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

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 H2O2 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. The incorporation of the S atom triggers the monodispersion of cobalt phthalocyanine on nitrogen and sulfur co‐doped graphene (NSG‐CoPc), as well as evokes the electronic localization among the axial Co─N coordination. The strong electronic interaction lowers the H2O2 activation energy barrier and confers NSG‐CoPc with boosted H2O2 oxidation and sensing performance.