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

Abstract

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have attracted enormous attention in recent years.R ecently,M OF@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 p-delocalization. Aaproof-of-concept, the obtained aza-MOFs@COFs is used as electrode in supercapacitors displaying specific capacitance of 20.35 mFcm À2 and high volumetric energy density of 1.16 Fcm À3 .O ur 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.

Imparting multi-functionality to covalent organic framework nanoparticles by the dual-ligand assistant encapsulation strategy

“…Apart from silica-based surface, the functional entities with other surface properties can also be integrated with COFs by this dual ligands assistant strategy. In previous works, complicated modification steps are required to introduce functional groups onto the surface of cores for the growth of COFs 40 , 41 . Here, the commonly used PEI and PVP ligands can be readily modified onto various nanomaterials to regulate the heterogeneous nucleation and growth of COF shell.…”

Integration of metal-organic frameworks and covalent organic frameworks: Design, synthesis, and applications

“…The aza-Diels-Alder reaction between aryl imine and phenylacetylene resulted in the successful conversion of the imine bridges into corresponding quinoline-linked aza-MOF@COF, which can greatly improve the stability of MOF@COF hybrid architectures (Figure 8). 50 COF@MOF Recently, the core-shell COF@MOF composites, which were produced by hybridization of COFs and MOFs that serve as cores and shells, respectively, have also received considerable attention. Similar to the synthesis of MOF@COF composites, several synthetic approaches have been developed for the formation of COF@MOF composites.…”

“…As can be seen in the SEM or TEM images of MOF@COF composites, in most cases MOFs usually play a decisive role in the final morphology of MOF@COF composites. 44,45,49,50,67 Except for growing COFs on the surface of MOFs, one can also grow COFs inside the well-chosen MOFs by taking the latter as template. In this situation, the MOF-templated COFs may inherit the regular morphology and fine crystallinity of the mother MOFs.…”

“…). 50 The proposed post-synthetic modification methods can also be adopted for rational design and fabrication of other eye-catching materials in energy storage.…”

Reagent Reactivity and Solvent Choice Determine Metal–Organic Framework Microstructure during Postsynthetic Modification

“…Clever manipulation of the various classes of postsynthetic methods − have given rise to sophisticated MOFs, ,− demonstrating internal and external control over the MOF crystal. Crystal overgrowth is a common method by which MOF microstructure is controlled; ,,, this technique is incorporated into the creation of advanced forms, including hollow, Matryoshka, , and double-shell hollow , MOFs. Postsynthetic linker exchange ,− and transmetalation have also been shown to affect MOF microstructure.…”