Cobalt Phthalocyanine Axially Coordinated with Carbon Nanotubes for Electrochemical Carbon Dioxide Reduction into Methanol

The electrocatalytic conversion of CO₂ to methanol (MeOH) in aqueous media represents a key pathway toward achieving sustainable carbon recycling and utilization, particularly in the context of carbon neutrality goals. Cobalt phthalocyanine (CoPc), a well-established molecular catalyst with tunable active sites, has been investigated for CO₂-to-MeOH conversion. However, its efficiency for methanol production is often limited by facile desorption of the critical *CO intermediate. Herein, we report a molecular electrocatalyst featuring CoPc axially coordinated with hydroxyl-functionalized carbon nanotubes (CNT-OH). The catalyst demonstrates a significant enhancement in methanol production, achieving a Faradaic efficiency of up to 32.0%. Density functional theory (DFT) calculations and experiments indicate that the axial coordination of hydroxyl groups to the cobalt centers strengthens the chemisorption of the *CO intermediate and promotes electron transfer to the active site Co-N₄. This work offers a strategy for manipulating key intermediates in the CO₂RR and underscores the potential of phthalocyanine-based molecular electrocatalysts for achieving carbon neutrality.