Degradation of Methylene Blue Using Porous WO3, SiO2-WO3, and Their Au-Loaded Analogs: Adsorption and Photocatalytic Studies

A facile sonochemical approach was used to deposit 3-5 nm monodisperse gold nanoparticles on porous SiO2-WO3 composite spheres, as confirmed by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). High-resolution TEM (HR-TEM) and energy dispersive X-ray spectroscopy (EDS) further characterized the supported Au nanoparticles within the Au-SiO2-WO3 composite. These analyses showed isolated Au nanoparticles within both SiO2- and WO3-containing regions. Selective etching of the SiO2 matrix from Au-SiO2-WO3 yielded a pure Au-WO3 material with well-dispersed 10 nm Au nanoparticles and moderate porosity. This combined sonochemical-nanocasting technique has not been previously used to synthesize Au-WO3 photocatalysts. Methylene blue (MB) served as a probe for the adsorption capacity and visible light photocatalytic activity of these WO3-containing catalysts. Extensive MB demethylation (azures A, B, C, and thionine) and polymerization of these products occurred over WO3 under dark conditions, as confirmed by electrospray ionization mass spectrometry (ESI-MS). Photoirradiation of these suspensions led to further degradation primarily through demethylation and polymerization pathways, regardless of the presence of Au nanoparticles. Ring-opening sulfur oxidation to the sulfone was a secondary photocatalytic pathway. According to UV-vis spectroscopy, pure WO3 materials showed superior MB adsorption compared to SiO2-WO3 composites. Compared to their respective nonloaded catalysts, Au-SiO2-WO3 and Au-WO3 catalysts exhibited enhanced visible light photocatalytic activity toward the degradation of MB. Specifically, the rates of MB degradation over Au-WO3 and Au-SiO2-WO3 during 300 min of irradiation were faster than those over their nonloaded counterparts (WO3 and SiO2-WO3). These studies highlight the ability of Au-WO3 to serve as an excellent adsorbant and photodegradation catalyst toward MB.