Interrupted chalcogenide-based zeolite-analogue semiconductor: atomically precise doping for tunable electro-/photoelectrochemical properties.

Abstract

Incorporation of semiconductor property into zeolite materials is a plausible approach to graft oxide zeolites with multifunctionality in which both electronic/optoelectronic functions and high porosity are integrated. However, creating such semiconductor zeolites, especially the ones with controllable function regulation still remains as a great synthetic challenge over the years. Hereby, we reported the first case of an interrupted chalcogenide-based zeolite-analog semiconductor with an entirely new boracite-related framework and specific sites at the interrupted section. The semiconducting nature and band structure of this open-framework n-type semiconductor material were characterized with solid-state UV/Vis diffuse reflectance spectroscopy and Mott-Schottky measurements. More importantly, the In-Se chalcogenide zeolite analog was for the first time explored as an effective electrocatalyst for the oxygen reduction reaction (ORR). The specific indium sites served as active centers and proved to be responsible for a superior ORR activity. Meanwhile, these specific sites could be precisely replaced by bismuth(III) ions, leading to facile manipulation in their electro-/photoelectrochemical properties. Such atomically precise doping successfully implemented at the semiconductor zeolite material with specifically interrupted sites presents a very promising route for accurately regulating electronic structure and photoelectrical properties of other open-framework semiconductor materials.