Emergent electrochemical functions and future opportunities of hierarchically constructed metal-organic frameworks and covalent organic frameworks

Designing spatial and architectural features across from the molecular to bulk scale is one of the most important topics in materials science which has received a lot of attention in recent years. Looking back to the past research, findings on the influences of spatial features denoted as porous structures on the applications related to mass transport phenomena have been widely studied in traditional inorganic materials, such as ceramics over the past two decades. However, due to the difficulties in precise control of the porous structures at the molecular level in this class of materials, the mechanistic understanding of the effects of spatial and architectural features across from the molecular level to meso-/macroscopic scale is still lacking, especially in electrochemical reactions. Further understanding of fundamental electrochemical functions in well-defined architectures is indispensable for the further advancement of key next-generation energy devices. Furthermore, creating periodic porosity in reticular structures is starting to be recognized as an emerging approach to control the electronic structure of materials. In this review, we focus on the investigations on preparing well-defined molecular-level crystalline porous materials known as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) into hierarchically constructed architectures from molecular structures lower than the reticular frameworks to meso-/macroscopic scale structures. By connecting well-defined nanosized porous structures in MOFs/COFs and additional length-scale space or shapes, emergent electrochemical functions towards emerging devices, such as beyond Li-ion batteries including all-solid-state rechargeable batteries, are expected to be obtained. By summarizing recent advancements in synthetic strategies of hierarchically constructed MOF/COF based materials and fundamental investigation of their structural effect in a wide spectrum of electrochemical applications, we highlight the importance and future direction of this developing field of hierarchically constructed MOFs/COFs, while emphasizing the required chemical stability of the MOFs/COFs which meet the use in the game-changing electrochemical devices.