Rekha Rani Agarwal et al.

, IJSID, 2012, 2 (5), 448-456

ISSN:2249-5347

IJSID

International Journal of Science Innovations and Discoveries

Research Article

An International peer Review Journal for Science

Available online through www.ijsidonline.info

PHOTO CATALYTIC DEGRADATION OF M-DINITROBENZENE USING SEMICONDUCTOR ZnO AND H 2O2 Rekha Rani Agarwal and Sangita Gupta* Global College of Technology, Sitapura, Jaipur, India

ABSTRACT Received: 15-07-2012 Accepted: 08-10-2012

*Corresponding Author

various parameters such as pH (5-10), irradiation time (0.0-180min.), light intensity catalyst (0.06-0.22grams) and concentration of H2O2(0.05-0.35mL/h) etc. H2O2 is 0.30mL/h respectively.

(40.0-90.0mW/cm2), concentration of substrate (0.10mM-2.50mM), concentration of pH 8.5, light intensity 70 mW/cm2, with concentration of ZnO is 0.14grams and conc. of Keywords : Photo catalytic degradation, Zinc Oxide, m-Dinitrobenzene.

Photo catalytic degradation of chemical pollutant in water was investigated for The m-

Dinitrobenzene acts as a substrate, ZnO acts as a photo catalyst and H 2O2 used as an accelerator. The photo catalytic degradation of 10mM m-Dinitrobenzene is optimum at

Address: Name: Sangita Gupta Place: Global College of Technology, Jaipur, India. E-mail: sangita.uor@gmail.com

INTRODUCTION

INTRODUCTION

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Rekha Rani Agarwal et al., IJSID, 2012, 2 (5), 448-456 This electron can be used for reducing a substrate, whereas the hole may be utilized for oxidation. Thus the chemical reactions that occur in the presence of a semiconductor and light are collectively termed as photo catalytic reaction. Semiconductor can agents, medicine and the synthesis of pharmaceuticals. Nitro aromatic compounds (NAC) are widely used in chemical is an important compound used as an intermediate or precursor in the manufacture of organic dyes, pesticides ,antiseptic large-scale manufacture and use of NAC has led to significant contamination of soils and groundwater. Biological treatment of wastewater. Photocatalytic oxidation with Ti[O.sub.2] [5, 6]; various advanced oxidation processes (AOPs) including ozone, UV Photo catalysis is a phenomenon, in which an electron-hole pair is generated on exposing a semiconducting material. INTRODUCTION

be used as a photo catalyst and degrade organic pollutants in water to less harmful in organic material [1]. m-Dinitrobenzene industries (synthesis of dyes, pesticides, explosives, etc.) and have been associated with groundwater contamination [2]. The aqueous solutions of NAC is a complicated problem. NAC are not well biodegraded [3]. Their biological treatment is limited by their toxicity at high concentrations to microorganisms and sometimes produces recalcitrant or toxic by-products [4]. Some radiation, and hydrogen peroxide [7, 8]; elemental iron ([Fe.sup.0])/ultrasound [9]; etc.. The photo catalytic degradation of various types of pollutants using solar radiation was studied at pilot scale. This technology has been developed and it is technology to achieve complete mineralization of toxic organic pollutants has received much attention in recent years [15]. The sun can be used as an economic and ecological source of light, which will save the installation and energy consumption treatments of organic contaminants in wastewater[18-22].

chemical oxidation methods have been recommended as a pre-treatment step for the purification of NAC-containing currently being evaluated for application at pilot plant and semi-industrial scales of testing (Zhang et al., 1994)[10]. The use of

photochemical technologies has been shown to be a promising alternative for the detoxification of industrial effluents [11-13], expenses of an artificial light source [16]. Hussein et al.[17] reported that TiO 2 and ZnO have good photo catalytic properties in the range of solar radiation. Semiconductors (ZnO, TiO 2) and mediated photo catalysis are fast emerging technology for the EXPERIMENTAL were used. Measurements of pH, irradiation time, light intensity and optical density were carried out using digital pH meter

especially from the environmental point of view [14]. The possibility of combining heterogeneous catalysis with solar nominated both catalyst to be promising substrate for photo-degradation of water pollutant and show the appropriate activity Solutions were prepared in absolute alcohol and double distilled water. Reagent such as p- nitro aniline, H2O2 and ZnO

