DFT calculations are used to study the effect of heterocyclic ligands attached to a Co-porphyrin catalyst (Co-PMOF) on the molecular orbitals and free energies of the conversion from CO<sub>2</sub> to CO.  Geometries were optimized for each of the 9 steps of the reaction mediated by three different catalysts: the original Co-PMOF complex, a catalyst-pyridine complex, and a catalyst-imidazole complex, with the heterocyclic ligands added to the cobalt atom of the catalyst.  The goal of the study is to explain the increased efficiency of the reaction when a heterocycle is attached to the Co-PMOF.  Initial optimizations were carried out at the B3LYP level and 3-21G or LANL2DZ basis sets, and ultimately re-optimized with the M06 level and pc-2 basis and a polarizable continuum solvation model.  Visualization of the MOs is used to justify the effect of the ligands on the free energies of the states at the rate determining step, and to interpret the observed improvement in reaction efficiency.

DFT modeling of Co-PMOF catalyzed conversion of CO<sub>2</sub> to CO

ACS Spring 2022

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DFT modeling of Co-PMOF catalyzed conversion of CO2 to CO

DFT modeling of Co-PMOF catalyzed conversion of CO₂ to CO