Multiple CO2 reduction mediated by heteronuclear metal carbide cluster anions RhTaC2−

Abstract

Noble metals dispersed on transition-metal carbides exhibit extraordinary activity in CO₂ catalytic conversion and bimetallic carbides generated at the interface were proposed to contribute to the observed activity. Heteronuclear metal carbide clusters (HMCCs) that compositionally resemble the bimetallic carbides are suitable models to get a fundamental understanding of the reactivity of the related condensed-phase catalysts, while the reaction of HMCCs with CO₂ has not been touched in the gas phase. Herein, benefiting from the newly designed double ion trap reactors, the reaction of laser-ablation generated and mass-selected RhTaC₂⁻ clusters with CO₂ was studied. The experimental results identified that RhTaC₂⁻ can reduce four CO₂ molecules consecutively and generate the product RhTaC₂O₄⁻. The pivotal roles of Rh–Ta synergy and the C₂ ligand in driving CO₂ reduction were rationalized by theoretical calculations. The presence of an attached CO unit on the product RhTaC₂O₄⁻ was evidenced by the collision-induced dissociation experiment, providing a fundamental strategy to alleviate carbon deposition under a CO₂ atmosphere at elevated temperatures.