Tungsten Oxide Morphology-Dependent Au/TiO2/WO3 Heterostructures with Applications in Heterogenous Photocatalysis and Surface-Enhanced Raman Spectroscopy

Abstract

Developing highly efficient Au/TiO2/WO3 heterostructures with applications in heterogeneous photocatalysis (photocatalytic degradation) and surface-enhanced Raman spectroscopy (dye detection) is currently of paramount significance. Au/TiO2/WO3 heterostructures were obtained via heat or time-assisted synthesis routes developed by slightly modifying the Turkevich–Frens synthesis methods and were investigated by TEM, SEM, XRD, Raman spectroscopy, XPS, photoluminescence, and UV–vis DRS techniques. Structural features, such as WO3 crystalline phases, TiO2 surface defects, as well as the WO3 (220) to TiO2-A (101) ratio, were the key parameters needed to obtain heterostructures with enhanced photocatalytic activity for removing oxalic acid, phenol, methyl orange, and aspirin. Photodegradation efficiencies of 95.9 and 96.9% for oxalic acid; above 96% (except one composite) for phenol; 90.1 and 97.9% for methyl orange; and 81.6 and 82.1% for aspirin were obtained. By employing the SERS technique, the detection limit of crystal violet dye, depending on the heterostructure, was found to be between 10−7–10−8 M. The most promising composite was Au/TiO2/WO3-HW-TA it yielded conversion rates of 82.1, 95.9 and 96.8% for aspirin, oxalic acid, and phenol, respectively, and its detection limit for crystal violet was 10−8 M. Au/TiO2/WO3-NWH-HA achieved 90.1, 96.6 and 99.0% degradation efficiency for methyl orange, oxalic acid, and phenol, respectively, whereas its limit of detection was 10−7 M. The Au/TiO2/WO3 heterojunctions exhibited excellent stability as SERS substrates, yielding strong-intensity Raman signals of the pollutant molecules even after a long period of time.