| Summary: | In this work, Au-modified F-TiO<sub>2</sub> is developed as a simple and efficient photocatalyst for H<sub>2</sub>O<sub>2</sub> production under ultraviolet light. The Au/F-TiO<sub>2</sub> photocatalyst avoids the necessity of adding fluoride into the reaction medium for enhancing H<sub>2</sub>O<sub>2</sub> synthesis, as in a pure TiO<sub>2</sub> reaction system. The F<sup>−</sup> modification inhibits the H<sub>2</sub>O<sub>2</sub> decomposition through the formation of the ≡Ti–F complex. Au is an active cocatalyst for photocatalytic H<sub>2</sub>O<sub>2</sub> production. We compared the activity of TiO<sub>2</sub> with F<sup>−</sup> modification and without F<sup>−</sup> modification in the presence of Au, and found that the H<sub>2</sub>O<sub>2</sub> production rate over Au/F-TiO<sub>2</sub> reaches four times that of Au/TiO<sub>2</sub>. In situ electron spin resonance studies have shown that H<sub>2</sub>O<sub>2</sub> is produced by stepwise single-electron oxygen reduction on the Au/F-TiO<sub>2</sub> photocatalyst.
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