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Homolytic H2 dissociation for enhanced hydrogenation catalysis on oxides

Author

Listed:
  • Chengsheng Yang

    (Fudan University)

  • Sicong Ma

    (Chinese Academy of Sciences)

  • Yongmei Liu

    (Fudan University)

  • Lihua Wang

    (Chinese Academy of Sciences)

  • Desheng Yuan

    (Fudan University)

  • Wei-Peng Shao

    (Shanghai Tech University)

  • Lunjia Zhang

    (Shanghai Tech University)

  • Fan Yang

    (Shanghai Tech University)

  • Tiejun Lin

    (Chinese Academy of Sciences)

  • Hongxin Ding

    (Fudan University)

  • Heyong He

    (Fudan University)

  • Zhi-Pan Liu

    (Fudan University
    Chinese Academy of Sciences)

  • Yong Cao

    (Fudan University)

  • Yifeng Zhu

    (Fudan University)

  • Xinhe Bao

    (Fudan University
    Chinese Academy of Sciences)

Abstract

The limited surface coverage and activity of active hydrides on oxide surfaces pose challenges for efficient hydrogenation reactions. Herein, we quantitatively distinguish the long-puzzling homolytic dissociation of hydrogen from the heterolytic pathway on Ga2O3, that is useful for enhancing hydrogenation ability of oxides. By combining transient kinetic analysis with infrared and mass spectroscopies, we identify the catalytic role of coordinatively unsaturated Ga3+ in homolytic H2 dissociation, which is formed in-situ during the initial heterolytic dissociation. This site facilitates easy hydrogen dissociation at low temperatures, resulting in a high hydride coverage on Ga2O3 (H/surface Ga3+ ratio of 1.6 and H/OH ratio of 5.6). The effectiveness of homolytic dissociation is governed by the Ga-Ga distance, which is strongly influenced by the initial coordination of Ga3+. Consequently, by tuning the coordination of active Ga3+ species as well as the coverage and activity of hydrides, we achieve enhanced hydrogenation of CO2 to CO, methanol or light olefins by 4-6 times.

Suggested Citation

  • Chengsheng Yang & Sicong Ma & Yongmei Liu & Lihua Wang & Desheng Yuan & Wei-Peng Shao & Lunjia Zhang & Fan Yang & Tiejun Lin & Hongxin Ding & Heyong He & Zhi-Pan Liu & Yong Cao & Yifeng Zhu & Xinhe Ba, 2024. "Homolytic H2 dissociation for enhanced hydrogenation catalysis on oxides," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-44711-7
    DOI: 10.1038/s41467-024-44711-7
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    References listed on IDEAS

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    1. Waiz Karim & Clelia Spreafico & Armin Kleibert & Jens Gobrecht & Joost VandeVondele & Yasin Ekinci & Jeroen A. van Bokhoven, 2017. "Catalyst support effects on hydrogen spillover," Nature, Nature, vol. 541(7635), pages 68-71, January.
    2. Shuang Xiang & Lin Dong & Zhi-Qiang Wang & Xue Han & Luke L. Daemen & Jiong Li & Yongqiang Cheng & Yong Guo & Xiaohui Liu & Yongfeng Hu & Anibal J. Ramirez-Cuesta & Sihai Yang & Xue-Qing Gong & Yanqin, 2022. "A unique Co@CoO catalyst for hydrogenolysis of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    3. Yijing Liu & Rankun Zhang & Le Lin & Yichao Wang & Changping Liu & Rentao Mu & Qiang Fu, 2023. "Direct observation of accelerating hydrogen spillover via surface-lattice-confinement effect," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
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