Direct Coupling of Methane and Carbon Dioxide on Tantalum Cluster Cations

Understanding molecular-scale reaction mechanisms is crucial for the design of modern catalysts with industrial prospect. Through joint experimental and computational studies, we investigate the direct coupling reaction of CH₄ and CO₂ , two abundant greenhouse gases, mediated by Ta_1,4 ⁺ ions to form larger oxygenated hydrocarbons. Coherent with proposed elementary steps, we expose products of CH₄ dehydrogenation [Ta_1,4 CH₂ ]⁺ to CO₂ in a ring electrode ion trap. Product analysis and reaction kinetics indicate a predisposition of the tetramers for C-O coupling with a conversion to products of CH₂ O, whereas atomic cations enable C-C coupling yielding CH₂ CO. Selected experimental findings are supported by thermodynamic computations, connecting structure, electronic properties, and catalyst function. Moreover, the study of bare Ta_1,4 ⁺ compounds indicates that methane dehydrogenation is a significant initial step in the direct coupling reaction, enabling new, yet unknown reaction pathways.