of a Cu/TiO2 nanofiber composite catalyst, which exhibits unparalleled performance in converting methane to oxygenates under mild conditions. Furthermore, this study emphasizes the pivotal role of valuable insights in advancing the development of non-noble metal/semiconductor materials with significantly enhanced catalytic performance.

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·h−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 CuI 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.

Keywords

TiO2 nanofibercopper nanoparticlesphoto-deposition methodmethane oxidationC1 oxygenates

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Nano Research
Volume 17 Issue 5,
May 2024
Pages 3844-3852
DOI: 10.1007/s12274-023-6356-9
Cite this article:
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 Research, 2024, 17(5): 3844-3852. https://doi.org/10.1007/s12274-023-6356-9
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