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Abstract 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 2 S 4 @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.
Li et al. (Wed,) studied this question.