GC-DFT-Based\nDynamic Product Distribution Reveals\nEnhanced CO<sub>2</sub>‑to-Methanol Electrocatalysis Durability\nby Heterogeneous CoPc

Heterogeneous cobalt phthalocyanine has emerged as a\npromising\nmolecular catalyst for electrochemical reduction of CO<sub>2</sub> to methanol. Boosting both electrocatalytic durability and selectivity\nremains a great challenge, which is more difficult with unknown regulation\nfactors for the HER side reaction. Herein, to discover the key to\nbalancing the durability and selectivity, as well as HER regulation,\nwe carried out GC-DFT calculations, based on which dynamic product\ndistribution modeling was conducted to visually present the variation\nof the product distribution within the applied voltage range. The\nstrongly electron-donating NMe<sub>2</sub>-substituted CoPc is found\nto be an excellent candidate. The dynamic product distribution reveals\nthat the key to selectivity and durability balance is to regulate\nboth the potential of the highest methanol Faradaic efficiency and\nthe corresponding energy barrier of the selectivity-determining step\nfor hydrogenated CoPc. The pivotal factor in HER regulation stems\nfrom hindered H adsorption due to ligand hydrogenation, arising from\nthe decreased Co-to-H charge transfer. The dynamic product distribution\nanalysis provides intuitive theoretical guidance for highly selective\nand durable CO<sub>2</sub> electroreduction.