(Systronics Model 335), 200W tungsten lamp (Philips), Solarimeter (Surya Mapi Model CEL201) and spectrophotometer (Systronics Model 106). The solution of 10mM m-Dinitrobenzene was prepared by dissolving in absolute alcohol and double exposed to light, third part added with ZnO and it was kept in dark and last fourth part containing above solution and ZnO,

distilled water. H2O2 was added in this solution and it was divided into four parts. First part was kept in dark, second part was measured in each solution. There was no change in the optical density of first three solutions; however in the fourth solution catalytic route. The solution of 10mM m-Dinitrobenzene with pH = 8.5 was prepared taking, and added the quantity of ZnO = 0.14gram and H2O2 = 0.30mL/h. It was then exposed to 200W tungsten lamp. The optical density of this solution was observed International Journal of Science Innovations and Discoveries, Volume 2, Issue 5, September-October 2012 at regular time intervals. It was observed that the amount of p- nitro aniline decreases with increasing time of exposure as

was exposed to light. After keeping these solutions for three hours, the amount of unreacted M m-Dinitrobenzene was this observation one can conclude that this reaction requires presence of light as well as ZnO and this reactions follows photo

the concentration of unreacted M m-Dinitrobenzene decreases with exposure of light, it means optical density changes. From

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shown in Table 1. A plot of 1+log O.D. (optical density) against time was linear as shown in Fig. 1. The rate constant was calculated with this expression: k = 2.303 slope . Effect of pH depicted in Table 1(a) and graphically represented in Fig. 1(a) Effect of concentration of m-Dinitrobenzene and Fig. 1(b) .

Rekha Rani Agarwal et al., IJSID, 2012, 2 (5), 448-456

The above same procedure was repeated at different pH (5.0-10.0) and rate constant was calculated. The effect of pH is concentrations of m-Dinitrobenzene, keeping all other factors constant. The results obtained are summarized in Table 1(b) Time (min.) 0 15 30 45 60 75 90 105 120 135 150 165 180 TABLE-1 1+log (O.D.) 0.6253 0.6052 0.5934 0.5803 0.5683 0.5564 0.5477 0.5286 0.5204 0.5114 0.4941 0.4805 0.4704

The effect of concentration of m-Dinitrobenzene on the rate of its photo catalytic degradation was studied by variation in

pH 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 Effect of concentration of photo catalyst

TABLE-1(a)

The effect of variation in the amount of photo catalyst on the rate of photo catalytic degradation of m-Dinitrobenzene was performed. The results give in Table 1(c) and Fig. 1(c) Effect of concentration of hydrogen peroxide investigated. The results give in Table 1(d) & Fig.1(d).

K 105 (sec -1) 1.9 2.13 2.38 2.59 2.77 2.98 3.16 3.26 3.1 2.98 2.83

The effect of addition of amount of H2O2 on the rate of the photo catalytic degradation of m-Dinitrobenzene was also

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Rekha Rani Agarwal et al., IJSID, 2012, 2 (5), 448-456 The effect of variation of light intensity on the photo catalytic degradation of m-Dinitrobenzene was also investigated and the Effect of light intensity observations are summarized in Table 1 (e) and Fig1 (e). [ m-Dinitrobenzene] 10-2M 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 TABLE-1(b) k 105(sec -1) 1.41 1.67 1.72 1.83 1.97 2.25 2.71 3.26 2.93 2.55 2.44 k 105 (sec-1) 2.16 2.27 2.36 2.8 3.26 3.24 3.25 3.22 3.24

Amount of photo catalyst(g) 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.20 0.22 H2O2(mLh-1) 0.05 0.1 0.15 0.2 0.25 0.3 0.35

TABLE-1(c)

TABLE-1(d)

The results of experimental observations have been reported in above Tables 1 (a-e) and Fig. 1(a-e). The effect of various RESULTS AND DISCUSSION parameters on the rate of photo catalytic degradation of m-Dinitrobenzene is being presented as follows:

Light Intensity (mW cm-2) 40 50 60 70 80 90

TABLE-1(e)

k 105 (sec -1) 2.45 2.6 2.74 2.96 3.11 3.26 3.27 k 105 (sec -1) 1.67 2.08 2.51 3.26 3.86 4.4

