Boosting the photocatalytic oxidative desulfurization of dibenzothiophene by decoration of MWO4 (M=Cu, Zn, Ni) on WO3

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The surface of WO3 was partially decorated with transition metal tungstate MWO4 (M = Cu, Zn, Ni) using impregnation method followed by solid-state reaction. It is found that MWO4/WO3 photocatalysts showed a higher activity for photocatalytic oxidative desulfurization (PODS) of dibenzothiophene (DBT) than pure WO3 or MWO4 under visible light irradiation. Moreover, the activity for PODS of DBT on MWO4/WO3 depends on the content of MWO4 decoration on WO3 surfaces. 0.2% CuWO4/WO3, 1% ZnWO4/WO3, and 0.5% NiWO4/WO3 exhibited the highest activity among CuWO4/WO3, ZnWO4/WO3 and NiWO4/WO3 samples. However, as compared with 1% ZnWO4/WO3 and 0.5% NiWO4/WO3, the 0.2% CuWO4/WO3 sample exhibited superior visible light photocatalytic activity for DBT conversion. Brunauer-Emmett-Teller method (BET), SEM, and ultraviolet-visible diffuse reflectance spectra (UV–vis DRS), high resolution transmission electron microscope (HRTEM), photoluminescence spectroscopy (PL), and a series of titration experiments were used to seek the reason for the positive impact of MWO4 on the photocatalytic activity of WO3. As compared with pure WO3, no notable changes of specific surface areas, morphologies, and light absorption are observed after MWO4 (M = Cu, Zn, Ni) decoration. The formation of heterojunction structure between MWO4 and WO3, which promotes charge separation efficiency, was the main reason for the high photocatalytic activity of MWO4/WO3 photocatalyst. Moreover, difference in PODS activity between MWO4/WO3 heterojunctions is proved to be affected by their charge separation and transfer efficiency and amount of active species.