The activation of an inert C(sp³)–H bond in selective oxidation of hydrocarbons under mild conditions is a critical and challenging process. Herein, we report a stable chlorine-coordinated metal–organic framework (MOF) photocatalyst, MIL-101(Fe), for efficient visible-light-driven photocatalytic selective oxidation of toluene to benzaldehyde in air under ambient conditions. Encouragingly, a benzaldehyde formation yield of 3.11 mmol·g^–1·h^–1 with a selectivity of 92.1% is achieved in 5 h, which is superior to most of the reported works. Based on the experimental results and characterizations, the high catalytic performance is mainly due to the promoted rate-limiting step of C(sp³)–H bond activation by a chlorine radical (Cl·) from the coordinated −Cl in the MIL-101(Fe) structure. In addition, the present photocatalyst possesses good substrate tolerance for photocatalytic selective oxidation of various toluene derivatives under optimized conditions.

中文翻译：

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常温条件下氯配位 MIL-101(Fe) 光催化选择性氧化甲苯


在温和条件下烃类选择性氧化中惰性C( sp ³ )–H键的活化是一个关键且具有挑战性的过程。在此，我们报道了一种稳定的氯配位金属有机骨架（MOF）光催化剂MIL-101（Fe），可在环境条件下有效地将可见光驱动的光催化选择性氧化空气中的甲苯生成苯甲醛。令人鼓舞的是，5小时内苯甲醛的形成产率为3.11 mmol·g ^–1 ·h ^–1 ，选择性为92.1%，优于大多数报道的工作。根据实验结果和表征，高催化性能主要归因于MIL-101中配位-Cl的氯自由基(Cl·)促进了C( sp ³ )–H键活化的限速步骤(Fe)结构。此外，本发明的光催化剂在优化条件下对各种甲苯衍生物的光催化选择性氧化具有良好的底物耐受性。