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Photocatalytic Bleaching of Evans Blue Over Zinc Oxide Particulate

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Photocatalytic Bleaching of Evans Blue Over Zinc Oxide Particulate Indian Journal of Chemistry Vol. 46A, March 2007, pp. 432-435 8 Photocatalytic bleaching of Evans blue over Matsuo and Udea have used SrTiO3-TiO2 composite zinc oxide particulate system powder for the photocatalytic bleaching of methylene blue. Preparation and characterization of ZnO/TiO2, Sharad Kothari*, Preeti Ameta & Rameshwar Ameta photocatalyst and their photocatalytic activity were reported by Liao et al.9 PG Department of Chemistry, Government College, 10,11 Banswara 327 001, India Sehili et al. have investigated the photocatalytic Email: [email protected] transformation of chloroaromatic derivatives such as Received 10 May 2006; revised 31 January 2007 chlorophenol and dichlorobenzenes on ZnO involving the formation of an adduct between OH• radicals and Evans blue, an azo dye, and its mixture with amaranth are 12 degraded photocatalytically in presence of zinc oxide. The aromatic compound. Driessen et al. have studied optimum conditions for photobleaching of these dyes, like surface band(CB) and gas phase products and concentration of dye, pH, amount of semiconductor, light intermediates with FT-IR spectroscopy during intensity, etc., have been studied. During the photocatalytic photocatalytic oxidation of trichloroethylene on ZnO. degradation, the semiconductor (ZnO) remains unaffected as Synthesis and photocatalytic activity of ZnO/ZrO2 evident from its FT-IR. The studied dyes are commonly used in 13 dyeing, printing and textile industries and hence, the present work composite have been reported by Hsu and Wu. Riaj will be helpful in the treatment of coloured effluents from these et al.14 used ZnO as a photocatalyst for the industries. photocatalytic bleaching of rhodamine-6G. 8 Photocatalytic bleaching of Evan blue (EB) has not IPC Code: Int. Cl. B01J8/00 been reported in literature although it is extensively used in dyeing, printing and textile industries. It was Various technologies and methodologies ranging from thus, thought worthwhile to study the present reaction. physical methods to biodegradable processes are available for removing colour from water. However, these methods are not cost-effective. The effluents Experimental from dyeing and printing industries when discharged Evan blue (EB, I), amaranth and zinc oxide were analytical grade chemicals. The stock solution (1.00 × into the river, ponds not only disturb the ecosystem -3 but are also a serious health hazard for the human 10 M) of EB was prepared in doubly distilled water beings. With the increase in the environmental (0.0960 g/100 mL). Some controlled experiments awareness all over the world, search for new cost were carried out to confirm that this reaction follows effective and green routes to treat water contaminated the photocatalytic pathway. Zinc oxide (0.60 g) was -5 with dye effluents has increased in recent years. The added to 50.0 mL of 1.50 × 10 M EB solution. The heterogeneous photocatalytic processes give an pH of the solution was adjusted to the desired value excellent pathway to treat the coloured water to make by addition of previously standardized H2SO4/NaOH it colourless, which may then be used for cleaning, solutions. The pH of the solution was measured by a cooling and irrigation purposes1. digital pH meter (Systronics, model 335). Sakthivel et al.2,3 reported that the photocatalytic NH OH efficiency of ZnO in the photodegradation of dyes is 2 OH NH2 4 NaO S SO3Na 3 NN NN slightly higher than that of TiO2. Sharma et al. have investigated the photocatalytic bleaching of Orange-G CH 5 3 CH3 in aqueous ZnO solutions. Ameta et al. used ZnO as NaO3S SO3Na a photocatalyst for the photocatalytic bleaching of basic blue-24. Effect of TiO acidic pre-treatment on 2 its photocatalytic properties for phenol degradation 6, 6′- [(3, 3′- Dimethyl [1, 1′-biphenyl]-4, 4′-diyl] bis (azo)] bis 6 7 has been reported by Colon et al. while Wang et al. [4-amino-5-hydroxy-1, 3-naphthalene-disulphonic acid] tetra have reported the photocatalytic degradation of sodium salt (Evans blue) biphenyl–A on TiO2 enhanced by β-cyclodextrin. (I) NOTES 433 A 500 W tungsten lamp (Mysore) was used for molecules to the semiconductor surface will be irradiation. The intensity of light was measured by a retarded due to repulsive force between two Surya Mapi (CEL SM 201) solarimeter. A water filter negatively charged species (OH¯ ions and the electron was used to cut-off thermal radiations. The progress rich dye). This will result in a corresponding decrease of the reaction was measured using a in the rate of photocatalytic bleaching of Evans blue spectrophotometer (Systronics, model 116). The at higher pH value i.e., pH > 8.0. solution was made free from ZnO particles and other impurities by centrifuging before absorbance Effect of dye concentration