Reverse water-gas shift catalyzed by RhVO_3,4^- (n = 3-7) cluster anions under variable temperatures

A fundamental understanding of the exact structural characteristics and reaction mechanisms of interface active sites is vital to engineering an energetic metal-support boundary in heterogeneous catalysis. Herein, benefiting from a newly developed high-temperature ion trap reactor, the reverse water-gas shift (RWGS) (CO₂ + H₂ → CO + H₂O) catalyzed by a series of compositionally and structurally well-defined RhVO_3,4^- (n = 3-7) clusters were identified under variable temperatures (298-773 K). It is discovered that the Rh_5-7VO_3,4^- clusters can function more effectively to drive RWGS at relatively low temperatures. The experimentally observed size-dependent catalytic behavior was rationalized by quantum-chemical calculations; the framework of RhVO_3,4^- is constructed by depositing the Rh clusters on the VO_3,4 "support", and a sandwiched base-acid-base [Rh_out^--Rh_in⁺-VO_3,4^-; Rh_out and Rh_in represent the outer and inner Rh atoms, respectively] feature in Rh_5-7VO_3,4^- governs the adsorption and activation of reactants as well as the facile desorption of the products. In contrast, isolated Rh_5-7^- clusters without the electronic modification of the VO_3,4 "support" can only catalyze RWGS under relatively high-temperature conditions.