Single‐Site Heterogenized Molecular Catalysts towards CO2 Hydrogenation to Formates, Formamides and Methanol

Abstract Harnessing CO 2 in conjunction with inexpensive reusable H 2 for catalytic hydrogenation is a viable method for lowering the environmental impact of industrial operations while producing useful chemicals and fuels. To make the process more sustainable, particular emphasis was paid to the heterogeneous catalyst system in this regard. Intending to profit from both homogeneous and heterogeneous catalysis in real‐world circumstances for the CO 2 hydrogenation reaction, heterogenized molecular catalysts are receiving a lot of attention among heterogeneous catalysts. This review is devoted to significant developments in single‐site heterogenized molecular catalysts for CO 2 hydrogenation reactions. Attempting to illustrate the state‐of‐the‐art developments in this domain, the present work meticulously summarizes several recently reported heterogenized molecular catalysts for the CO 2 hydrogenation process producing formic acid/formate, N‐formamide, and methanol. The fundamental structure–activity relationships and mechanistic understanding are given particular attention since they offer solid foundations for sensible catalyst architectural design. Important variables that influence catalytic activity are also emphasized, such as electron density, metal dispersion, porous nature, surface area, a robust backbone, and coordination environment of metal sites. Finally, a short assessment is given as potential directions for further research.