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 multi point hydrogen-bonding hangman to accelerate the reaction rate. We found that such changes to the second coordination sphere significantly increased the turn over frequency (TOF) for CO(2 )reduction to ca.360 s(-1) 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 I-cat/I-pas that achieved by Fe porphyrins derivates, while saving up to 0.55 V in over potential with respect to the latter.