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Rekha Rani Agarwal et al., IJSID, 2012, 2 (5), 448-456 It is evident from the data in the tables that the rate of photo catalytic degradation of m-Dinitrobenzene increases with Effect of pH basic medium. Perret and holleck [23] observed that ArNO 2 show bathochromic effect with increasing pH. The effect of pH is similar to that observed earlier in the case of trinitrotoluene[24-26] on increasing the pH further a decrease in the rate of max is also shifted to the red shift, so that it will not permit the desired light intensity to reach the surface of ZnO. Effect of concentration of p- nitro aniline increase in pH up to 8.5 and further increase in pH decreases the rate of reaction. It was observed that the m-Dinitrobenzene degradation was observed. The bathochromic shift and hypochromic effect will make the solution dark yellow in color and its reaches an optimum for (m-Dinitrobenzene) =10 mM and further increase in concentration, decreases the rate of reaction. It compound will start acting like a filter for incident light. Effect of concentration of photo catalyst

degrade photo catalytically in the presence of H2O2 at pH 8.5. The neutral compound m-Dinitrobenzene degrades in slightly

It was observed that the rate of photocatalytical degradation increases on increasing the concentration of m-Dinitrobenzene may be concluded that the concentration of m-Dinitrobenzene was increased, more molecules were available for excitation It was observed that the rate of photo catalytically degradation was increased on increasing concentration of photo catalyst layer at the bottom of the vessel. and then the energy transfer but if the concentration of m-Dinitrobenzene was increased above a particular limit, this

and it was constant with further increase the concentration of photo catalyst. When the amount of semiconductor was increased, the exposed surface area also increases but after the certain amount (0.14g) of ZnO was increased then there were Effect of concentration of hydrogen peroxide

no increases in the surface area of the photo catalyst because these saturation points will also increases the thickness of the It was observed that as the rate of addition and consequently amount of H 2O2 was increased; the rate of reaction was increased and it attained an optimum value at 0.30mLh-1. Virtually no further or negligible increase in the rate of reaction was observed attributed to an acceleration of the dark reaction by a higher concentration of oxygen formed (27). However, the saturation like behavior was observed due to the excess of H2O2. Effect of Light Intensity

on increasing the rate of addition further. The increase in reaction rate at higher H 2O2 concentration can consequently be It has been observed that on increasing the light intensity, the rate of reaction was increased. A linear behavior between light

intensity and rate of reaction was observed. It can be attributed to the fact that any increase in the light intensity will increase the number of photons striking per unit area of the semiconductor, which in turn will increase the number of electrons hole higher intensities of light avoidable. MECHANISM ArNO2 increase the temperature of the reaction mixture. Thus thermal may occur in place of photo catalytic reaction and therefore presence of semiconductor ZnO and H2O2 ArNO2*+H2O2

pairs. This increase is clearly reflected in term of increased rate of the reaction. Further increase in the intensity of light may On the basis of above observations a mechanism has been proposed for the photo catalytic degradation of ArNO 2 in general in ArNO2* ArNO2 +H2O2*

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2H2O2* SC

ArNO2*+e H2O2+ eArNO2+. ArNO2.

2H2O + O2 HO. + OHArNO2 +. ArNO2-.

Rekha Rani Agarwal et al., IJSID, 2012, 2 (5), 448-456

ArNO2-. + O2 ArNO2*+ h+

e-(CB) + h+(VB) ArNO2 + O2-. ArNO2.+ H+

Aromatic nitro compounds (ArNO2) absorbs incident radiation and it is excited to ArNO 2*, which may transfer its energy to radiations generating electron hole pair. The electron from the CB may be accepted by exited nitro aromatics to form anion and thus, forming the corresponding cationic radical. It may release a proton and a radical give the decomposition product. Fig.1 radicals. However a conductive pathway is reported to in effective for photo degradation of nitro aromatics [28]. This anion

H2O2 and gives the excited state of H2O2*. It may degrade into water and oxygen; the zinc oxide will also absorb suitable radical will transfer its electron to the O2 generating oxygen radical anion. The (ArNO2) may also transfer its electron to hole

Decomposition products

Fig. 1(a)

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Rekha Rani Agarwal et al., IJSID, 2012, 2 (5), 448-456 Fig.1(b)

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Rekha Rani Agarwal et al., IJSID, 2012, 2 (5), 448-456

ZnO could be used powerfully in photo catalytic degradation of textile industrial waste water. The catalyst system is active CONCLUSION under the solar radiation which results the photo degradation of nitro aromatic compound in dyes in waste water ACKNOWLEDGEMENT providing the necessary facilities. 1. 2. 3. 4. 5. 6. 7. 8. 9. Authors wish to thanks the Head, Dept. of Chemistry, Mohan Lal Sukhadiya University, Udaipur and GCT, Sitapura Jaipur for Fang Bai Li, Xian Zhang Li and Kok Wai Cheah, Environmental Chemistry, 2005, 2 (2), 130 . REFERENCES Technol., 2001, 35, 406-410. 22, 519-534.

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