Strengthening Intermediate Adsorption on a Cobalt Phthalocyanine Assembly by Polymeric Modification for Electrochemical Carbon Dioxide Reduction into Methanol.

Electrochemical carbon dioxide reduction (CO2R) to generate value added methanol (MeOH) in water has been considered as a potential strategy to realize efficient carbon cycle and reutilization. Cobalt phthalocyanine (CoPc) represents as a classical molecular catalyst carrying precisely tunable active sites, which has been widely explored for the CO2-to-MeOH conversion, but optimization of performance is suffering from relatively easiness in desorption of *CO intermediate. To this end, we developed a novel molecular assembly of CoPc nanotubes (CoT) driven by van der Waals force with surface being modified by poly(4-vinylpyridine). The as-derived catalyst exhibited an exceptional performance of MeOH production for the turnover frequency enhanced by more than 14-fold compared to the pristine CoT, and the Faradaic efficiency is up to 40% at a moderate potential. It revealed that the pyridyl groups of P4VP axially coordinated with the Co catalytic centers shifted the d-band center toward the Fermi level, which strengthened the chemisorption and activation of *CO intermediates, thereby decreasing the whole barrier to produce MeOH. This work demonstrates a novel insight into intermediate manipulation of CO2R and highlights the potential of molecular electrocatalysis for carbon valorization.