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Spatially Manipulating Polar Centers of Covalent Organic Frameworks for Boosting Hydrogen Peroxide Photosynthesis and
Fuyang Liu1,2,3, Yanghui Hou1,2,3, Jingfeng Wu1,2,3
1College of Environmental Sciences and Engineering, Peking University, Beijing, People's Republic of China.
Abstract:
Hydrogen peroxide (H2O2) photosynthesis from H2O and O2 using covalent organic frameworks (COFs) is a sustainable approach, yet its efficiency is restricted by a sluggish water oxidation reaction (WOR) due to insufficient water adsorption and charge separation. Herein, we propose a facile and universal polar center spatial-manipulation strategy to enable efficient H2O2 photosynthesis by COFs via converting high-polarity C═N linkages into 4-carboxyl-quinolyl linkages with weakened-polarity quinoline backbones and ultra-polar carboxyl side chains (forming COF-TBC). This polar-center side-shifting strategy concurrently enhances water adsorption (via the polar carboxyl side chain) and water activation (enabled by efficient exciton formation and separation along the low-polarity quinoline backbone) by COF-TBC, lowering the energy barrier of the rate-determining WOR and achieving outstanding and stable H2O2 photosynthesis from O2 and H2O without sacrificial agents (5624 µmol g-1 h-1, accumulating to 41 mM, solar-to-chemical efficiency of 0.72%). The polar-center side-shifting strategy can be extended to modify other COFs for enhancing H2O2 photosynthesis, indicating its universality. COF-TBC maintains high H2O2 yield in complex real-water matrices and can be integrated into membrane-based and continuous-flow reactors for successive H2O2 generation under natural sunlight. COF-TBC also exhibits efficient photocatalytic performance toward organic contaminant degradation and microorganism inactivation, highlighting its broad potential for water purification.
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