title: Degradation of methylene blue using porous WO3, SiO2-WO3, and their Au-loaded analogs: adsorption and photocatalytic studies.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Vermont , 82 University Place, Burlington, Vermont 05405, United States.
authors.forename: Daniel P
authors.initials: DP
authors.lastname: DePuccio
authors.forename: Pablo
authors.initials: P
authors.lastname: Botella
authors.forename: Bruce
authors.initials: B
authors.lastname: O'Rourke
authors.forename: Christopher C
authors.initials: CC
authors.lastname: Landry
keywords: demethylation; gold nanoparticles; photocatalyst; sonochemical; tungsten oxide