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Journal of Environmental Science and Health, Part A: Toxic/Hazardous Substances and Environmental Engineering
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Photocatalytic treatment of municipal wastewater using modified neodymium doped TiO2 hybrid nanoparticles
Behzad Shahmoradi , Ibrahim A. Ibrahim , Naonori Sakamoto , Sannaiah Ananda , Rudrappa Somashekar , Tagur N. Guru Row & Kullaiah Byrappa
a e f g a b c d

Faculty of Environmental Health Engineering, Kurdistan University of Medical Sciences, Sanandaj, Iran
b c d e f

Central Metallurgical R&D Institute CMRDI, Hellwan, Egypt Shizuoka University, Naka-ku, Hamamatsu-shi, Japan Department of Chemistry, University of Mysore, Manasagangotri, Mysore, India Department of Physics, University of Mysore, Manasagangotri, Mysore, India

Department of Solid State and Structural Chemistry, Indian Institute of Science, Bangalore, India
g

Department of Geology, University of Mysore, Manasagangotri, Mysore, India

Available online: 08 Jul 2010

To cite this article: Behzad Shahmoradi, Ibrahim A. Ibrahim, Naonori Sakamoto, Sannaiah Ananda, Rudrappa Somashekar, Tagur N. Guru Row & Kullaiah Byrappa (2010): Photocatalytic treatment of municipal wastewater using modified neodymium doped TiO2 hybrid nanoparticles, Journal of Environmental Science and Health, Part A: Toxic/Hazardous Substances and Environmental Engineering, 45:10, 1248-1255 To link to this article: http://dx.doi.org/10.1080/10934529.2010.493807

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Journal of Environmental Science and Health Part A (2010) 45, 12481255 Copyright C Taylor & Francis Group, LLC ISSN: 1093-4529 (Print); 1532-4117 (Online) DOI: 10.1080/10934529.2010.493807

Photocatalytic treatment of municipal wastewater using modied neodymium doped TiO2 hybrid nanoparticles
BEHZAD SHAHMORADI1 , IBRAHIM A. IBRAHIM2 , NAONORI SAKAMOTO3 , SANNAIAH ANANDA4 , RUDRAPPA SOMASHEKAR5 , TAGUR N. GURU ROW6 and KULLAIAH BYRAPPA7
1 2

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Faculty of Environmental Health Engineering, Kurdistan University of Medical Sciences, Sanandaj, Iran Central Metallurgical R&D Institute CMRDI, Hellwan, Egypt 3 Shizuoka University, Naka-ku, Hamamatsu-shi, Japan 4 Department of Chemistry, University of Mysore, Manasagangotri, Mysore, India 5 Department of Physics, University of Mysore, Manasagangotri, Mysore, India 6 Department of Solid State and Structural Chemistry, Indian Institute of Science, Bangalore, India 7 Department of Geology, University of Mysore, Manasagangotri, Mysore, India

Photocatalytic degradation of municipal wastewater was investigated using reagent grade TiO2 and modied neodymium doped TiO2 hybrid nanoparticles. For the rst time, surface modication of Nd3+ doped TiO2 hybrid nanoparticles were carried out with n-butylamine as surface modier under mild hydrothermal conditions. The modied nanoparticles obtained were characterized by Powder XRD, FTIR, DLS, TEM, BET surface area, zeta potential and UV-Vis Spectroscopy. The characterization results indicated better morphology, particle size distribution and low agglomeration of the nanoparticles synthesized. It was found that photodegradation of wastewater using surface modied neodymium doped TiO2 nanoparticles was more compared to pure TiO2 , which can be attributed to the doping and modication with n-butylamine. Keywords: Photocatalytic, municipal wastewater, Nd3+ -doped TiO2 nanoparticles, n-butylamine, surface modication, hydrothermal technique.

