B. Neppolian

SOLAR PHOTOCATALYTIC DEGRADATION OF AZO DYE: COMPARISON OF PHOTOCATALYTIC EFFICIENCY OF ZNO AND TIO2

Abstract The photocatalytic activity of commercial ZnO powder has been investigated and compared with that of Degussa P25 TiO2. Laboratory experiments with acid brown 14 as the model pollutant have been carried out to evaluate the performance of both ZnO and TiO2 catalysts. Solar light was used as the energy source for the photocatalytic experiments. These catalysts were examined for surface area, particle size and crystallinity. The effect of initial dye concentration, catalyst loading, irradiation time, pH, adsorption of acid brown 14 on ZnO and TiO2, intensity of light and comparison of photocatalytic activity with different commercial catalysts were studied. The progress of photocatalytic degradation of the acid brown 14 has been observed by monitoring the change in substrate concentration of the model compound employing HPLC and measuring the absorbance in UV–Visible spectrophotometer for decolourisation. The photodegradation rate was determined for each experiment and the highest values were observed for ZnO suggesting that it absorbs large fraction of the solar spectrum and absorption of more light quanta than TiO2. The complete mineralisation was confirmed by total organic carbon (TOC) analysis, COD measurement and estimation of the formation of inorganic ions such as NH4+, NO3−, Cl− and SO42−.

Solar/UV-induced photocatalytic degradation of three commercial textile dyes

The photocatalytic degradation of three commercial textile dyes with different structure has been investigated using TiO(2) (Degussa P25) photocatalyst in aqueous solution under solar irradiation. Experiments were conducted to optimise various parameters viz. amount of catalyst, concentration of dye, pH and solar light intensity. Degradation of all the dyes were examined by using chemical oxygen demand (COD) method. The degradation efficiency of the three dyes is as follows: Reactive Yellow 17(RY17) > Reactive Red 2(RR2) > Reactive Blue 4 (RB4), respectively. The experimental results indicate that TiO(2) (Degussa P25) is the best catalyst in comparison with other commercial photocatalysts such as, TiO(2) (Merck), ZnO, ZrO(2), WO(3) and CdS. Though the UV irradiation can efficiently degrade the dyes, naturally abundant solar irradiation is also very effective in the mineralisation of dyes. The comparison between thin-film coating and aqueous slurry method reveals that slurry method is more efficient than coating but the problems of leaching and the requirement of separation can be avoided by using coating technique. These observations indicate that all the three dyes could be degraded completely at different time intervals. Hence, it may be a viable technique for the safe disposal of textile wastewater into the water streams.

Solar light induced and TiO2 assisted degradation of textile dye reactive blue 4.

Aqueous solutions of reactive blue 4 textile dye are totally mineralised when irradiated with TiO2 photocatalyst. A solution containing 4 x 10(-4) M dye was completely degraded in 24 h irradiation time. The intensity of the solar light was measured using Lux meter. The results showed that the dye molecules were completely degraded to CO2, SO4(2-), NO3-, NH4+ and H2O under solar irradiation. The addition of hydrogen peroxide and potassium persulphate influenced the photodegradation efficiency. The rapidity of photodegradation of dye intermediates were observed in the presence of hydrogen peroxide than in its absence. The auxiliary chemicals such as sodium carbonate and sodium chloride substantially affected the photodegradation efficiency. High performance liquid chromatography and chemical oxygen demand were used to study the mineralisation and degradation of the dye respectively. It is concluded that solar light induced degradation of textile dye in wastewater is a viable technique for wastewater treatment.

Sonolytic degradation of methyl tert-butyl ether: the role of coupled fenton process and persulphate ion

The sonolytic degradation of methyl tert-butyl ether (MTBE) has been investigated at ultrasonic frequency of 20 kHz. The observed pseudo-first-order rate constant decreased from 1.25 x 10(-4) to 5.32 x 10(-5) s(-1) as the concentration of MTBE increased from 2.84 x 10(-2) to 2.84 x 10(-1) mM. The rate of degradation of MTBE increased with the increase of the power density of ultrasonicator and also with the rise in reactor system temperature. In the presence of oxidising agent, potassium persulphate, the sonolytic rate of degradation of MTBE was accelerated substantially. Tert-butyl formate (TBF) and acetone were found to be the major intermediates of the degradation of MTBE. It is found that the ultrasound/Fe2+/H2O2 method is promising process for the degradation of MTBE. More than 95% degradation of MTBE (2.84 x 10(-2) mM) along with its intermediate products has been achieved during the coupled ultrasound/Fe2+/ H2O2 method. Hence, the coupled ultrasound/Fe2+/H2O2 may be a viable method for the degradation MTBE within a short period of time than the ultrasound irradiation process only. A kinetic model, based on the initial rates of degradation of MTBE and TBF, provides a good agreement with the experimental results.

