Effect of nanostructuring on the interaction of CO₂ with molybdenum carbide nanoparticles

Transition metal carbides are increasingly used as catalysts for the transformation of CO₂ into useful chemicals. Recently, the effect of nanostructuring of such carbides has started to gain relevance in tailoring their catalytic capabilities. Catalytic materials based on molybdenum carbide nanoparticles (MoC_y) have shown a remarkable ability to bind CO₂ at room temperature and to hydrogenate it into oxygenates or light alkanes. However, the involved chemistry is largely unknown. In the present work, a systematic computational study is presented aiming to elucidate the chemistry behind the bonding of CO₂ with a representative set of MoC_y nanoparticles of increasing size, including stoichiometric and non-stoichiometric cases. The obtained results provide clear trends to tune the catalytic activity of these systems and to move towards more efficient CO₂ transformation processes.