Recent advances in room-temperature synthesis of covalent organic frameworks

Covalent organic frameworks (COFs) have become a promising class of highly-crystalline polymers with layered stacking structures, ordered porous channels, and highly-tailorable structures. To date, most COFs have been synthesized via high-temperature solvothermal methods, which require complicated optimization of factors including temperature, solvent ratio, catalyst, and reaction time. Additionally, solvothermal conditions with high temperature and high pressure restrict the facile and large-scale synthesis of COFs for practical applications. In addition, the insolubility and lack of processability of the COF powders obtained via solvothermal methods hinder their potential application in film-related fields. Energy-efficient and environmentally benign synthetic methods to resolve these problems are highly desired. In this review, we provide an overview of the recent progress in room-temperature synthetic strategies for constructing COF powders or COF films. We first discuss in situ characterization technologies for exploring the COF growth mechanism. Then, we present representative room-temperature synthesis methods for COFs, including solid-liquid interfacial synthesis, liquid-liquid interfacial synthesis, on-water surface synthesis, water-phase synthesis, electrosynthesis, sonochemical synthesis, single-solution phase synthesis, mechanochemical synthesis, high-energy ionizing radiation synthesis, and photochemical synthesis. Finally, perspectives on room-temperature synthesis are proposed in the areas of single-crystal domains, novel room-temperature reaction types, crystallization mechanism, the design of chemical structures and green synthesis.