Homolytic H2 dissociation for enhanced hydrogenation catalysis on oxides

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 Ga 2 O 3 , that is useful for enhancing hyd...

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Published in:Nature communications Vol. 15; no. 1; pp. 540 - 11
Main Authors: Yang, Chengsheng, Ma, Sicong, Liu, Yongmei, Wang, Lihua, Yuan, Desheng, Shao, Wei-Peng, Zhang, Lunjia, Yang, Fan, Lin, Tiejun, Ding, Hongxin, He, Heyong, Liu, Zhi-Pan, Cao, Yong, Zhu, Yifeng, Bao, Xinhe
Format: Journal Article
Language:English
Published: London Nature Publishing Group UK 15.01.2024
Nature Publishing Group
Nature Portfolio
Subjects:
119/118
140/146
639/638/675
639/638/77/885
639/638/77/887
Alkenes
Carbon dioxide
Catalysis
Coordination
Gallium oxides
Humanities and Social Sciences
Hydrides
Hydrogen
Hydrogenation
Infrared analysis
Low temperature
multidisciplinary
Oxides
Science
Science (multidisciplinary)
ISSN:2041-1723, 2041-1723
Online Access:Get full text
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Summary: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 Ga 2 O 3 , 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 Ga 3+ in homolytic H 2 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 Ga 2 O 3 (H/surface Ga 3+ 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 Ga 3+ . Consequently, by tuning the coordination of active Ga 3+ species as well as the coverage and activity of hydrides, we achieve enhanced hydrogenation of CO 2 to CO, methanol or light olefins by 4-6 times. Zhu et al. report a quantitative and time-resolved analysis of hydrogen activation on Ga 2 O 3 , specifically shedding light on the long-standing puzzle of homolytic dissociation as opposed to the heterolytic pathway on oxides.
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ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-024-44711-7