Homolytic H2 dissociation for enhanced hydrogenation catalysis on oxides

AbstractThe 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.

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Published: Jan 15, 2024
Vol/Issue: 15(1)
License: View

Authors

Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, 29 Zhongguancun East Road, Haidian District, Beijing 100190, China; School of Future Technology, University of Chinese Academy of Sciences, Beijing 100039, China; Information Science Academy, China Electronics Technology Group Corporation, Beijing 100086, China

F

Fan Yang

Guilin Medical University

T

Tiejun Lin

CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, P. R. China

Collaborative Innovation Center of Chemistry for Energy Material, Key Laboratory of Computational Physical Science (Ministry of Education), Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200433, China

Y

Yong Cao

National Institute of Biological Sciences, Beijing 102206, China

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China; Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Funding

National Natural Science Foundation of China Award: 22CAA00915

Cite This Article

Chengsheng Yang, Yongmei Liu, Lihua Wang, et al. (2024). Homolytic H2 dissociation for enhanced hydrogenation catalysis on oxides. Nature Communications, 15(1). https://doi.org/10.1038/s41467-024-44711-7

Homolytic H2 dissociation for enhanced hydrogenation catalysis on oxides

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