Incorporating photocatalysis into benzylic C(sp³)H oxidation represents a recent advance of organic synthesis in a sustainable manner. Although photoinduced charge carriers enable the C(sp³)H bond to be activated under mild conditions, the reaction scale and activity remain hindered by the photoactivation efficiency. Herein, we present that the 1.0% V₂O₅@CN photocatalyst, a visible-light-active C₃N₄-based material, is striking active for the aerobic oxidation of benzylic C(sp³)H bonds, affording a conversion rate 11.6 times higher than that of independent CN. The enhanced activity and C(sp³)H bond photoactivation, as well as the induction period shortening and active period acceleration, are rationalized by the low-E_VB hole injection from V₂O₅ into CN and the boosted charge separation. The durability and utility are affirmed in multiple catalytic cycles, scalable long-term reactions, and available substrate scopes. Reactive intermediate studies by EPR demonstrate the involvement of CH₂Ph, O₂⁻, and OH radicals in photoredox catalysis. The mechanism that causes the change of main product species is attributed to the formation of OH in the later reaction stage. This work indicates a unique photoactive V₂O₅@CN catalysis mode, opening up the efficient use of CN in scalable photocatalytic toluene oxidation.

将光催化并入苄基C（sp ³）H氧化代表了有机合成以可持续方式的最新进展。尽管光诱导的电荷载体使C（sp ³）H键在温和的条件下被激活，但反应规模和活性仍然受到光激活效率的阻碍。在这里，我们提出1.0％V ₂ O ₅ @CN光催化剂，一种可见光活性的基于C ₃ N ₄的材料，对于苄基C（sp ³）H键的需氧氧化具有显着活性，从而提供了转化比率是独立CN的11.6倍。增强的活性和C（sp ³）通过从V ₂ O ₅向CN注入低E _VB空穴和增强电荷分离，可以合理地实现H键的光活化以及诱导期的缩短和激活期的加速。在多个催化循环，可扩展的长期反应以及可用的底物范围中都证实了其耐用性和实用性。通过EPR反应中间体的研究表明参与CH ₂ pH值，Ø ₂ ^-和OH自由基在photoredox催化。引起主要产物种类变化的机理归因于在反应后期的OH的形成。这项工作表明一个独特的光敏V ₂O ₅ @CN催化模式，开启了CN在可扩展的光催化甲苯氧化中的有效利用。