Enlarging the π-Conjugation of Cobalt Porphyrin for Highly Active and Selective CO₂ Electroreduction

Heterogeneous molecular catalysts have attracted considerable attention as carbon dioxide reduction reaction (CO₂RR) electrocatalysts. The π-electron system of conjugated ligands in molecular catalysts may play an important role in determining the activity. In this work, by enlarging π-conjugation through appending more aromatic substituents on the porphyrin ligand, altered π-electron system endows the as-prepared 5,10,15,20-tetrakis(4-(pyren-1-yl)phenyl)porphyrin Co^II with high Faradaic efficiency (ca. 95 %) for CO production, as well as high turnover frequency (2.1 s⁻¹ at −0.6 V vs. RHE). Density functional theory calculation further suggests that the improved electrocatalytic performance mainly originates from the higher proportion of Co (Formula presented.) orbital and the CO₂ π* orbital in the HOMO of the (Co−porphyrin−CO₂)⁻ intermediate with larger π-conjugation, which facilitates the CO₂ activation. This work provides strong evidence that π-conjugation perturbation is effective in boosting the CO₂RR.