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Selective Photo-oxidation of Methane to Methanol with Oxygen over Dual-Cocatalyst-Modified Titanium Dioxide

  • Hui Song
    Hui Song
    International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
    Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0814, Japan
    More by Hui Song
  • Xianguang Meng*
    Xianguang Meng
    International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
    Hebei Provincial Laboratory of Inorganic Nonmetallic Materials, College of Materials Science and Engineering, North China University of Science and Technology, Tangshan 063210, P. R. China
    *Email: [email protected]
  • Shengyao Wang*
    Shengyao Wang
    International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
    College of Science, Huazhong Agricultural University, Wuhan 430070, P. R. China
    *Email: [email protected]
  • Wei Zhou
    Wei Zhou
    Department of Applied Physics, Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparing Technology Faculty of Science, Tianjin University, Tianjin 300072, P. R. China
    More by Wei Zhou
  • Shuang Song
    Shuang Song
    International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
    More by Shuang Song
  • Tetsuya Kako
    Tetsuya Kako
    International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
    More by Tetsuya Kako
  • , and 
  • Jinhua Ye*
    Jinhua Ye
    International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
    Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0814, Japan
    TJU-NIMS International Collaboration Laboratory, School of Material Science and Engineering, Tianjin University, Tianjin 300072, P. R. China
    *Email: [email protected]
    More by Jinhua Ye
Cite this: ACS Catal. 2020, 10, 23, 14318–14326
Publication Date (Web):November 23, 2020
https://doi.org/10.1021/acscatal.0c04329
Copyright © 2020 American Chemical Society
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Abstract

Direct and selective oxidation of CH4 with dioxygen to methanol is a “dream reaction” in modern catalysis yet remains a great challenge. Here, we report that TiO2 loaded with dual cocatalysts, that is, nanometals and cobalt oxide (CoOx) nanoclusters, is capable of selectively catalyzing CH4 to CH3OH at room temperature under photoexcitation using abundant and inexpensive O2 as an oxidant. The best activity for the formation of the primary products, CH3OOH and CH3OH, is up to 50.8 μmol for 2 h with 95% selectivity. Mechanistic studies elucidate that the superior activity and selectivity result from the synergistic effect of nanometals and CoOx. Nanometals enhance CH4 conversion by promoting the separation of the photoexcited electron and the reduction of O2. The CoOx mediates a mild CH4 oxidation process by suppressing the formation of highly oxidative OH radicals that can further oxidize CH3OH to HCHO and CO2, thereby preserving a high selectivity toward oxygenated products. This work provides a prototype in designing efficient photocatalysts for selective oxidation of CH4 to CH3OH with O2 under mild conditions.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.0c04329.

  • Additional experimental data and results including physicochemical properties of catalysts, 1H NMR spectrum, AQE calculation, photocatalytic activity, comparison of catalytic activity in methane oxidation to methanol, TEM image, SAED pattern, EPR spectra, GC–MS spectra, and DFT calculations (PDF)

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