Introduction
Most wastewater treatment processes are intended to remove organic compounds, which are resistant to biodegradation and their discharge without proper treatment to the water body can reduce the auto-purication capacity of the water body and lead into eutrophication. There are a number of waste disposal methods currently in practice with various degrees of success. Unit operations and processes are grouped together to provide various levels of treatment known as primary, advanced primary, secondary and advanced treatment systems.[13] An ideal waste treatment process should completely mineralize all the toxic species present in the waste stream without leaving behind any

Address correspondence to Behzad Shahmoradi, Faculty of Environmental Health Engineering, Kurdistan University of Medical Sciences, Sanandaj, Iran; E-mail: bshahmorady@gmail.com or Behzad shahmorady@yahoo.com Received January 31, 2010.

hazardous residues. It must be cost-effective. Most of the conventional treatments such as activated sludge or trickling lters require subsequent treatment, which results in high cost. Photodegradation of wastewater is an ecofriendly technique, which produces no sludge. Until now, many kinds of nanoparticles have been studied as photocatalyst including TiO2 , ZnO, CdS, and WO3 .[4] Nano-sized TiO2 is an excellent candidate for a multipurpose photocatalyst, because of its optical properties, including a high refractive index leading to a hiding power and whiteness, as well as it chemical stability, relatively low production cost and high efciency.[5] One of the most crucial subjects in the case of photodegradation is to enhance the interfacial charge-transfer reaction. This can be acheived by implanting,[6] doping and depositing suitable transitional metal ions,[7] noble metals,[8] semiconductor metallic oxides,[9] or nonmetal ions[10] into TiO2 structure. Several methods of TiO2 nanoparticles fabrication such as sol-gel,[11] microemulsion,[12] and hydrothermal[13] have been reported. The fabrication of titanium dioxide

Photocatalytic treatment of municipal wastewater

nanoparticles is a challenging task because of its properties greatly depending upon its size and morphology. The conventional synthesis routes yield highly agglomerated TiO2 particles without any control over their morphology and size, and in some of the preparation processes require post-treatment in order to achieve highly crystalline products with desired properties. Although hydrothermal and solvothermal techniques are more effective in obtaining high quality nanoparticles because of the highly controlled diffusion during the synthesis process, still the problem of size and morphology control cannot be achieved through normal routes. To resolve agglomeration and dispersibility problems, hence, an appropriate capping agent or organic ligand or surfactant or chelating agent is added to achieve a control over the size and morphology for these TiO2 particles and thereby the properties could be effectively tailored.[14] Based on the required criteria for suitable surfactant for in-situ modication of TiO2 catalyst, n-butylamine with different molar ratio was tried and its effect on the synthesized neodymium doped TiO2 hybrid nanoparticles has been discussed in this paper.

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Characterization of the modied neodymium oxide-doped TiO2 hybrid nanoparticles The products fabricated were characterized using different analytical techniques. The Fourier Transform Infrared spectra were recorded using FTIR, JASCO-460 PLUS, Japan, at resolution of 4 cm1 . The Powder X-ray diffraction patterns were recorded using Bruker, D8 Advance, Germany, with Cu K, =1.542 A radiation, Voltage= 40mV, Current=30Ma, Scan speed 2.3 min1 . The data were collected in the 2 range 5100 . The optical properties were studied by using UV-Vis spectrophotometer. Particle size and its distribution were measured using dynamic light scattering (DLS) (Horiba particle size analyzer, LB550, Japan). TEM images of the neodymium doped TiO2 hybrid nanoparticles were recorded using JEM 2000FX II (JOEL. Ltd., Tokyo, Japan). Zeta potential and BET surface area was measured using Zetasizer 2000 instrument (Malvern instruments). Photocatalytic degradation of municipal wastewater The municipal wastewater sample was collected, preserved according to the manual Standard Methods for Water and Wastewater Examinations and treated with 2 mL H2 SO4 per litre of sample[15] . A certain amount of nanoparticles synthesized were added to a 50 ml beaker containing various concentrations of the wastewater collected from the outlet of screening unit of Mysore City main wastewater treatment plant, India. This was exposed to a light source without the external supply of air or oxygen. The detention time, photocatalyst concentration and light source with respect to the percentage of dopants in the modied neodymium doped TiO2 hybrid nanoparticles synthesized were used as variables. A blank sample was used for the comparison purpose to nd out their effect and efciency. The intensity of sunlight and UV (8 W, Sankyo Denki, Japan) was estimated by photolysis of uranyl oxalate; it was estimated that the intensity of sunlight was 6.435 1016 quanta/s, and the intensity of UV was 2.984 1015 quanta/s. About 2-3 mL of the sample that was exposed to the light was taken and centrifuged for 45 min at 1500 rpm and then used to measure the percent transmission (%T) at 540 nm using UV-vis spectrophotometer. The treated samples were ltered to remove the photocatalysts. Then the chemical oxygen demand (COD) test was carried out at a regular interval of 30 minutes up to 3 hr. Open Reux Method (ORM) was used to measure COD.

