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

Comprehensive Summary Photocatalytic synthesis of hydrogen peroxide (H 2 O 2 ) 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(NH 2 ) exhibiting exceptional photocatalytic H 2 O 2 production rate of 44.8 mmol·g –1 ·h –1 (80.6 times higher than that of UiO‐66(NH 2 )) 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 H 2 O/BA biphasic interface, enabling spontaneous phase segregation of photogenerated H 2 O 2 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(NH 2 ) and AQ to drive efficient charge separation, facilitating the generation of abundant electrophilic singlet oxygen ( 1 O 2 ) via energy transfer (EnT) process. Mechanistic analysis reveals an unconventional H 2 O 2 synthesis pathway, in which the generated 1 O 2 is subsequently reduced by electrons to superoxide radicals (•O 2 – ), which then couple with protons to yield H 2 O 2 . This strategy offers a sustainable route for concurrent H 2 O 2 and value‐added chemical production.