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Unusual facet and co-catalyst effects in TiO2-based photocatalytic coupling of methane

Author

Listed:
  • Huizhen Zhang

    (Xiamen University)

  • Pengfei Sun

    (Xiamen University)

  • Xiaozhen Fei

    (Xiamen University)

  • Xuejiao Wu

    (Xiamen University)

  • Zongyi Huang

    (Xiamen University)

  • Wanfu Zhong

    (Xiamen University)

  • Qiaobin Gong

    (Xiamen University)

  • Yanping Zheng

    (Xiamen University)

  • Qinghong Zhang

    (Xiamen University)

  • Shunji Xie

    (Xiamen University
    Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM))

  • Gang Fu

    (Xiamen University
    Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM))

  • Ye Wang

    (Xiamen University
    Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM))

Abstract

Photocatalytic coupling of methane to ethane and ethylene (C2 compounds) offers a promising approach to utilizing the abundant methane resource. However, the state-of-the-art photocatalysts usually suffer from very limited C2 formation rates. Here, we report our discovery that the anatase TiO2 nanocrystals mainly exposing {101} facets, which are generally considered less active in photocatalysis, demonstrate surprisingly better performances than those exposing the high-energy {001} facet. The palladium co-catalyst plays a pivotal role and the Pd2+ site on co-catalyst accounts for the selective C2 formation. We unveil that the anatase {101} facet favors the formation of hydroxyl radicals in aqueous phase near the surface, where they activate methane molecules into methyl radicals, and the Pd2+ site participates in facilitating the adsorption and coupling of methyl radicals. This work provides a strategy to design efficient nanocatalysts for selective photocatalytic methane coupling by reaction-space separation to optimize heterogeneous-homogeneous reactions at solid-liquid interfaces.

Suggested Citation

  • Huizhen Zhang & Pengfei Sun & Xiaozhen Fei & Xuejiao Wu & Zongyi Huang & Wanfu Zhong & Qiaobin Gong & Yanping Zheng & Qinghong Zhang & Shunji Xie & Gang Fu & Ye Wang, 2024. "Unusual facet and co-catalyst effects in TiO2-based photocatalytic coupling of methane," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-48866-1
    DOI: 10.1038/s41467-024-48866-1
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    References listed on IDEAS

    as
    1. Wenqing Zhang & Cenfeng Fu & Jingxiang Low & Delong Duan & Jun Ma & Wenbin Jiang & Yihong Chen & Hengjie Liu & Zeming Qi & Ran Long & Yingfang Yao & Xiaobao Li & Hui Zhang & Zhi Liu & Jinlong Yang & Z, 2022. "High-performance photocatalytic nonoxidative conversion of methane to ethane and hydrogen by heteroatoms-engineered TiO2," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    2. Shijia Mu & Honglei Lu & Qianbao Wu & Lei Li & Ruijuan Zhao & Chang Long & Chunhua Cui, 2022. "Hydroxyl radicals dominate reoxidation of oxide-derived Cu in electrochemical CO2 reduction," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    3. Hua Gui Yang & Cheng Hua Sun & Shi Zhang Qiao & Jin Zou & Gang Liu & Sean Campbell Smith & Hui Ming Cheng & Gao Qing Lu, 2008. "Anatase TiO2 single crystals with a large percentage of reactive facets," Nature, Nature, vol. 453(7195), pages 638-641, May.
    4. Lili Zhang & Le Liu & Ziye Pan & Rui Zhang & Zhuoyang Gao & Guangming Wang & Keke Huang & Xiaoyue Mu & Fuquan Bai & Yan Wang & Wei Zhang & Zhonghua Cui & Lu Li, 2022. "Visible-light-driven non-oxidative dehydrogenation of alkanes at ambient conditions," Nature Energy, Nature, vol. 7(11), pages 1042-1051, November.
    5. Ningdong Feng & Huiwen Lin & Hui Song & Longxiao Yang & Daiming Tang & Feng Deng & Jinhua Ye, 2021. "Efficient and selective photocatalytic CH4 conversion to CH3OH with O2 by controlling overoxidation on TiO2," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
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