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Materials and methods

Preparation of modied neodymium doped TiO2 hybrid nanoparticles Neodymium-doped TiO2 hybrid nanoparticles were synthesized under mild hydrothermal conditions (T=150 C, P= autogeneous). 1M of pure TiO2 (Loba Chemie, GR, 99%) was taken as starting material and the dopant (Nd2 O3 : 2 M %; 5 M %) was added into it. A certain amount of 1M HCl was added as mineralizer to the precursors. At the same time different concentrations (0.8, 1.0, 1.2, 1.4 and 1.6M) of nbutylamine (Sisco Research Lab PVT, Ltd., Mumbai India, Assay (GC, 99.5%)) was added to the preceding mixture and it was stirred vigorously for a few minutes. The nal compound was then transferred to the Teon liner (Vll =10 mL), which was later placed inside a General-Purpose autoclave. Then the assembled autoclave was kept in an oven with a temperature programmer-controller for 818 hr. The temperature was kept at 150 C. After the experimental run, the autoclave was cooled to the room temperature. The product in Teon liner was then transferred to a clean beaker, washed with double-distilled water, and later allowed the product to settle down. The surplus solution was removed using a syringe and the remnants were centrifuged for 20 minutes at 1500 rpm. The product was recovered and dried in a hot air oven at 4050 C for a few hours. The dried particles were subjected to a systematic characterization and photocatalytic studies. The nanoparticles fabricated stored in desiccators.

Results and discussion

The powder XRD results indicate that the nanoparticles synthesized match well with I41/amd space group, and also there is a slight change in the lattice parameters of

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Fig. 1. Powder XRD Pattern of: a) pure TiO2 , b) non-doped surface modied TiO2 with 1.0 M n-butylamine, c) 2M% Nd3+ doped TiO2 ; and d) 5M% Nd3+ -doped TiO2 modied using 1.0 M n-butylamine.

neodymium-doped TiO2 nanoparticles (TiO2 -X, X=2, 5% neodymium oxide) at a-axis and c-axis when compared to pure TiO2 , this conrms the existence of neodymium atoms in TiO2 nanoparticles. The radii of Nd (III) ion is bigger than that of Ti (VI), so the doping of Nd3+ should make the cell parameter bigger than that of pure TiO2 . The powder XRD patterns of surface modied neodymium doped TiO2 hybrid nanoparticles show ve primary peaks at 25.22 , 37.74 , 47.94 , 53.82 and 62.64 for 2 M % doping and 25.32 , 37.82 , 48.06 , 55.08 and 62.70 for 5 M% doping (Fig. 1), which can [16] be attributed to different diffraction planes of TiO2 . The powder XRD data indicate that the cell volume of neodymium doped TiO2 hybrid nanoparticles has slightly increased with 2 M% and 5 M% Neodymium doping (Table 1).

The functional groups present in the modied nanoparticles can be studied using FTIR Spectroscopy. Figure 2 shows the FTIR spectra of the pure TiO2 , non-doped surface modied TiO2 , neodymium (2 and 5 M %) doped TiO2 nanoparticles with n-butylamine as surface modier. The FTIR spectra of the modied hybrid nanoparticles show the presence of new peaks imply that the reagents were chemically immobilized on the surface of nanoparticles. Thus, it can be concluded that the neodymium doped TiO2 nanoparticles synthesized with the above said modier, have organic coverage on their surfaces, which has changed surface property of nanoparticles by adding new functional group on the surface of the modied neodymium-doped TiO2 hybrid nanoparticles. The intensity of the peaks was more for 1.6 M surface modied neodymium doped TiO2 nanoparticles compared to 0.8 M surface modied

Photocatalytic treatment of municipal wastewater

Table 1. Cell parameters of TiO2 . Catalyst Reagent grade TiO2 Used TiO2 Surface modied TiOa 2 Nd2 O3 (2 M %) doped TiO2 Nd2 O3 (5 M %) doped TiO2
a b

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a (A) 3.7845 3.7918 3.7881 3.7876 3.7869

c( A) 9.5143 9.5296 9.5230 9.5164 9.5087

a:c ratio 0.3977 0.3979 0.3978 0.3980 0.3982

V (A ) 136.27 137.02 136.65 136.52 136.36

Ref. [17] Pb p P P

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without dopant. P = Present work.

