College of Chemistry, State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou, 350116, China.
Angew Chem Int Ed Engl. 2023 May 22;62(22):e202303054. doi: 10.1002/anie.202303054. Epub 2023 Apr 19.
Photocatalytic epoxide alcoholysis through C-O bond cleavage and formation has emerged as an alternative to synthesizing anti-tumoral pharmaceuticals and fine chemicals. However, the lack of crucial evidence to interpret the interaction between reactants and photocatalyst surface makes it challenging for photocatalytic epoxide alcoholysis with both high activity and regioselectivity. In this work, we report the hierarchical ZnIn S @CdS photocatalyst for epoxide alcoholysis with high regioselectivity nearly 100 %. Mechanistic studies unveil that the precise activation switch on exposed Zn acid sites for C-O bond polarization and cleavage has a critical significance for achieving efficient photocatalytic performance. Furthermore, the establishment of Z-scheme heterojunction facilitates the interface charge separation and transfer. Remarkably, the underlying regioselective photocatalytic reaction pathway has been distinctly revealed.
通过 C-O 键的断裂和形成进行光催化环氧化物醇解,已经成为合成抗肿瘤药物和精细化学品的一种替代方法。然而,缺乏解释反应物与光催化剂表面相互作用的关键证据,使得具有高活性和区域选择性的光催化环氧化物醇解变得具有挑战性。在这项工作中,我们报告了具有高区域选择性(接近 100%)的分级 ZnInS@CdS 光催化剂用于环氧化物醇解。机理研究表明,暴露的 Zn 酸位上 C-O 键极化和断裂的精确活化开关对于实现高效的光催化性能具有至关重要的意义。此外,Z 型异质结的建立有利于界面电荷的分离和转移。值得注意的是,明确揭示了潜在的区域选择性光催化反应途径。