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

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 OMFI-framework atoms and one & horbar;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. Herein, a precisely fabricated Cu@ZSM-5 catalyst with single [Cu(OH)]+ species anchored in a specific position of the ZSM-5 framework exhibits a competitive photocatalytic activity in benzene hydroxylation to phenol. This work provides a new strategy for designing conductive catalysts in photocatalytic catalysis. image