Low Power, Low Temperature and Atmospheric Pressure Plasma‐Induced Polymerization: Facile Synthesis and Crystal Regulation of Covalent Organic Frameworks

Abstract Low temperature and atmospheric pressure plasma‐induced polymerization was demonstrated as a fast and facile strategy for tailoring of packing phase of COF‐1 as well as preparing diverse covalent organic frameworks (COFs) including both two‐dimensional (2D) COFs and three‐dimensional (3D) COFs. By regulating the solvents, the fast construction of well‐ordered AB staggered COF‐1 and AA eclipsed COF‐1 was facilely realized in minutes. The plasma approach presented here led to the rapid preparation of eight classical 2D COFs, including boronate ester‐linkage (COF‐5, COF‐8 and COF‐10), azine‐linkage (NUS‐2), β‐ketoenamine‐linkage (TpPa, TPBD), imine‐linkage (ILCOF‐1, Py‐COF), and 3D‐COF‐102 (boroxine linkage) in less than 1 hour. Different from conventional methods, the proposed methodology required much less time, lower power, no extra heating, inert‐gas protection and pressure. The fast nucleation and growth of COFs with good crystallinity, morphology and thermal stability can be achieved under mild conditions.