Monodispersed Molecular Phthalocyanine with Sulfur‐Driven Electron Delocalization for Enhanced Electrochemical Biosensing

Abstract Heterogenizing the molecular catalysts on conductive scaffolds to achieve the isolated molecular dispersion and expected coordination structures is significant yet still challenging. Herein, a sulfur‐driving strategy to anchor monodispersed cobalt phthalocyanine on nitrogen and sulfur co‐doped graphene (NSG‐CoPc) is demonstrated. Experimental and theoretical analysis prove that the incorporation of S dramatically improves the adsorption capability of NSG and evokes the monodispersion of the CoPc molecule, promoting the axial Co─N coordination and the electron delocalization of the Co catalytic center. Benefiting from the reduced activation energy barrier and boosted electron transfer, as well as the maximized active site utilization, NSG‐CoPc exhibits outstanding H 2 O 2 oxidization and sensing performance (used as a representative reaction). Moreover, the usage of NSG as a substrate can be readily extended to other metal (Ni, Cu, and Fe) phthalocyanine molecules with molecular‐level dispersion. This work clarifies the mechanism of heteroatoms decoration and provides a new paradigm in devising monodispersed molecular catalysts with modulated chemical surroundings for broad applications.