Graphene oxide based Pt-TiO2 photocatalyst: ultrasound assisted synthesis, characterization and catalytic efficiency.

An ultrasound-assisted method was used for synthesizing nanosized Pt-graphene oxide (GO)-TiO2 photocatalyst. The Pt-GO-TiO2 nanoparticles were characterized by diffused reflectance spectroscopy, X-ray diffraction, N2 BET adsorption-desorption measurements, atomic force microscopy and transmission electron microscopy. The photocatalytic and sonophotocatalytic degradation of a commonly used anionic surfactant, dodecylbenzenesulfonate (DBS), in aqueous solution was carried out using Pt-GO-TiO2 nanoparticles in order to evaluate the photocatalytic efficiency. For comparison purpose, sonolytic degradation of DBS was carried out. The Pt-GO-TiO2 catalyst degraded DBS at a higher rate than P-25 (TiO2), prepared TiO2 or GO-TiO2 photocatalysts. The mineralization of DBS was enhanced by a factor of 3 using Pt-GO-TiO2 compared to the P-25 (TiO2). In the presence of GO, an enhanced rate of DBS oxidation was observed and, when doped with platinum, mineralization of DBS was further enhanced. The Pt-GO-TiO2 catalyst also showed a considerable amount of degradation of DBS under visible light irradiation. The initial solution pH had an effect on the rate of photocatalytic oxidation of DBS, whereas no such effect of initial pH was observed in the sonochemical or sonophotocatalytic oxidation of DBS. The intermediate products formed during the degradation of DBS were monitored using electrospray mass spectrometry. The ability of GO to serve as a solid support to anchor platinum particles on GO-TiO2 is useful in developing new photocatalysts.

Sonochemical oxidation of arsenic(III) to arsenic(V) using potassium peroxydisulfate as an oxidizing agent

The sonochemical oxidation of As(III) in the presence of peroxydisulfate ion (PDS) has been investigated. Sulfate anion radicals and OH radicals produced during acoustic cavitation readily oxidized As(III) to As(V) in an aqueous environment. The rate of oxidation of As(III) was remarkably high ( approximately 10 times) with respect to the concentration of PDS. The As(III) oxidation was found to be independent of the initial pH of the solution in the range 3-8. It was relatively low at pH above 8, however, this could be circumvented by increasing the concentration of PDS. The presence of oxygen in solution played a significant role in the rate of oxidation of As(III). Around 40% oxidation of As(III) was observed in the absence of oxygen compared to 80% oxidation in the presence of dissolved oxygen (10mg/L) over a sonication time of 5 min. The addition of humic acid (HA) retarded the oxidation rate of As(III), but the effect could be offset by using larger amounts of PDS. The effects of ultrasound intensity, and frequency on the rate of the oxidation of As(III) were also studied. The rate of the oxidation of As(III) was not significantly dependent on the acoustic power applied, for the concentrations of As(III) used in this study. At an ultrasound frequency of 211 kHz, the rate of oxidation of As(III) was lower than that observed at 20 kHz. It is concluded that the sonochemical treatment of As(III) solutions in the presence of PDS is a simple and viable technique for the oxidation of As(III) to As(V).

