New Insight into the Electronic Effect for Cu Porphyrin Catalysts in Electrocatalytic of CO₂ into CH₄

Perturbation of the copper (Cu) active site by electron manipulation is a crucial factor in determining the activity and selectivity of electrochemical carbon dioxide (CO₂) reduction reaction (e-CO₂RR) in Cu-based molecular catalysts. However, much ambiguity is present concerning their electronic structure–function relationships. Here, three molecular Cu-based porphyrin catalysts with different electron densities at the Cu active site, Cu tetrakis(4-methoxyphenyl)porphyrin (Cu─T(OMe)PP), Cu tetraphenylporphyrin (Cu─THPP), and Cu tetrakis(4-bromophenyl)porphyrin (Cu─TBrPP), are prepared. Although all three catalysts exhibit e-CO₂RR activity and the same reaction pathway, their performance is significantly affected by the electronic structure of the Cu site. Theoretical and experimental investigations verify that the conjugated effect of ─OCH₃ and ─Br groups lowers the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbitals (LUMO) gap of Cu─T(OMe)PP and Cu─TBrPP, promoting faster electron transfer between Cu and CO₂, thereby improving their e-CO₂RR activity. Moreover, the high inductive effect of ─Br group reduces the electron density of Cu active site of Cu─TBrPP, facilitating the hydrolysis of the bound H₂O and thus creating a preferable local microenvironment, further enhancing the catalytic performance. This work provides new insights into the relationships between the substituent group characteristics with e-CO₂RR performance and is highly instructive for the design of efficient Cu-based e-CO₂RR electrocatalysts.