Vitamin B₁₂ on Graphene for Highly Efficient CO₂ Electroreduction

Combining the advantages of homogeneous and heterogeneous catalytic systems has emerged as a promising strategy for electrochemical CO₂ reduction although developing robust, active, product-selective, and easily available, catalysts remains a major challenge. Herein, we report the electroreduction of CO₂ catalyzed by cobalt and benzimidazole containing Vitamin B₁₂ immobilized on the surface of reduced graphene oxide (rGO). This hybrid system with a naturally abundant molecular catalyst produces CO with high selectivity and a constant current density in an aqueous buffer solution (pH 7.2) for over 10 h. A Faradaic efficiency (FE) of 94.5% was obtained for converting CO₂ to CO at an overpotential of 690 mV with a CO partial current density (j_CO) of 6.24 mA cm^-2 and a turnover frequency (TOF) of up to 28.6 s^-1. A higher j_CO (13.6 mA cm^-2) and TOF (52.4 s^-1) can be achieved with this system at a higher overpotential (790 mV) without affecting the product selectivity (∼94%) for CO formation. Our experimental findings are corroborated with density functional theory (DFT) studies to understand the influence of the covalently attached and redox-active benzimidazole unit. To the best of our knowledge, this is the first example of naturally abundant vitamin being immobilized on a conductive surface for highly efficient CO₂ electroreduction.