Decomposition–Reassembly Synthesis of a Silverton-Type Polyoxometalate 3D Framework: Semiconducting Properties and Photocatalytic Applications

Abstract

Polyoxometalate-based all-inorganic three-dimensional (3D) frameworks have recently attracted attention as a unique class of materials due to their unique physicochemical properties and a wide field of application with excellent prospects. We herein synthesized a novel all-inorganic 3D framework material based on cobalt-substituted Silverton-type polyoxometalate, H₆{Co₆W₁₀O₄₂[Co(H₂O)₄]₃}·2H₂O (Co₉W₁₀), which was successfully constructed using Na₁₂[WCo₃^II(H₂O)₂(Co^IIW₉O₃₄)₂]·46-48H₂O (Co₅W₁₉) and Co(NO₃)₂·6H₂O as starting materials in a hydrothermal reaction via a decomposition-reassembly route together with the rational adjustment of pH values. Co₉W₁₀ has been structurally characterized using single-crystal X-ray diffraction. Photocurrent response, band-gap (<i>E</i>_g) value, and the VB-XPS spectrum have been measured to reveal the semiconducting property of Co₉W₁₀. Furthermore, we synthesized <i>x</i>% PTh/Co₉W₁₀ composites (PTh = polythiophene, <i>x</i> = 0.5, 1, 2, 5) for photodegradation of tetracycline hydrochloride (TH) to evaluate the photocatalytic activities of title composites. Due to the optimal molar ratio of hybrids and matching energy levels, 2% PTh/Co₉W₁₀ composites show the best photocatalytic activities among these composites.