Unveiling the Neighboring Screening Effect and Strong p‐d Coupling in CO₂ Reduction on Graphene‐Supported Metal‐Free and Iron Phthalocyanine

Phthalocyanine and its metal complex, with the support of graphene as the single atomic catalysts (SACs), have gained significant attention in electroreduction applications. However, the contributions from the neighbor atoms of the reaction site and the graphene support in CO 2 reduction reaction (CO 2 RR) are not clear due to the complex reaction pathways involved. To explore the catalytic potential in CO 2 RR, a theoretical study on phthalocyanine (H 2 Pc) and iron phthalocyanine (FePc) is conducted to reveal detailed influences of adsorbing sites, reaction energy, and electron behaviors of the C 1 pathway. The screening shielding effect arising from the strong p‐d coupling of the FeN binding is observed on the 2nd nearest neighboring site, thus, suppressing the neighboring effect. Meanwhile, two catalysts supported by graphene are fully investigated based on thermodynamic factors and the electron behaviors of graphene are interpreted. A higher CO 2 RR activity facilitated by electrostatic repulsions of graphene is discovered on both catalysts. This work establishes a theoretical framework for metal phthalocyanine SACs integrated with graphene in CO 2 RR catalysis and uncovers the trends of electron activities and catalytic performances.