GC-DFT-Based Dynamic Product Distribution Reveals Enhanced CO₂-to-Methanol Electrocatalysis Durability by Heterogeneous CoPc

Heterogeneous cobalt phthalocyanine has emerged as a promising molecular catalyst for electrochemical reduction of CO₂ to methanol. Boosting both electrocatalytic durability and selectivity remains a great challenge, which is more difficult with unknown regulation factors for the HER side reaction. Herein, to discover the key to balancing the durability and selectivity, as well as HER regulation, we carried out GC-DFT calculations, based on which dynamic product distribution modeling was conducted to visually present the variation of the product distribution within the applied voltage range. The strongly electron-donating NMe₂-substituted CoPc is found to be an excellent candidate. The dynamic product distribution reveals that the key to selectivity and durability balance is to regulate both the potential of the highest methanol Faradaic efficiency and the corresponding energy barrier of the selectivity-determining step for hydrogenated CoPc. The pivotal factor in HER regulation stems from hindered H adsorption due to ligand hydrogenation, arising from the decreased Co-to-H charge transfer. The dynamic product distribution analysis provides intuitive theoretical guidance for highly selective and durable CO₂ electroreduction.