Keto-anthraquinone covalent organic framework for H<sub>2</sub>O<sub>2</sub> photosynthesis with oxygen and alkaline water.

Zhang, Xiangcheng; Cheng, Silian; Chen, Chao; Wen, Xue; Miao, Jie; Zhou, Baoxue; Long, Mingce; Zhang, Lizhi · Nat Commun · 2024

basic_science · Level V

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Abstract

Hydrogen peroxide photosynthesis suffers from insufficient catalytic activity due to the high energy barrier of hydrogen extraction from H<sub>2</sub>O. Herein, we report that mechanochemically synthesized keto-form anthraquinone covalent organic framework which is able to directly synthesize H<sub>2</sub>O<sub>2</sub> (4784 μmol h<sup>-1</sup> g<sup>-1</sup> at λ > 400 nm) from oxygen and alkaline water (pH = 13) in the absence of any sacrificial reagents. The strong alkalinity resulted in the formation of OH<sup>-</sup>(H<sub>2</sub>O)<sub>n</sub> clusters in water, which were adsorbed on keto moieties within the framework and then dissociated into O<sub>2</sub> and active hydrogen, because the energy barrier of hydrogen extraction was largely lowered. The produced hydrogen reacted with anthraquinone to generate anthrahydroquinone, which was subsequently oxidized by O<sub>2</sub> to produce H<sub>2</sub>O<sub>2</sub>. This study ultimately sheds light on the importance of hydrogen extraction from H<sub>2</sub>O for H<sub>2</sub>O<sub>2</sub> photosynthesis and demonstrates that H<sub>2</sub>O<sub>2</sub> synthesis is achievable under alkaline conditions.