Modulating the Charge Transfer Channels via Constructing Charge‐Assisted Hydrogen‐Bonded Organic Frameworks for Enhanced Photosynthesis of Hydrogen Peroxide

ABSTRACT The production of H ₂ O ₂ via artificial photosynthesis is often limited by inefficient charge‐carrier separation, causing significant charge recombination and slow electron transfer. Herein, we report a facile strategy to regulate the photogenerated charge carrier transportation in hydrogen‐bonded organic frameworks (HOFs) via the construction of charge‐assisted hydrogen bonds. Specifically, the amount of charge transfer channels in the pyrene‐based HOFs can be modulated from one in FDU‐HOF‐3 to two in WYU‐HOF‐1 (WYU = Wuyi University) and three in WYU‐HOF‐2, as evidenced by the in situ characterization and theoretical calculations, leading to the highest separation/transfer efficiency in WYU‐HOF‐2. In addition, the fluorine‐functionalized WYU‐HOF‐2 also contributes to the enhanced charge migration and separation. Catalytic studies reveal that WYU‐HOF‐2 shows the highest H ₂ O ₂ generation rate from water, oxygen, and light without sacrificial agents, which is 3.4‐ and 62‐fold higher than that of WYU‐HOF‐1 and FDU‐HOF‐3, respectively. Mechanistic studies disclose that both of WYU‐HOF‐1 and WYU‐HOF‐2 facilitate photocatalytic H ₂ O ₂ production via the 2e ⁻ oxygen reduction reaction (ORR) and the 2e ⁻ water oxidation reaction (WOR) pathways. This work offers a promising strategy for regulating charge carrier transport in HOFs, thereby enhancing their photocatalytic performance.