Confined Cu Single Sites in ZSM‐5 for Photocatalytic Hydroxylation of Benzene to Phenol

Abstract Zeolites with band‐like charge transport properties have exhibited their potential activities in sensing, optics, and electronics. Herein, a precisely designed Cu@ZSM‐5 catalyst is presented with an ultra‐wide bandgap of 4.27 eV, showing excellent photocatalytic activity in hydroxylation of benzene with benzene conversion 27.9% and phenol selectivity 97.6%. The SXRD and Rietveld refinement results illustrate that Cu@ZSM‐5 has an average of 0.8 Cu atoms per unit cell and the single Cu atoms located in the cross‐section of the sinusoidal and straight channels. XANES and EXAFS further demonstrate that the Cu atoms have an oxidation state of +2, coordinated with three O MFI‐framework atoms and one ─OH group. Detailed characterizations demonstrate that the Cu@ZSM‐5 with tailored bandgap is able to enhance the photoinduced electron‐hole separation and hence promote selective hydroxylation of benzene to phenol via the superoxide radical route. This work may open a new way for designing electrically conductive zeolite‐supported photocatalysts.