Alternative Pathway of CO(2) Hydrogenation by Lewis-Pair-Functionalized UiO-66 MOF Revealed by Metadynamics Simulations

[Image: see text] The reaction between H(2) and CO(2) catalyzed by an intramolecular frustrated Lewis pair, which is covalently bonded to a UiO-66 metal–organic framework (MOF), is considered in this work. Free energy surfaces (FESs) for this reaction are generated throughout finite-temperature density functional theory (DFT) metadynamics (MD) simulations. The simulated FESs indicate an alternative stepwise pathway for the hydrogenation of CO(2). Furthermore, indications of weaker binding of CO(2) than H(2) to the Lewis pair centers have been observed via metadynamics simulations. These findings were unknown from the results of static-DFT calculations, which proposed a concerted reduction of CO(2). The results of the present work may influence the design of new efficient heterogeneous Lewis pair (LP)-functionalized MOFs to catalyze capture and conversion of CO(2) to high-value chemicals.