Converting CO₂ to formic acid by tuning quantum states in metal chalcogenide clusters

The catalytic conversion of CO₂ into valuable chemicals is an effective strategy for reducing its adverse impact on the environment. In this work, the formation of formic acid via CO₂ hydrogenation on bare and ligated Ti₆Se₈ clusters is investigated with gradient-corrected density functional theory. It is shown that attaching suitable ligands (i.e., PMe₃, CO) to a metal-chalcogenide cluster transforms it into an effective donor/acceptor enabling it to serve as an efficient catalyst. Furthermore, by controlling the ratio of the attached donor/acceptor ligands, it is possible to predictably alter the barrier heights of the CO₂ hydrogenation reaction and, thereby, the rate of CO₂ conversion. Our calculation further reveals that by using this strategy, the barrier heights of CO₂ hydrogenation can be reduced to ~0.12 eV or possibly even lower, providing unique opportunities to control the reaction rates by using different combinations of donor/acceptor ligands.