In-modified Ni/CeO2 for reverse water-gas shift: Cooperation between oxygen vacancies and intermetallic compounds

•Ni-In IMCs with active site isolation and Ni-In electronic interaction are dispersed on the surface of CeO2.•*CO is an important intermediate during CO2 hydrogenation.•The poor amount and transfer ability of active *H on IMCs drive the *CO to desorb from 10Ni-5In-CeO2.•CeO2 with abundant oxygen vacancies is identified as the most suitable support with the highest CO2 conversion.•The incorporation of In into Ni/CeO2 catalysts significantly improves the RWGS reaction. The reverse water–gas shift (RWGS) reaction has been identified as one of the most techno-economically viable strategies for handling with antropogenic CO2 emissions, but high-efficiency RWGS catalysts are still challenging. Herein, a series of In-modified Ni-based catalysts with variations of the support and the Ni/In ratio were prepared by a simple wet impregnation method. The high activity for RWGS reaction is achieved on the CeO2-supported catalysts. The incorporation of In into Ni/CeO2 catalysts significantly increases CO selectivity. The optimal 10Ni-5In-CeO2 catalyst shows 97.2 % CO selectivity at CO2 conversion rate of 52.8 mmol gNi−1 h−1 for 100 h without obvious deactivation at 350 °C. The oxygen vacancies on CeO2 and the active *H species on Ni-In intermetallic compounds (IMCs) are responsible for the enhancement of RWGS reaction. This work provides a guidance to high-efficiency catalysts for CO2 hydrogenation by cooperation between active metal and oxide support.