Heterojunctions for Photocatalytic Wastewater Treatment: Positive Holes, Hydroxyl Radicals and Activation Mechanism under UV and Visible Light

Forming heterojunctions by coupling two or more semiconductors is an important strategy to develop stable and efficient photocatalysts able to operate both under near-UV and visible light. Five novel heterojunction systems were synthesized in the present study, using a modified sol-gel method: Bi2Mo3O12/TiO2, ZnFe2O4/TiO2, FeTiO3/TiO2, WO3(US)/TiO2 and WO3/TiO2. These heterojunction semiconductors were characterized by using XRD, SEM and EDX, UV-Vis diffuse reflectance spectroscopy and BET. Their photocatalytic activities were evaluated using methyl orange (MO) degradation under both near-UV and visible light. From the various heterojunctions developed, the WO3(US)/TiO(2 )photocatalyst was the one that showed the highest photocatalytic efficiency with this being assigned to the formation of a double heterojunction involving anatase, rutile and monoclinic WO3 phases. On this basis, a photocatalyst activation mechanism applicable to near-UV and visible light irradiation was proposed. This mechanism explains how the photogenerated electrons (e(-)) and positive holes (h(+)) can be transferred to the various phases. As a result, and given the reduced holes and electron recombination surface, hydroxyl radicals found were more abundant. To confirm this assumption, hole formation in the valence band was studied, using hole-scavenging reactions involving ion iodine (I-), while hydroxyl radical production used fluorescence spectroscopy.