In-situ Engineered Metal-Organic Framework with Anthraquinone for Boosting Synergistic Co-photosynthesis of Hydrogen Peroxide and Value-Added Chemicals in Two-Phase System

Abstract

Photocatalytic synthesis of hydrogen peroxide (H₂O₂) in systems integrating efficient catalytic reactions, product separation, and in situ collection remains a tremendous challenge. Herein, we report one-pot synthesis of anthraquinone (AQ)-functionalized UiO-66(NH₂) exhibiting exceptional photocatalytic H₂O₂ production rate of 44.8 mmol·g^–1·h^–1 (80.6 times higher than that of UiO-66(NH₂)) under visible light and 191 mmol·g^–1·h^–1 under simulated sunlight, coupled with 96% selectivity for benzyl alcohol (BA) oxidation to value-added benzaldehyde (BzH). The designed photocatalyst can be selectively dispersed in H₂O/BA biphasic interface, enabling spontaneous phase segregation of photogenerated H₂O₂ and BzH for autonomous product separation and continuous collection without external energy. Notably, a remarkable cumulative concentration of 681.6 mM (5452.8 μmol) was attained within 14 h. The results showcase that AQ integration enhances oxygen adsorption and establishes a robust built-in electric field (IEF) between UiO-66(NH₂) and AQ to drive efficient charge separation, facilitating the generation of abundant electrophilic singlet oxygen (¹O₂) via energy transfer (EnT) process. Mechanistic analysis reveals an unconventional H₂O₂ synthesis pathway, in which the generated ¹O₂ is subsequently reduced by electrons to superoxide radicals (•O₂^–), which then couple with protons to yield H₂O₂. This strategy offers a sustainable route for concurrent H₂O₂ and value-added chemical production.

Keywords

Photocatalysis / Hydrogen peroxide production / Anthraquinone / Metal-organic frameworks / Two-phase interface / Selective alcohol oxidation

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2025 SIOC, CAS, Shanghai, & WILEY-VCH GmbH