Synthesis, characterisation, and activity of novel TiO2-based photocatalysts for organic pollutant photodestruction under UV and visible-light irradiation

摘要

Titania-based photocatalysts have been extensively studied for the oxidative photodestruction of organic pollutants in wastewaters, releasing non-toxic substances such as CO2, HCl, and water. However, commercial exploitation of this process is limited by the fact that titania is only active under UV irradiation (wavelength below about 388 nm), which is only less than 5% of solar light energy. Sol-gel synthesised catalyst specimens were characterised to determine the correlation between preparation conditions on morphology (XRD, SEM), optical (bandgap energy level) and physicochemical properties (BET surface area, pore volume, acid site density, acid site strength and type) of the photocatalysts. These spesific properties would then be linked to their photoactivity using aqueous aliphatic and aromatic model pollutants. This study has demonstrated that sol-gel synthesised doped titania photocatalysts, especially Pt/TiO2, may be used to effectively degrade non-volatile acids (DL-malic acid, dichloroacetic acid, and p-hydroxybenzoic acid) under visible light and UV irradiation with significant photoactivity suitable for the solar light application of photocatalytic wastewater treatment. A significant drop in band-gap energy was found for all titania sol-gel catalysts doped with Pt, Co, and Ce with values between 1.41 to 1.78 eV. The BET areas of the photocatalysts were also higher (65-117 m2/g) than that of Degussa P25 (50 m2/g). The visible-light photomineralisation of the three pollutants with Pt-TiO2 specimen were further extended to evaluate the effects of major variables in a bubble-column photoreactor on the photodegradation activities. Those major variables were lamp intensity, oxygen concentration, initial pH, catalyst dosage, and inital pollutant concentration. All the three pollutants seemed to follow the Langmuir-Hinselwood model with dual adsorption sites which implicated a bimolecular surface rate-limiting step probably between the adsorbed organic substrate and a surface hydroxyl (or peroxy) radical. A study of the CeyCoxTi(1-x)O3+d perovskite was conducted to investigate the influence of metal composition and pH on the intrinsic optophysical attributes as well as p-hydroxybenzoic acid degradation under UV irradiation. The perovskite UV photoactivities were lower than that of pure TiO2 likely due to excessive loading (metal content) creating new oxide phases act as electron-hole recombination center, regardless better physicochemical attributes of some of the perovskite samples. The role of aging time and calcination temperature on the sol-gel synthesised TiO2 was also explored. Higher calcination temperature (from 250 to 700 0C) resulted in TiO2 photocatalysts with better crystallinity, which is important for OH group formation as active sites for photodegradation. Despite of some advantages from higher temperature preparation, some detrimental effects such as decreased acidity attributes, surface area, and pore volume were also observed. The significant red-shift of sol-gel synthesized TiO2 into visible light, especially for 250 0C specimen since 600 or 700 0C had extremely low activities, has promising implications that this specimen might be used for solar application to substitute Pt-doped TiO2 in order to produce a more cost effective photocatalyst. Aging period (1 to 14 days) did not have any discernible effect on the band-gap value and acid-site density. Even so, the highest acid site strength was obtained with an aging time of 10 days. From the overall perspective, aging time longer than 3 days did not bring noticeable benefits to both catalyst attributes and photoactivities.