Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO₂ Conversion to CO

Photosynthetic CO 2 fixation is mediated by the enzyme RuBisCo, which employs a nonredox-active metal (Mg 2+ ) to bind CO 2 adjacent to an organic ligand that provides reducing equivalents for CO 2 fixation. Attempts to use porphyrins as ligands in reductive catalysis have typically encountered severe stability issues owing to ligand reduction. Here, a synthetic zinc–bacteriochlorin is reported as an effective and robust electrocatalyst for CO 2 reduction to CO with an overpotential of 330 mV, without undergoing porphyrin-like ligand degradation (or demetalation) even after prolonged bulk electrolysis. The reaction has a CO Faradaic efficiency of 92% and sustains a total current density of 2.3 mA/cm 2 at −1.9 V vs Ag/AgCl. DFT calculations highlight the molecular origin of the observed stability and provide insights into catalytic steps. This bioinspired study opens avenues for the application of bacteriochlorin compounds for reductive electrocatalysis with extended life beyond that seen with porphyrin counterparts.