Dual-Redox-Sites Enable Two-Dimensional Conjugated Metal–Organic Frameworks with Large Pseudocapacitance and Wide Potential Window

Advanced supercapacitor electrodes require the development of materials with dense redox sites embedded into conductive and porous skeletons. Two-dimensional (2D) conjugated metal–organic frameworks ( c -MOFs) are attractive supercapacitor electrode materials due to their high intrinsic electrical conductivities, large specific surface areas, and quasi-one-dimensional aligned pore arrays. However, the reported 2D c -MOFs still suffer from unsatisfying specific capacitances and narrow potential windows because large and redox-inactive building blocks lead to low redox-site densities of 2D c -MOFs. Herein, we demonstrate the dual-redox-site 2D c -MOFs with copper phthalocyanine building blocks linked by metal-bis(iminobenzosemiquinoid) (M 2 [CuPc(NH) 8 ], M = Ni or Cu), which depict both large specific capacitances and wide potential windows. Experimental results accompanied by theoretical calculations verify that phthalocyanine monomers and metal-bis(iminobenzosemiquinoid) linkages serve as respective redox sites for pseudocapacitive cation (Na + ) and anion (SO 4 2– ) storage, enabling the continuous Faradaic reactions of M 2 [CuPc(NH) 8 ] occurring in a large potential window of −0.8 to 0.8 V vs Ag/AgCl (3 M KCl). The decent conductivity (0.8 S m –1 ) and high active-site density further endow the Ni 2 [CuPc(NH) 8 ] with a remarkable specific capacitance (400 F g –1 at 0.5 A g –1 ) and excellent rate capability (183 F g –1 at 20 A g –1 ). Quasi-solid-state symmetric supercapacitors are further assembled to demonstrate the practical application of Ni 2 [CuPc(NH) 8 ] electrode, which deliver a state-of-the-art energy density of 51.6 Wh kg –1 and a peak power density of 32.1 kW kg –1 .