Synthesis of Robust MOFs@COFs Porous Hybrid Materials via an Aza‐Diels–Alder Reaction: Towards High‐Performance Supercapacitor Materials

Metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) have attracted enormous attention in recent years. Recently, MOF@COF are emerging as hybrid architectures combining the unique features of the individual components to enable the generation of materials displaying novel physicochemical properties. Herein we report an unprecedented use of aza‐Diels–Alder cycloaddition reaction as post‐synthetic modification of MOF@COF‐LZU1, to generate aza‐MOFs@COFs hybrid porous materials with extended π‐delocalization. A a proof‐of‐concept, the obtained aza‐MOFs@COFs is used as electrode in supercapacitors displaying specific capacitance of 20.35 μF cm−2 and high volumetric energy density of 1.16 F cm−3. Our approach of post‐synthetic modification of MOFs@COFs hybrids implement rational design for the synthesis of functional porous materials and expands the plethora of promising application of MOFs@COFs hybrid porous materials in energy storage applications. The functional porous hybrid material aza‐MOF@COF is synthesised through post‐synthesis modification of MOF@COF‐LZU1 by a cycloaddition‐based aza‐Diels–Alder reaction. The aza‐MOF@COF exhibits a high specific capacitance of 20.35 μF cm−2 and an exceptional stack capacitance of 1.16 F cm−3.