Diffused sunlight driven highly synergistic pathway for complete mineralization of organic contaminants using reduced graphene oxide supported photocatalyst

Diffused sunlight is found to be an effective light source for the efficient degradation and mineralization of organic pollutant (methyl orange as a probe) by sono-photocatalytic degradation using reduced graphene oxide (rGO) supported CuO-TiO2 photocatalyst. The prepared catalysts are characterized by XRD, XPS, UV-vis DRS, PL, photoelectrochemical, SEM-EDS and TEM. A 10 fold synergy is achieved for the first time by combining sonochemical and photocatalytic degradation under diffused sunlight. rGO loading augments the activity of bare CuO-TiO2 more than two fold. The ability of rGO in storing, transferring, and shuttling electrons at the heterojunction between TiO2 and CuO facilitates the separation of photogenerated electron-hole pairs, as evidenced by the photoluminescence results. The complete mineralization of MO and the by-products within a short span of time is confirmed by TOC analysis. Further, hydroxyl radical mediated degradation under diffused sunlight is confirmed by LC-MS. This system shows similar activity for the degradation of methylene blue and 4-chlorophenol indicating the versatility of the catalyst for the degradation of various pollutants. This investigation is likely to open new possibilities for the development of highly efficient diffused sunlight driven TiO2 based photocatalysts for the complete mineralization of organic contaminants.

Heterogeneous Catalytic Oxidation of Phenanthrene by Hydrogen Peroxide in Soil Slurry: Kinetics, Mechanism, and Implication

The degradation of phenanthrene sorbed on soil has been carried out using a H2O2/goethite heterogeneous catalytic oxidation process. The effect of operating variables, such as the goethite concentration, pH, H2O2 concentration, soil organic matter, and bicarbonate ions has been investigated. The reaction followed pseudo-first order kinetics. The rate constants were evaluated and varied between 2.0×10−4 and 1.1×10−3 min−1 depending on the H2O2 concentration. The highest rate of degradation of phenanthrene was observed at a H2O2 concentration of 5 M and 134.0 g/kg goethite. The intermediate product formed during the degradation of phenanthrene was identified to be salicylic acid that finally degraded to CO2 and H2O. H2O2 consumption continued as the OH radical attacked the salicylic acid. More than 80% consumption of the 5 M H2O2 took place within 30 min, and the degradation was almost complete after 3 h of reaction. Neutral pH was found to be effective in the removal of phenanthrene. Both soil organic matter (SOM) and bicarbonate ions in the soil inhibited the oxidation rate of phenanthrene.

Degradation of textile dye by solar light using TiO2 and ZnO photocatalysts

Abstract The photocatalytic degradation of a textile dye, reactive red 2 in presence of sunlight using TiO2 and ZnO as photocatalysts is reported. The experimental studies have indicated complete decolourisation of the dye in a short period and degradation within 8 hr of irradiation. ZnO was found to be more effective in the removal of colour than TiO2, but the degradation efficiency was found to be more with TiO2. ZnO decomposes on prolonged irradiation while TiO2 is not photocorrosive. The percent degradation of the dye is high for both the catalysts at an optimum concentration of the catalysts. The first order rate constant is found to increase with decreasing dye concentration.

Preparation and properties of visible light responsive ZrTiO4/Bi2O3 photocatalysts for 4-chlorophenol decomposition

In this work, visible light responsive (VLR) ZrTiO(4)/Bi(2)O(3) photocatalysts were successfully synthesized by a hydrothermal method. The prepared ZrTiO(4)/Bi(2)O(3) photocatalysts were characterized by X-ray diffraction studies (XRD), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), photoluminescence (PL) and transmission electron microscopy (TEM) analyses. DRS results revealed that the extent of light absorption towards the visible region of the spectrum increased with an increase in the calcination temperature of the catalysts up to 450 degrees C and then started to decrease. The decrease in absorption at high temperatures was mainly due to the formation of polycrystalline ZrTiO(4)/Bi(2)O(3) from the tetragonal Bi(2)O(3) pure oxide particles. All the metals present in the ZrTiO(4)/Bi(2)O(3) composite nano-particles also exhibited corresponding oxide states. Particle sizes of about 7 nm were obtained during this combined method of preparation, especially with the catalysts calcined at 450 degrees C. The photocatalytic activity of the catalysts was measured using 4-chlorophenol as a model pollutant for these environmental remediation studies. Among the catalysts calcined at different temperatures, the samples calcined at 450 degrees C showed the most remarkable degradation of 4-chlorophenol, higher than not only the other calcined catalysts but also the commercially available Degussa P-25. This is due to the formation of smaller particle sizes, a higher surface area and stronger absorption in the visible light irradiation for these catalysts calcined at 450 degrees C. Thus, such new VLR photocatalysts can be expected to work effectively under visible light regions as an applicable alternative photocatalyst for commercial scale use.