Catalytic hydrogenation of CO₂ to methanol in a Lewis pair functionalized MOF

Capture and conversion of CO₂ to methanol using a renewable source of H₂ is a promising way to reduce net CO₂ emissions while producing valuable fuels. Design of an efficient heterogeneous catalyst for CO₂ hydrogenation is critical for the large-scale implementation of the CO₂ to methanol process. Combining both capture and conversion of CO₂ in a single material has the potential to reduce the overall cost through process intensification. We have used density functional theory to computationally design a catalyst capable of producing methanol from CO₂ and H₂, including calculating the reaction pathways and barriers of each step. The catalyst consists of a microporous metal organic framework (UiO-67) functionalized with catalytically active Lewis pair functional groups. Our calculations indicate that this novel catalyst facilitates the heterolytic dissociation of H₂ to generate hydridic and protic H atoms bound to Lewis acid and base sites, respectively, which facilitates a series of simultaneous transfer of two hydrogens to produce methanol: (Chemical Equation Presented). Importantly, our catalyst binds H₂ more strongly than CO₂, which prevents CO₂ from poisoning the Lewis acid and base sites.