Enhanced Catalytic Activity of Cobalt Porphyrin in CO₂ Electroreduction upon Immobilization on Carbon Materials

In a comparative study of the electrocatalytic CO₂ reduction, cobalt meso-tetraphenylporphyrin (CoTPP) is used as a model molecular catalyst under both homogeneous and heterogeneous conditions. In the former case, employing N,N-dimethylformamide as solvent, CoTPP performs poorly as an electrocatalyst giving low product selectivity in a slow reaction at a high overpotential. However, upon straightforward immobilization of CoTPP onto carbon nanotubes, a remarkable enhancement of the electrocatalytic abilities is seen with CO₂ becoming selectively reduced to CO (>90 %) at a low overpotential in aqueous medium. This effect is ascribed to the particular environment created by the aqueous medium at the catalytic site of the immobilized catalyst that facilitates the adsorption and further reaction of CO₂ . This work highlights the significance of assessing an immobilized molecular catalyst from more than homogeneous measurements alone.