A cofacial iron tetraphenyl porphyrin dimer, , bio-inspired by the Ni-Fe containing metalloenzyme, carbon monoxide dehydrogenase (CODH), efficiently and selectively catalyses the electrochemical reduction of CO2 to CO in DMF/10% H2O solution at the electro-generated Fe(0)(por) species with high Faradic efficiency (95%) and TOF (4300 s(-1)) at a moderate overpotential, η = 0.66 V.

Electrocatalytic water splitting to oxygen and hydrogen has much attention as one of the most promising approaches for sustainable production of hydrogen as a carbon-neutral fuel. To establish efficient electrocatalytic...

Efficient reduction of CO2 into useful carbon resources particularly CO is an essential reaction for developing alternate sources of fuels and for reducing the greenhouse effect of CO2. The binuclear Ni, Fe−containing carbon monoxide dehydrogenase (CODHs) efficiently catalyzes the reduction of CO2 to CO. The location of Ni and Fe at proper positions allows their cooperation for CO2 to CO conversion through a push−pull mechanism. Bio−inspired from CODHs, we used several cofacial porphyrin dimers with different substituents as suitable ligands for holding two Fe ions with suitable Fe−Fe separation distance to efficiently and selectively promote CO2 to CO conversion with high turnover frequencies, TOFs. The substituents on the porphyrin rings greatly affect the catalysis process. By introducing electron-withdrawing/-donating groups, e.g. electron-withdrawing perfluorophenyl, at all meso positions of the porphyrin rings, the catalysis overpotential, η was minimized by ≈0.3 V compared to that obtained by introducing electron-donating mesityl groups. The Fe porphyrin dimers among reported catalysts are the most efficient ones for CO2 to CO conversion. Control experiments indicate that the high performance of the current CO2 to CO conversion catalysts is due to the presence of binuclear Fe centers at suitable Fe−Fe separation distance.