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ISSN: 2395-7549
K Jagadish Dr.S.Srikantaswamy
Research Scholar Associate Professor
Centre for Materials Science and Technology University of DOS in Environmental Science University of
Mysore Mysore
M.R Abhilash
Research Scholar
DOS in Environmental Science University of Mysore
Abstract
In recent years pharmaceutical wastes (PW) deposal of has become a major difficulty for the environment. Therefore,
pharmaceutical waste removal is very necessary before its discharge from the pharma industry. The separation of drugs
containing organic compounds in wastewater streams is failed by convectional and biological treatments. Thus, the reduction of
harmful effects of pharmaceutical compounds is possible by heterogeneous photocatalysis process. Herein we reported the
degradation of pharmaceutical concentration in pharmaceutical waste by heterogeneous photocatalyst ZnO doped with Selenium
prepared by cost effective hydrothermal method. In addition the heavy metals in pharmaceutical waste were also removed by
ZnO/Se nanocomposite. The average band gap of nanocomposite (~2.5 eV) increase the photocatalytic activity and degrade the
organic compounds in pharmaceutical waste. The heavy metals get adsorbed on the high surface area of nanocomposite and
removed completely by filtration method. The Selenium doped ZnO photocatalyst semiconductor was characterized by scanning
electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM/EDAX) and also the characteristic crystalline
forms of ZnO/Se nanocomposite was confirmed by XRD. The functional groups and particle size distribution of ZnO/Se
nanocomposite was characterized by FTIR and DLS respectively. The reduction of organic compounds in the pharmaceutical
waste was confirmed by COD analysis and removal of heavy metals was performed by AAS analysis.
Keywords: Sol-gel, Hydrothermal, Nanocomposite, Pharmaceutical, Water Purification
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I. INTRODUCTION
The investigation of visible-light active semiconductor photocatalysts has gained huge applications in environmental
nanotechnology. The degradation of organic compounds in pharmaceutical wastewater using ZnO and its composites is
becoming the most extensive photocatalyst. The primary step in photocatalysis is the creation of pairs of Electron - hole further
increasing excitation of band-gap ZnO. Oxidizing species will yield by migration of these pairs interface. Among various
semiconductor photocatalysts (Fe2O3, ZnO, WO3, ZnS, CdS and SrTiO3) used, ZnO has emerged to be more efficient catalyst
because its higher rate mineralization and efficient generation of more number of H 2O2 [1]. ZnO nanoparticle has more number
of active sites with high surface activity. Among the various semiconducting materials, the investigation of TiO2 is widely
employed, however for the degradation of organic compounds in aquatic systems ZnO exhibits better efficiency than TiO2 [2].
ZnO Doped with metal ions can influence the performance and affects the interfacial charge transfer of the photocatalysts. The
largest enhancement of photoactivity through doping can be found in nanosized particles. However, ZnO has a wide band-gap
(~3.37 eV) [3] and is excited by sun-light irradiation. Charge separation distances within the ZnO semiconductor particle,
recombination speed of e/h+ is too fast and resulting very less quantum yield [4]. A good photocatalyst ZnO nanocomposite has
efficiency of e/h+ pair separation and many research developed with focusing on increasing the photocatalytic efficiency in
visible region. The modification of ZnO with metal, non-metal ion, rare earth metals and surface modificatio [5-16]. Transition
metal ions like Fe3+, Cr3+, Co2+ and Mo2+ are usually employed to lower the band-gap and enhance the photocatalytic activity of
ZnO. Metal ion doped ZnO nanoparticle has considerable effects in the photocatalytic activity that photocatalytic degradation
increases with metal ions doping.
In our previous article the industrial wastewater treatment was carried out by using multiwalled carbon nanotube and
polyvinyl alcohol nanocomposite for the degradation of organic compounds and removal of heavy metals [17]. The motivation of
this study is in the published paper by Amal et al. [18]. The authors investigated the characteristics of selenium (Se IV) ions in
aqueous TiO2 suspensions and they observed that a red-shift in the absorption threshold. In this research work, the attempt was
made to dope ZnO with selenium (IV) ions to obtain a visible-light active photocatalyst. Song et al. [19] have synthesized Se
(II)-doped In OOH by a mild solvothermal method and concluded that Se (II)-doping narrows the band-gap of the photocatalyst.
This paper has the purpose of determining the photocatalytic properties of Se doped nano-ZnO, to elucidate the chemical nature,
morphology and the effect of the selenium dopant on the activity of the photocatalyst. In the experimental part of the study, a
series of Se doped ZnO nano-photocatalysts were prepared by means of a hydrothermal method and characterized by structural,
chemical techniques. The photocatalytic activity of the Se doped ZnO was also determined by investigating the photocatalytic
degradation of pharmaceutical and industrial wastewater.
