Reaction-induced regioselective reconstruction of Ni-doped Ce(OH)₃/CeO₂ enables exceptional activity and selectivity for reverse water-shift reaction.

Abstract

Reconstruction of catalysts by reaction environments represents a viable approach to create highly performed active sites. Herein, we develop a reaction-induced regioselective reconstruction of Ni-doped Ce(OH)₃/CeO₂ nanorods to form dual-active sites composed of carburized Ni clusters and frustrated Lewis pairs (FLPs), delivering exceptional activity, selectivity and stability for reverse water-gas shift reaction. Ni aggregation in the Ce(OH)₃ region, coupled with in-situ carbonization by catalytically generated CO during reaction, induces the formation of the carburized Ni clusters, which effectively promoted H₂ dissociation. Additionally, Ni doping in the CeO₂ region and Ce(OH)₃-to-CeO₂ phase transition introduce more oxygen vacancies and thereby generated FLPs in CeO₂, which facilitate CO₂ adsorption and subsequent hydrogenation by spilled *H species from the carburized Ni clusters. Weak CO adsorption on both the carburized Ni clusters and FLPs significantly suppresses the methanation side-reaction. This reaction-induced regioselective reconstruction strategy provides a new avenue for designing highly performed catalysts.