Tuning the Metal Electronic Structure of Anchored Cobalt Phthalocyanine via Dual‐Regulator for Efficient CO2 Electroreduction and Zn–CO2 Batteries

Abstract Heterogeneous macromolecule catalysts have been known as efficient electrocatalysts for CO 2 reduction reaction, however, manipulating the activity of heterogeneous molecules via controllable metal electronic structure is still challenging. Herein, different CO 2 activated 3D, robust, nitrogen‐doped hollow carbon spheres are synthesized to anchor cobalt phthalocyanine as molecularly dispersed electrocatalysts, where the electron‐withdrawing coeffect of carbon defects and heteroatom N is responsible for tuning the electronic structure of metal center. The optimal electrocatalyst reveals high CO faradaic efficiency (FE CO ) of 95.68%, turnover frequency of 13.80 s −1 , and current density of 16.49 mA cm −2 at an overpotential of 760 mV. The control experiment and DFT calculations unveil that the significant activity is mainly ascribed to the optimal electron‐withdrawing coeffect of carbon defects and pyrrolic N, which reduce the electron density of Co center to facilitate CO 2 activated to form *COOH intermediate on Co(I) active sites during electrocatalysis. The 2 p ‐charge loss of Co is summarized as an activity descriptor, which steers the current density and production rate toward CO. Furthermore, the design strategy can universally fabricate the hybrid MPc catalyst with transitional metal (Ni, Fe) site while a rechargeable Zn–CO 2 battery is devised to deliver a maximal power density of 1.02 mW cm −2 .