Electrochemical CO₂ Reduction by Urea Hangman Mn Terpyridine species

Based on our previous study in chemical subtleties of the proton tunneling distance for metal hydride formation (PTD-MH) to regulate the selectivity of CO₂ reduction reaction (CO₂RR), we have developed a family of Mn terpyridine derivatives, in which urea groups functions as multipoint hydrogen-bonding hangman to accelerate the reaction rate. We found that such changes to the second coordination sphere significantly increased the turnover frequency (TOF) for CO₂ reduction to ca. 360 $$ with this family of molecular catalysts while maintaining high selectivity (ca. 100 %±3) for CO even in the presence of a large amount of phenol as proton source. Notably, the compounds studied in this manuscript all exhibit large value for $$ as that achieved by Fe porphyrins derivates, while saving up to 0.55 V in overpotential with respect to the latter.