Reverse water–gas shift reaction over ceria nanocube synthesized by hydrothermal method

• A well-defined ceria nanocube with six (100) planes was successfully prepared by a facile hydrothermal method
• Ceria nanocube showed good performance of RWGS reaction, while nickel on ceria evidently promoted the hydrogenation of CO2.
• An oxygen-transformation and metal-dissociation mechanism for RWGS reaction is proposed.

A well-defined ceria nanocube with six (100) planes was successfully prepared by a facile hydrothermal method. Hydrogenation tests on the carbon dioxide, and several advanced analysis techniques, were used to investigate the catalytic performance of ceria nanocube for reverse water–gas shift (RWGS) and understand the governing reaction mechanism. The results demonstrated that the obtained ceria was a typical mesoporous material with a fluorite structure, and mainly had cerium with + 4 valence oxidation state. As-obtained ceria nanocube showed good performance for RWGS reaction, while nickel on ceria evidently promoted the hydrogenation of CO2. An oxygen-transformation and metal-dissociation mechanism for RWGS reaction was proposed. The dissociation of carbon dioxide over ceria by directly oxidized oxygen vacancy was considered as a main reaction pathway of RWGS. Meanwhile, dissociated adsorption of CO2 and hydrogen over nickel surface directly formed CO and supplied spillover hydrogen to nearby oxygen vacancies, respectively. The neighboring oxygen vacancies at the interface of nickel and ceria were considered as efficient active sites for CO2 hydrogenation.