Revealing a Double‐Volcano‐Like Structure‐Activity Relationship for Substitution‐Functionalized Metal‐Phthalocyanine Catalysts toward Electrochemical CO2 Reduction

Abstract Electron‐donating/‐withdrawing groups (EDGs/EWGs) substitution is widely used to regulate the catalytic performance of transition‐metal phthalocyanine (MPc) toward electrochemical CO 2 reduction, but the corresponding structure‐activity relationships and regulation mechanisms are still ambiguous. Herein, by investigating a series of substitution‐functionalized MPc (MPc‐X), this work reveals a double‐volcano‐like relationship between the electron‐donating/‐withdrawing abilities of the substituents and the catalytic activities of MPc‐X. The weak‐EDG/‐EWG substitution enhances whereas the strong‐EDG/‐EWG substitution mostly lowers the CO selectivity of MPc. Experimental and calculation results demonstrate that the electronic properties of the substituents influence the symmetry and energy of the highest occupied molecular orbitals of MPc‐X, which in turn determine the CO 2 adsorption/activation and lead to diverse CO 2 reduction pathways on the EWG or EDG substituted MPc via different CO 2 adsorption modes. This work provides mechanism insights that could be guidance for the design and regulation of molecular catalysts.