Activation and transformation of carbon dioxide by gas-phase species: Mechanisms and advances

The activation and transformation of carbon dioxide (CO2) are of fundamental importance to sustainable energy and environmental remediation. Here, we review our group’s advances in employing gas-phase ions to mediate these processes, an approach that affords unique molecular-level mechanistic understanding by combining mass spectrometry and density functional theory calculations. This review is structured around three fundamental reaction types of CO2 transformation: reduction to carbon monoxide (CO) through oxygen-atom transfer to a suitable oxygen acceptor, B−C bond formation via reactions with metal borides, C−N bond formation by coupling with NH3 or N2. The fundamental knowledge uncovered in these gas-phase studies establishes a foundational framework for future research and the rational design of novel catalytic systems for CO2 conversion.