Tunable Mesoporous Porphyrin‐Based Conjugated Polymer Capable of Boosting Four‐Electron Zn‐I₂ Batteries

Abstract Porphyrin‐based conjugated polymers (PCPs) have garnered significant attention due to their exceptional conjugated π‐electron system and remarkable physical/chemical properties, further endowing them with ordered mesoscopic architecture to break the intrinsic non/microporous restriction is highly desirable, but it still remains a great challenge. Herein, a facile bottom‐up approach for fabricating ordered mesoporous PCPs (mPCPs) with tunable mesoporous channels through colloid‐mediated self‐assembly are presented. The resultant orders mesoscopic architecture featuring a substantial specific surface area (99.3 m² g⁻¹) and polar skeleton, remarkably improved anchoring properties for iodine chloride molecule. Meanwhile, the optimized mass transport facilitated by the robust mesoporous channels, coupled with the increased accessibility of polar functional groups, renders the structures with an ideal nanoreactor for the highly synergistic stabilization of the four‐electron I⁺/I₂/I⁻ conversion process. Therefore, the mPCPs host exhibits a high specific capacity (321 mA h g⁻¹ at 0.5 A g⁻¹), excellent rate performance, and cycle stability (266 mAh g⁻¹ at 3.0 A g⁻¹ after 1800 cycles), underscoring its potential as an effective platform for zinc‐iodine batteries. This study will provide a new method for precise control and engineering of mesoporous structures tailored for specific functionalities and electrochemical requirements, thereby facilitating the development of advanced materials based on multi‐electron energy storage applications.