Hydrothermal Synthesis of Highly Crystalline Zwitterionic Vinylene-Linked Covalent Organic Frameworks with Exceptional Photocatalytic Properties

Ionic covalent organic frameworks (COFs) featuring both crystallinity and ionic characteristics have attracted tremendous attention in recent years. Compared with single anion- or cation-containing ionic COFs, zwitterionic COFs possess unique functionalities beyond single ionic COFs such as tunable charge density and superhydrophilic and highly ion-conductive characteristics, endowing them with huge potential in various applications. However, it remains a considerable challenge to directly synthesize robust, highly crystalline zwitterionic COFs from the original building blocks. Herein, we report a green hydrothermal synthesis strategy to prepare highly crystalline zwitterionic vinylene-linked COFs (ZVCOFs) from the predesigned zwitterionic building block by utilizing 4-dimethylaminopyridine (DMAP) as the high-efficiency catalyst for the first time. Detailed theoretical calculations and experiments revealed that both the high catalytic activity of DMAP and the unique role of water contributed to the formation of highly crystalline ZVCOFs. It was found that the participation of water could not only remarkably reduce the activation energy barrier and thus enhance the reaction reversibility but also enable the hydration of zwitterionic sites and facilitate ordered layered arrangement, which are favorable for the ZVCOF crystallization. Benefiting from the highly π-conjugated structure and hydrophilic characteristic, the obtained ZVCOFs achieved an ultrahigh sacrificial photocatalytic hydrogen evolution rate of 2052 μmol h-1 under visible light irradiation with an apparent quantum yield up to 47.1% at 420 nm, superior to nearly all COF-based photocatalysts ever reported. Moreover, the ZVCOFs could be deposited on a support as a photocatalytic film device, which demonstrated a remarkable photocatalytic performance of 402.1 mmol h-1 m-2 for hydrogen evolution.