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Unraveling the formation mechanism of hydroxyl radicals (OH˙) is one of the outstanding issues in photocatalytic reactions, where 5,5-dimethyl-1-pyrroline N-oxide (DMPO) is widely utilized as a trapping agent to detect OH˙ radicals in experiments. In this study, we carry out density functional theory calculations to reveal the origin and formation process of OH˙ radicals by investigating the interaction of water with DMPO on a rutile TiO2(11 surface. Our results clearly show that the OH˙ radicals trapped by DMPO stem from water upon il
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