Covalently Grafting Cobalt Porphyrin onto Carbon Nanotubes for Efficient CO₂ Electroreduction

Molecular complexes with inexpensive transition-metal centers have drawn extensive attention, as they show a high selectivity in the electrochemical conversion of CO₂ to CO. In this work, we propose a new strategy to covalently graft cobalt porphyrin onto the surface of a carbon nanotube by a substitution reaction at the metal center. Material characterization and electrochemical studies reveal that the porphyrin molecules are well dispersed at a high loading of 10 wt. %. As a result, the turnover frequency for CO formation is improved by a factor of three compared to traditional physically-mixed catalysts with the same cobalt content. This leads to an outstanding overall current density of 25.1 mA cm^-2 and a Faradaic efficiency of 98.3 % at 490 mV overpotential with excellent long-term stability. This work provides an effective pathway for the improvement of the performance of electrocatalysts that could inspire rational design of molecular catalysts in the future.