Molecular-Level Pore Tuning in 2D Conductive Metal–Organic Frameworks for Advanced Supercapacitor Performance

Two-dimensional (2D) electrically conductive metal–organic frameworks (MOFs) have emerged as viable candidates for active electrode materials in supercapacitors due to their high electrical conductivity, high specific surface area, and intrinsic redox-active sites. Despite their promising electrochemical performance, their pseudocapacitive behavior via fast and reversible charge transfer reactions remains yet to be fully exploited. Here, we investigate the electrochemical energy storage mechanism of Cu₃(HHTATP)₂ (HHTATP = 2,3,6,7,10,11-hexahydroxy-1,5,9-triaminotriphenylene), a 2D conductive MOF featuring characteristic redox-active pendant aromatic amines. Cu₃(HHTATP)₂ exhibited pseudocapacitive charge storage with an average gravimetric capacitance of 340 ± 15 F g^–1 at a discharge rate of 0.2 A g^–1 and maintained a capacitance retention over 90% after 7000 galvanostatic cycles at 5 A g^–1. The polar pendant amines not only enhanced capacitance via additional amine/imine redox activity but also reduced interfacial charge transfer resistance through modified electrode–electrolyte interactions. These results highlight the potential of molecular-level pore environment tuning as a strategic approach in materials design for energy storage applications.