Surface structures of CeO2 define the reactivities of reverse water gas shift reaction over CeO2 materials

The reverse water-gas shift (RWGS) reaction represents a pivotal pathway for enabling the resource utilization of CO 2 . CeO 2 has emerged as an ideal catalytic material for this reaction, owing to its unique oxygen storage/release capacity and tunable surface defect properties. In this study, three CeO 2 catalysts with distinct exposed facets—CeO 2 -NC primarily exposed (100) facets, CeO 2 -NP primarily exposed (111) facets, and CeO 2 -NR primarily exposed (110) facets—were synthesized via a hydrothermal method. Experimental results demonstrate that CeO 2 -NR, dominated by (110) facets, exhibits the highest catalytic activity, which is attributed to its highest oxygen vacancy concentration, superior low-temperature reducibility, and the strongest CO 2 adsorption and activation capability. Density functional theory (DFT) calculations and microkinetic analysis revealed the facet-dependent differences in reaction pathways at the atomic scale. This work provides critical insights into the structure-activity relationship between CeO 2 surface architecture and its catalytic performance in the RWGS reaction.