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Switching from Reforming to Selective Dehydrogenation for Ethane-CO2 Coconversion on CeO2-Based Catalysts via
Feigang Zhao1, Tiantian Xiao1,2, Yong Wang1
1Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin300072, P. R. China.
None:
CeO2-supported metal catalysts are highly efficient and widely employed in the ethane-CO2 coconversion reaction, offering a promising approach to natural gas utilization and greenhouse gas valorization. However, this kind of catalyst with metal-CeO2 interfaces predominantly favors dry reforming of ethane (DRE) to syngas, while achieving selective dehydrogenation to ethylene remains challenging. Here, a crystal-facet engineering strategy was adopted to fabricate nanoporous CeO2 (np-CeO2) with exposed high-index facets (HIFs). The relatively low-coordinated O atoms on HIFs render a stronger bonding with transition metals (e.g., Co), thereby forming more electron-deficient Co species. Consequently, the unique Coδ+-O-Ce interfaces deliver superior selectivity to ethylene (88% on the basis of ethane) for the ethane-CO2 coconversion, whereas Co on CeO2 samples with low-index facets (LIFs) mainly undergoes DRE with only 2% ethylene selectivity. Through combining multiple in situ characterizations and theoretical calculations, it was found that more electron-deficient Coδ+ moderates the adsorption and activation of C-H bonds, suppresses the formation of key DRE intermediates (C2H5O*), and weakens the hybridization with the π orbital of ethylene, thereby promoting product desorption and inhibiting C-C cleavage. This work provides new insights for designing catalysts that achieve high olefin selectivity and CO2 utilization in alkane-CO2 coconversion reactions.
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