Bio-mimetic self-assembled computationally designed catalysts of Mo and W for hydrogenation of CO2/dehydrogenation of HCOOH inspired by the active site of formate dehydrogenase

Abstract

Density functional theory modelling has been used to design Mo and W-based catalysts MoIII(tBu)(CO) and WIII(tBu)(CO) for CO₂ hydrogenation and HCOOH dehydrogenation, which are bio-mimics of the active site of formate dehydrogenase. Based on DFT calculations, the molybdenum and tungsten based complexes are good catalysts in the +3 oxidation state for CO₂ hydrogenation with free energies of 24.03 and 21.31 kcal mol⁻¹, respectively. Such a low barrier indicates that our newly designed Mo and W-based complexes are very efficient for CO₂ hydrogenation or HCOOH dehydrogenation catalysis. Overall, our computational results provide in depth insights that can serve as a great tool for the design and development of new and efficient molybdenum and tungsten based catalysts for CO₂ hydrogenation or HCOOH dehydrogenation.