Facile quantization of semiconductor compounds in the zeolite: characterization of quantum dots of Zn4S6+ and Zn2S2+ in zeolite Y

The extra-framework zinc sulfide cationic clusters, Zn4S6+ and Zn2S2+, have been introduced into zeolite Y (FAU, Si/Al = 1.56). The |Zn24.5Na12(Zn4S6+)0.5(Zn2S2+)5.5|[Si117Al75O384]-FAU was prepared by allowing aqueous 0.1 M Na2S solution to flow past a |Zn37.5|[Si117Al75O384]-FAU at 294 K for 2 days. Its structure was determined by single-crystal synchrotron X-ray diffraction techniques. The crystallographic study showed that one sulfide ion at the center of the sodalite cavity coordinates to four Zn2+ ions at site I’ to give a centered-tetrahedral cationic cluster, Zn4S6+, and the other sulfide ion opposite 6-ring in the sodalite cavity bridges between two Zn2+ ions at site I’ to give a cationic cluster with bent arrangement, Zn2S2+, in 6.3% and 68.8% of the sodalite cavity of zeolite Y, respectively. Through high-resolution transmission electron microscope image, zinc sulfide quantum dots (QDs) group with the size of one unit cell (ca. 3 nm) in which hundreds were distributed was identified. By using UV–vis diffuse reflectance spectroscopy, it was confirmed that the zinc sulfide QDs occupied in the structure of zeolite Y exhibited enhanced optical activity because of the quantum size effect compared with that of bulk zinc sulfide. In this study, a method for quantizing semiconducting compounds in the cavity of zeolite Y was presented more easily, and its properties were investigated in more depth. The results proved that zeolite could be applied and used as a quantum container for the quantization of semiconductor compounds. [Display omitted] •The synthesis of Zn4S6+ and Zn2S2+ quantum dots (QDs) in the cavity of zeolite Y was attempted by metathesis reaction.•The characterization of the zinc sulfide (ZnS) QDs in the cavity of zeolite Y was completed by SC-XRD, SEM-EDX, UV–vis spectroscopy, and HRTEM.•SC-XRD analysis provided the three-dimensional structure of Zn4S6+ and Zn2S2+ in the cavity of zeolite Y.•The differences in optical properties between bulk ZnS and ZnS QDs in the cavity of zeolite Y was compared.•The hundreds of ZnS QDs group corresponding to the size of unit cell in the zeolite Y structure were identified.