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Targeted reactant activation and spatial charge separation for efficient photocatalytic C(sp3)-H bond oxidation
Taoran Chen1,2, Yu Han1,2, Ying Tao1,2
1International Collaboration Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Institute of Microscale Optoelectronics, Shenzhen University Shenzhen 518060 China hlsun@szu.edu.cn.
None:
Semiconductor-based photo-redox catalysis offers a sustainable route for green organic synthesis, yet efficient C(sp3)-H bond oxidation remains challenging due to slow charge separation and limited surface reactivity. Here, we report a CsPCN (cesium doped polymeric carbon nitride)-Cs3Bi2Br9 heterojunction that promotes efficient charge separation while retaining strong hole oxidation capability of Cs3Bi2Br9 and superior oxygen and reactant activation ability of CsPCN. In situ experimental and theoretical studies confirm the photoelectron transfer pathway from Cs3Bi2Br9 to CsPCN driven by the interfacial electric field, empowering efficient spatial charge separation and high affinity and activation capability toward oxygen and reactants. As a result, the heterojunction exhibits efficient C(sp3)-H bond oxidation performance and broad substrate applicability under visible-light irradiation, achieving a conversion rate of ethylbenzene to acetophenone up to 8420 µmol g-1 h-1, 4.3 times higher than blank Cs3Bi2Br9 (1950 µmol g-1 h-1). This work demonstrates a rational heterostructure design strategy to couple charge separation with surface reactant activation for efficient lead-free perovskite based photocatalytic C(sp3)-H functionalization.
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