2D Conjugated Metal–Organic Frameworks Bearing Large Pore Apertures and Multiple Active Sites for High‐Performance Aqueous Dual‐Ion Batteries

Abstract 2D conjugated metal–organic frameworks (2D c ‐MOFs) with large pore sizes and high surface areas are advantageous for adsorbing iodine species to enhance the electrochemical performance of aqueous dual‐ion batteries (ADIBs). However, most of the reported 2D c ‐MOFs feature microporous structures, with few examples exhibiting mesoporous characteristics. Herein, we developed two mesoporous 2D c ‐MOFs, namely PA‐TAPA−Cu‐MOF and PA‐PyTTA−Cu‐MOF, using newly designed arylimide based multitopic catechol ligands (6OH‐PA‐TAPA and 8OH‐PA‐PyTTA). Notably, PA‐TAPA−Cu‐MOF exhibits the largest pore sizes (3.9 nm) among all reported 2D c ‐MOFs. Furthermore, we demonstrated that these 2D c ‐MOFs can serve as promising cathode host materials for polyiodides in ADIBs for the first time. The incorporation of triphenylamine moieties in PA‐TAPA−Cu‐MOF resulted in a higher specific capacity (423.4 mAh g −1 after 100 cycles at 1.0 A g −1 ) and superior cycling performance, retaining 96 % capacity over 1000 cycles at 10 A g −1 compared to PA‐PyTTA−Cu‐MOF. Our comparative analysis revealed that the increased number of N anchoring sites and larger pore size in PA‐TAPA−Cu‐MOF facilitate efficient anchoring and conversion of I 3 − , as supported by spectroscopic electrochemistry and density functional theory calculations.