Fig. 2: Morphology and microstructure analysis of a) ZnO and b) ZnO-Se nanocomposite by SEM
The SEM picture in Fig. 2a shows the typical ZnO nanoparticles have a diameter ranging from ~100 to 200 nm with a typical
length up to ~1 micrometer. Fig. 2b shows a SEM image of Se doped ZnO nanoparticles, the nanoparticles will be growing on
the sol gel and hydrothermal reaction and the non-uniformity of local precursor concentration and temperature causes the
morphology of the products. This explains the near exact similarity in the morphology and dimensions of Se doped ZnO
nanoparticles.
Energy-Dispersive X-Ray Spectroscopy (EDAX)
The energy-dispersive X-ray spectroscopy (EDAX) spectrum sample reveals only ZnO and Se signal peaks (Fig. 3). The
approximate atomic ratio of Zn, O and Se is found to be 67.13, 24.96 and 7.92 respectively. This spectrum indicates that the
ZnO/Se nanocomposite is in pure phase with showing nearly 10 at % doping of Se in the system. The EDAX spectrum also
shows the weight percentage of Zn, O and Se nanocomposite in which the weight such as 44.61, 23.82 and 31.36 respectively.
Fig. 8: Graphical representation of treatment of pharmaceutical waste with different weight of ZnO/Se composite
The pharmaceutical effluent was treated with 0.0, 0.1, 0.25 and 0.5 g of ZnO-Se nanocomposite semiconductor photocatalyst
in the presence of sunlight and the concentration was recorded before and after the treatment for the analysis of heavy metals
(Table 2). The pharmaceutical effluent treated with 0.5 g of ZnO/Se nanocomposite is found to be optimum and the reduction of
heavy metals concentration observed. The heavy metals such as nickel and zinc have removed completely and the gradual
reduction of copper concentration is possible by using ZnO/Se nanocomposite.
Here the pharmaceutical effluents were prepared for different pH conditions like 4, 7 and 10 by pH monitoring reagent 0.1 M
HCl and 0.1 M NaOH. And these effluents were treated with 0.5 g of ZnO-Se. The Fig.4.11 shows that all the heavy metals
degradation in pH 4 and pH 7 and pH 10. This shows that pH condition of the treatment method of the effluent alters the
degradation effectively. The degradation was more in pH 4 (acidic condition) when compare to pH 7 and 10 due to surface
charge on the nonmaterial, which increases the degradation process.
Fig. 9: Graphical representation of Heavy metal concentrations in PW after treatment with 0.5 g ZnO-Se composite at different pH condition
Chemical Oxygen Demand (COD)
The analysis of organic content in the pharmaceutical waste was analyzed by using COD technique. The titration value is
determined the organic content in mg/L (ppm) which is about presence of oxygen in the organic molecules which is present in
the industrial pharmaceutical effluent.
Table 3
COD analysis for the PW in different ZnO-Se composite (pH 7)
Sl No. ZnO/Se nanocomposite (g) COD (mg/kg)
1 0.0 1770
2 0.1 1650
3 0.25 960
4 0.5 250
Fig. 10: Graphical representation of COD in for the PW in different ZnO-Se composite (pH 7)
Table 4
COD analysis for the PW in different pH condition at 0.5 ZnO-Se concentrations
Sl. No. Different pH condition for the ZnO-Se metal concentration (0.5 g) COD values Mg/L
1 4 120
2 7 250
3 10 255
Chemical Oxygen demand for the untreated and treated PW using ZnO-Se metal nanocomposite was performed and found that
the presence of highest organic content in pharmaceutical waste. Furthermore 0.5 g of ZnO-Se metal nanocomposite to the PW at
the acidic condition reduces the organic content by degrade the organic molecule in the presence of sunlight.
IV. CONCLUSION
The above study is very much important considering the effect of removal of heavy metals and degradation of pharmaceutical
waste using ZnO/Se nanocomposite. The nanocomposite photocatalysts was prepared by an cost effective hydrothermal method
and its having high surface area and surface charge which act as semiconductor materials with effective band gap energy.
Characterization techniques showed that the Se is in OSeO linkages in the crystal lattice, the spherical images of nanomaterial
with high surface area, particle size distribution with average particlae size 184 nm and the band gap energy 2.5 eV with
semiconducting properties. The uses of selenium as dopant with ZnO nanoparticle increase the photocatalytic performance of
nanocomposite. The heavy metals in pharmaceutical waste such Cu, Pb, Ni, Zn, Cd and Cr were reduced and the Ni and Zn were
completely removed by treatment with the 0.5 g of nanocomposite. The COD values of pharmaceutical waste were reduced
gradually by treatment with nanocomposite in which the organic compound presents in waste were degraded to purify in the
pharmaceutical waste.
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