measurements. The effect of dye concentration on the rate of the reaction was studied by using different concentrations Results and discussion of EB solution. It was observed that as the The photocatalytic bleaching of EB was followed concentration of EB was increased; the rate of at λmax = 611 nm. UV-visible spectrum of the reaction photocatalytic bleaching also increases, reaching a mixture at different time intervals i.e. before maximum at 1.50 × 10-5 M. Further increase in exposure, during exposure and after complete concentration of dye resulted in a decrease in the rate experiment were recorded. It is clear from the spectral of photocatalytic bleaching. This may be due to the data that absorption at 611 nm (for EB) decreases fact that as the concentration of the dye increased, during the course of the reaction and ultimately there more dye molecules were available for excitation and is negligible absorption. There was no absorption consecutive energy transfer. band above 400 nm, which indicates that no colour But if the concentration of EB was increased above compounds (dye or its coloured components) are 1.50 × 10-5 M, the dye starts acting as a filter for the formed. The optimum condition was obtained at incident light and prohibits the desired light intensity [Evans blue] = 1.50 × 10-5 M, light intensity = 50.0 to reach the dye molecules near the semiconductor mW cm-2, pH = 8.0, ZnO = 0.60 g and temperature = particles. Thus, a decrease in the rate of photocatalytic 308 K. bleaching was observed. The plot of 2 + log O.D. versus exposure time was linear, which indicates that the photocatalytic Effect of amount of ZnO bleaching of Evans blue follows first order kinetics. The effect of amount of ZnO powder on the rate of The rate constant (k) for the reaction was determined photocatalytic bleaching of the EB was also studied. It using the expression (2). was observed that the rate of reaction increases with increase in the amount of ZnO up to 0.60 g. Beyond Effect of pH 0.60 g, the rate of reaction becomes virtually constant. The effect of pH on the rate of photocatalytic This may be due to the fact that as the amount of bleaching of EB was investigated. ZnO dissolves in semiconductor was increased in the initial stage, the highly acidic medium, and therefore, photocatalytic exposed surface area of the semiconductor also bleaching of EB could not be investigated in lower pH increases. However, after this limiting value (0.60 g), range. increase in the amount of semiconductor increases The rate of photocatalytic bleaching of EB only the thickness of the semiconductor layer and not increases with increase in pH up to pH 8.0 and with the exposed surface area. This was also confirmed by further increase, it decreases. This behaviour may be using reaction vessels of different dimensions. explained on the basis that an increase in the rate of To know the state of ZnO, the FT-IR spectrum of photocatalytic bleaching may be due to the increased ZnO were recorded in dry and wet state as well as at ¯ ¯ availability of OH ions at higher pH values. The OH the end of the experiment (Fig. 1). It is clear from the ● ions will generate more hydroxyl radicals ( OH) by FT-IR spectral data that there is no reasonable change, combining with holes, which are considered in the nature of ZnO during this photocatalytic responsible for the photocatalytic bleaching. process indicating that ZnO remains intact or is ¯ Above pH value 8.0, more OH ions will compete regenerated back. with the electron rich dye for adsorption on ¯ semiconductor surface. Also, the OH ions will make Effect of light intensity the surface of the semiconductor negatively charged The effect of light intensity on the rate of and as a consequence, the approach of Evans blue photocatalytic bleaching of EB was studied. The 434 INDIAN J CHEM, SEC A, MARCH 2007 results show that an increase in light intensity results It was observed that in the mixture of dyes (EB + in a corresponding increase in the rate of Amaranth), the rate of photocatalytic bleaching of EB photocatalytic bleaching. As the intensity of light was (9.60 × 10-5 s-1) decreases as compared to its increased, the number of photons striking per unit individual bleaching rate (1.22 × 10-4 s-1). This can be area of the semiconductor (ZnO) also increases. An explained on the basis that both these anionic dyes almost linear behaviour between light intensity and will not permit the same intensity of light to pass the rate of reaction was observed. Since an increase in through the solution to reach the semiconductor the light intensity also increases the temperature of surface under these conditions. dye solution leading to a thermal reaction, higher intensities were avoided. Mechanism On the basis of the observed data, the following Effect of mixing Amaranth tentative mechanism may be proposed for To investigate the effect of one phtocatalytic dye photocatalytic bleaching of EB.
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