ABSTRACT Aqueous zinc (Zn)‐ion batteries (AZIBs) hold great promise for large‐scale energy storage owing to their high theoretical volumetric capacity, intrinsic safety, and environmental benignity. However, the strong Zn 2+ ‐H 2 O coordination in conventional electrolytes induces dendrite growth, hydrogen evolution, and passivation, severely limiting reversibility and cycling stability. Herein, a molecular functionalization strategy using zinc tetraphenylporphyrin (ZnTPP) is proposed to achieve coupled regulation of Zn 2+ solvation and interfacial reaction kinetics. The π‐conjugated planar structure and pyrrolic nitrogen atoms of ZnTPP provide dual functions: the nitrogen atoms strongly coordinate with Zn 2+ to weaken Zn 2+ ‐H 2 O interactions and reduce desolvation barriers, while the conjugated plane adsorbs on the Zn surface to redistribute local charge density and suppress dendritic nucleation. Combined experimental and theoretical analyses reveal that ZnTPP stabilizes the primary solvation shell, increases the hydrogen evolution overpotential, and decreases the corrosion current density. Furthermore, ZnTPP increases the Zn 2+ transference number from 0.39 to 0.77, thereby mitigating concentration polarization and facilitating ion transport. This, in turn, lowers the charge‐transfer resistance and enables preferential Zn deposition along the thermodynamically favorable (002) facet, ultimately leading to uniform and compact Zn deposits. This study elucidates the porphyrin‐induced solvation‐interface coupling mechanism and offers a molecular design strategy for stable, high‐performance AZIBs.
Chen et al. (Wed,) studied this question.