Resolving Deactivation Pathways of Co Porphyrin-Based Electrocatalysts for CO₂ Reduction in Aqueous Medium

Carbon-supported first-row transition metal complexes drive electroreduction of CO 2 to CO in aqueous medium with remarkable activity and selectivity. However, their durability under negative potentials is quite low and the deactivation mechanisms are still not clear. Herein, we present an in-depth mechanistic study on the stability of Co porphyrin-based catalysts during CO 2 reduction in an aqueous electrolyte. The mechanisms of the degradation reactions were evaluated for Co tetraphenylporphyrin (CoTPP) using a combination of spectral, electrochemical, and theoretical methods. Our evidence shows that two major pathways contribute to the gradual activity loss. The first route is oxidative and yields the catalytically inactive complex [Co III TPP]OH. The second pathway is based on reductive carboxylation of the porphyrin ring via transient formation of [Co 0 TPP] 2– and [Co 0 TPP-CO] 2– . The latter reaction disrupts the π-system of the porphyrin structure and leads to the complete disintegration of the macrocyclic core. In contrast to the earlier reports, we found that the direct poisoning by CO, demetallation, and reduction to chlorins play no significant role in the deactivation process. It was further determined that the bulky donating functional groups disfavor the formation of dianionic species and restrict access of CO 2 to the vulnerable meso -position of the porphyrin ligand, thus improving the catalyst stability. The effect was found to be especially strong for the −OMe-substituted complex CoTPP-(OMe) 8 that shows excellent reusability under overpotentials below 500 mV. In turn, electronegative substituents such as fluorine suppress the activity of the catalyst and provide no advantages in terms of durability.