Enhanced photocatalytic performance of Bi-doped TiO2 under sunlight and UV light: mechanistic insights and comparative analysis.

Bismuth-doped metal oxides exhibit favourable photocatalytic features when exposed to both sunlight and UV light. In this approach, Bi0/TiO2 and Bi+3/TiO2 photocatalysts were prepared and their structural and optical properties are analysed using various characterization techniques. These developed photocatalysts were further tested for the photocatalytic elimination of Nitrobenzene in UV light and sunlight and compared with the performance of bare TiO2. The catalyst Bi+3/TiO2 performed better in UV light with 72.31% degradation, and 4.74 × 10-6 mol.litre-1.min-1 initial rate of reaction. However, when exposed to sunlight, Bi0/TiO2 outperformed with 73.85% degradation, and 4.63 × 10-6 mol.min-1 initial rate of reaction. This significant increase in photocatalytic activity of Bi0/TiO2 under sunlight could be accredited to increased light harvesting and enhanced efficiency in charge carrier separation, both of which were made possible by bismuth-induced surface plasmon resonance.

Mineralisation of 2,4-dichlorophenoxyacetic acid by acoustic or hydrodynamic cavitation in conjunction with the advanced Fenton process.

The mineralisation of 2,4-dichlorophenoxyacetic acid (2,4-D) in the presence of zero-valent iron and hydrogen peroxide (the advanced Fenton process--AFP) whilst being subjected to acoustic or hydrodynamic cavitation is reported. If the reaction is merely stirred then there is 57% removal of TOC whilst on irradiation the figure is 64% although the latter reaction is more rapid. Use of ultrasound alone results in only 11% TOC removal in 60 min of treatment time. Addition of iron powder marginally enhances the extent of degradation but an appreciable increase is observed in the presence of hydrogen peroxide which acts as a source for hydroxyl radicals by Fenton chemistry as well as by dissociation in the presence of ultrasound. The use of hydrodynamic cavitation in conjunction with the advanced Fenton process has also been found to be a useful tool for continuous remediation of water contaminated with 2,4-D. After 20 min of treatment the residual TOC is reduced to 30% and this probably represents the remaining highly recalcitrant small organic molecules.

Treatment of industrial wastewater effluents using hydrodynamic cavitation and the advanced Fenton process.

For the first time, hydrodynamic cavitation induced by a liquid whistle reactor (LWR) has been used in conjunction with the advanced Fenton process (AFP) for the treatment of real industrial wastewater. Semi-batch experiments in the LWR were designed to investigate the performance of the process for two different industrial wastewater samples. The effect of various operating parameters such as pressure, H2O2 concentration and the initial concentration of industrial wastewater samples on the extent of mineralization as measured by total organic carbon (TOC) content have been studied with the aim of maximizing the extent of degradation. It has been observed that higher pressures, sequential addition of hydrogen peroxide at higher loadings and lower concentration of the effluent are more favourable for a rapid TOC mineralization. In general, the novel combination of hydrodynamic cavitation with AFP results in about 60-80% removal of TOC under optimized conditions depending on the type of industrial effluent samples. The combination described herein is most useful for treatment of bio-refractory materials where the diminution in toxicity can be achieved up to a certain level and then conventional biological oxidation can be employed for final treatment. The present work is the first to report the use of a hydrodynamic cavitation technique for real industrial wastewater treatment.

Intensification of oxidation capacity using chloroalkanes as additives in hydrodynamic and acoustic cavitation reactors.

The effect of the presence and absence of the chloroalkanes, dichloromethane (CH(2)Cl(2)), chloroform (CHCl(3)) and carbon tetrachloride (CCl(4)) on the extent of oxidation of aqueous I(-) to I(3)(-) has been investigated in (a) a liquid whistle reactor (LWR) generating hydrodynamic cavitation and (b) an ultrasonic probe, which produces acoustic cavitation. The aim has been to examine the intensification achieved in the extent of oxidation due to the generation of additional free radicals/oxidants in the reactor as a result of the presence of chloroalkanes. It has been observed that the extent of increase in the oxidation reaction is strongly dependent on the applied pressure in the case of the LWR. Also, higher volumes of the chloroalkanes favour the intensification and the order of effectiveness is CCl(4)>CHCl(3)>CH(2)Cl(2). However, the results with the ultrasonic probe suggest that an optimum concentration of CH(2)Cl(2) or CHCl(3) exists beyond which there is little increase in the extent of observed intensification. For CCl(4), however, no such optimum concentration was observed and the extent of increase in the rates of oxidation reaction rose with the amount of CCl(4) added. Stage wise addition of the chloroalkanes was found to give marginally better results in the case of the ultrasonic probe as compared to bulk addition at the start of the run. Although CCl(4) is the most effective, its toxicity and carcinogenicity may mean that CH(2)Cl(2) and CHCl(3) offer a safer viable alternative and the present work should be useful in establishing the amount of chloroalkanes required for obtaining a suitable degree of intensification.

Intensification of hydroxyl radical production in sonochemical reactors.

The efficacy of sonochemical reactors in chemical processing applications has been well established in the laboratory scale of operation though at a given set of operating parameters and no efforts have been directed in terms of maximizing the free radical production. In the present work, the effect of different operating parameters viz. pH, power dissipation into the system, effect of additives such as air, haloalkanes, titanium dioxide, iron and oxygen on the extent of hydroxyl radical formation in a sonochemical reactor have been investigated using salicylic acid dosimetry. Possible mechanisms for oxidation of salicylic acid in the presence of different additives have also been established. It has been observed that acidic conditions under optimized power dissipation in the presence of iron powder and oxygen result in maximum liberation of hydroxyl radicals as quantified by the kinetic rate constant for production of 2,5- and 2,3-dihydroxybenzoic acid. The study has enabled the optimization of the conditions for maximum efficacy of sonochemical reactors where free radical attack is the controlling mechanism for the chemical processing applications.