Potential-driven structural distortion in cobalt phthalocyanine for electrocatalytic CO2/CO reduction towards methanol

Cobalt phthalocyanine immobilized on carbon nanotube has demonstrated appreciable selectivity and activity for methanol synthesis in electrocatalytic CO2/CO reduction. However, discrepancies in methanol production selectivity and activity between CO2 and CO reduction have been observed, leading to inconclusive mechanisms for methanol production in this system. Here, we discover that the interaction between cobalt phthalocyanine molecules and defects on carbon nanotube substrate plays a key role in methanol production during CO2/CO electroreduction. Through detailed operando X-ray absorption and infrared spectroscopies, we find that upon application of cathodic potential, this interaction induces the transformation of the planar CoN4 center in cobalt phthalocyanine to an out-of-plane distorted configuration. Consequently, this potential induced structural change promotes the transformation of linearly bonded *CO at the CoN4 center to bridge *CO, thereby facilitating methanol production. Overall, these comprehensive mechanistic investigations and the outstanding performance (methanol partial current density over 150 mA cm−2) provide valuable insights in guiding the activity and selectivity of immobilized cobalt phthalocyanine for methanol production in CO2/CO reduction. Immobilized cobalt phthalocyanine shows promise in CO2 electroreduction to methanol. However, the reaction mechanism remains unclear. This study reveals that cathodic potential critically influences methanol production by altering the symmetry and binding properties at the cobalt active center.