Chemical Coordination and Pore Confinement Enabling a Bifunctional Interface for Accelerated Desolvation and Oriented Deposition Toward Stable Zinc Metal Anodes

Aqueous zinc‐ion batteries show great potential for large‐scale energy storage; however, dendrites formation and corrosion on zinc anodes significantly hinder their practical applications. Uneven Zn deposition leads to dendrite growth, while H 2 O molecules in solvated Zn 2+ ions exacerbate surface corrosion and the hydrogen evolution reaction. Herein, we propose a Schiff‐base‐covalently‐grafted UiO‐66‐NH 2 metal‐organic framework to construct a bifunctional interface for stable zinc metal anodes. Specifically, the chemical chelation between Schiff base and Zn 2+ accelerates desolvation and suppresses side reactions. Meanwhile, the uniformly distributed Zn 2+ ‐chelated sites and the well‐defined confined pore channels of UiO‐66‐NH 2 scaffold guide a homogeneous Zn 2+ flux and promote Zn(002)‐oriented deposition. As a result, this bifunctional interface enables Zn plating/stripping with a high Coulombic efficiency of 99.8% over 2000 cycles at 5 mA cm −2 /1 mAh cm −2 . Furthermore, it achieves a capacity retention of over 90% after 4000 charge–discharge cycles in a Zn||MnO 2 full cell. This work is expected to open a new avenue for interfacial chemical regulation toward stabilizing zinc metal anodes.