Quantum Capacitance through Molecular Infiltration of 7,7,8,8-Tetracyanoquinodimethane in Metal–Organic Framework/Covalent Organic Framework Hybrids

Metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) have been extensively investigated during the last two decades. More recently, a family of hybrid materials (i.e., MOF@COF) has emerged as particularly appealing for gas separation and storage, catalysis, sensing, and drug delivery. MOF@COF hybrids combine the unique characteristics of both MOF and COF components and exhibit peculiar properties including high porosity and large surface area. In this work, we show that the infiltration of redox-active 7,7,8,8-tetracyanoquinodimethane (TCNQ) molecules into the pores of MOF@COF greatly improves the characteristics of the latter, thereby attaining high-performance energy storage devices. Density functional theory (DFT) calculations were employed to guide the design of a MOF@COF-TCNQ hybrid with the TCNQ functional units incorporated in the pores of MOF@COF. To demonstrate potential application of our hybrids, the as-synthesized MOF@COF-TCNQ hybrid has been employed as an active material in supercapacitors. Electrochemical energy storage analysis revealed outstanding supercapacitor performance, as evidenced by a specific areal capacitance of 78.36 mF cm–2 and a high stack volumetric energy density of 4.46 F cm–3, with a capacitance retention of 86.4% after 2000 cycles completed at 0.2 A cm–2. DFT calculation results strongly indicate that the high capacitance of MOF@COF-TCNQ has a quantum capacitance origin. Our liquid-phase infiltration protocol of MOF@COF hybrids with redox-active molecules represents a efficacious approach to design functional porous hybrids.