Scheelite-Type Wide-Bandgap ABO<sub>4</sub> Compounds (A = Ca, Sr, and Ba; B = Mo and W) as Potential Photocatalysts for Water Treatment
Marta Kowalkińska, Paweł Głuchowski, Tomasz Swebocki, Tadeusz Ossowski, Adam Ostrowski, Waldemar Bednarski, Jakub Karczewski, Anna Zielińska‐Jurek
Abstract
In the present study, alkaline earth metal scheelite-type ABO4 compounds (A = Ca, Sr, and Ba; B = Mo and W) synthesized by a hydrothermal method were systematically studied. The as-obtained photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area analysis, UV–vis diffuse reflectance (DR/UV–vis) spectroscopy, photoluminescence, and thermoluminescence (TL) spectroscopy together with charge carrier lifetime measurements, electron paramagnetic resonance (EPR) spectroscopy, and electrochemical impedance spectroscopy (EIS). The photocatalytic activity was studied in the reaction of phenol degradation under simulated solar light. The obtained tungstates and molybdates revealed excellent photocatalytic activity despite the low surface area and wide bandgap typical for insulators. The mechanism of phenol degradation proceeded through hydroquinone and catechol formation in the presence of hydroxyl and superoxide radicals. The presence of electron traps allowed absorption of light with lower energy than resulting from the absorption edge. BaWO4 and SrWO4, with the most extended average carrier lifetime, were the most efficient photocatalysts from the obtained series. In general, molybdates exhibited lower photocatalytic activity toward phenol degradation due to deeper trap states and lower average charge carrier lifetimes than tungstates. Additionally, electrochemical studies demonstrated that molybdates exhibit more insulating behavior than tungstates. The overall results showed that wide-bandgap semiconductors, mainly tungstates, can be applied as earth-abundant photocatalytic materials for the degradation of persistent organic pollutants.