Constructing Photocatalytic Covalent Organic Frameworks with Aliphatic Linkers.

Photocatalytic covalent organic frameworks (COFs) are typically constructed with rigid aromatic linkers for crystallinity and extended π-conjugation. However, the essential hydrophobicity of the aromatic backbone can limit their performances in water-based photocatalytic reactions. Here, we for the first time report the synthesis of hydrophilic COFs with aliphatic linkers [tartaric acid dihydrazide (TAH) and butanedioic acid dihydrazide] that can function as efficient photocatalysts for HO and H evolution. In these hydrophilic aliphatic linkers, the specific multiple hydrogen bonding networks not only enhance crystallization but also ensure an ideal compatibility of crystallinity, hydrophilicity, and light harvesting. The resulting aliphatic linker COFs adopt an unusual ABC stacking, giving rise to approximately 0.6 nm nanopores with an improved interaction with water guests. Remarkably, both aliphatic linker-based COFs show strong visible light absorption, along with a narrow optical band gap of ∼1.9 eV. The HO evolution rate for TAH-COF reaches up to 6003 μmol h g, in the absence of sacrificial agents, surpassing the performance of all previously reported COF-based photocatalysts. Theoretical calculations reveal that the TAH linker can enhance the indirect two-electron oxygen reduction reaction for HO production by improving the O adsorption and stabilizing the *OOH intermediate. This study opens a new avenue for constructing semiconducting COFs using nonaromatic linkers.