neodymium doped (2 M % and 5 M %) TiO2 hybrid nanoparticles. The peaks around 1633 and 3626 cm1 correspond to the presence of CH3 and N-H stretching bands. In addition, the appearance of new peaks around 2970 and 3420 cm1 corresponds to O-H and NH2 stretching band. The absorption peaks around 1674, 3600 and 3683 cm1 belong to C=O stretching band [18] . Figure 3 shows characteristic TEM images of 2 and 5 M% neodymium doped TiO2 hybrid nanoparticles modied with (0.8 and 1.6 M) n-butylamine. This gure shows a thin organic coverage of the surface modier on the synthesized nanoparticles. The agglomeration was less when a higher concentration of the surface modier was used. The surface modication has led to the controlling of growth direction, also particle size and preventing agglomeration. It is found that the surface modier cannot only affect the dispensability of the surface modied neodymium-doped TiO2 hybrid nanoparticles, but also change their growth

Fig. 3. TEM Image of Nd3+ doped TiO2 hybrid nanoparticles: a) 2M%Nd3+ , 0.8 M n-butylamine; b) 2M%Nd3+ , 1.6M nbutylamine, c) 5M%Nd3+ , 0.8M n-butylamine and d) 5M%Nd3+ , 1.6 M n-butylamine.

Fig. 2. FTIR Spectra of a) pure TiO2 , b) non-doped TiO2 nanoparticles modied with 1.0 M nbutylamine, c) 2M% Nd3+ doped TiO2 nanoparticles modied with 0.8M n-butylamine d) 2M% Nd3+ -doped TiO2 nanoparticles modied with 1.6 M nbutylamine, e) 5M%Nd3+ -doped TiO2 nanoparticles modied with 0.8M n-butylamine and f) 5M% Nd3+ doped TiO2 nanoparticles modied with 1.6M n-butylamine.

habit. The morphology achieved is quite suitable for the photodegradation purposes, since the neodymium-doped TiO2 hybrid nanoparticles are rounded, they can be more active in photodegradation of the organic pollutants presenting in the domestic wastewater and industrial efuents as well. Moreover, they were highly hydrophilic and individually dispersed in medium. Figure 4 shows the particle size distribution of the neodymium doped TiO2 hybrid nanoparticles synthesized conrming the nano-range of the particles. The range was narrower in the case of 2 M% neodymium-doped TiO2 hybrid nanoparticles. The average particle size was 7 nm in the case of 2 M % neodymium-doped TiO2 hybrid nanoparticles modied with 1.4 M surfactant and 65.7 nm for 5 M % neodymium-doped TiO2 hybrid nanoparticles modied with 1.6 M surfactant. These results are in agreement with powder XRD data and TEM images. The BET surface area for surface modied TiO2 nanoparticles was found to be 15.928 m2 /g, which is not matched well with TEM and DLS data. This low value may be contributed to the coverage of surfactant on the surface of modied TiO2 hybrid nanoparticles. Zeta potential of surface modied TiO2 nanoparticles Zeta ( ) potential measurement was performed for TiO2 nanoparticles in order to characterize the surface charge of nanoparticles and Figure 5 shows the result as a function

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Fig. 4. Particle size distribution using DLS for a) 2 M% Nd3+ -doped; and b) 5 M% Nd3+ -doped TiO2 hybrid nanoparticles modied using 1.0 M n-butylamine.

of pH. The potential obtained of the nanoparticles was found to decrease with increase of pH as is expected for a surface with acid-base group. The iso-electric point or point of zero charge (PZC) for TiO2 nanoparticles was found to be 4.8. The signicance of potential is that its value can be related to the stability of colloidal dispersions. The potential indicates the degree of repulsion between adjacent, similarly charged particles in dispersion. For small enough nanoparticles, a high potential will confer stability, i.e., the solution or dispersion will resist aggregation. When the potential is low, attraction exceeds repulsion and the dispersion will break and occulate.[1921] Therefore, colloids with high potential (negative or positive) are electrically stabilized while colloids with low zeta potentials tend to coagulate or occulate. As Figure 6 indicates, potential for

the surface modied TiO2 nanoparticles was -40 meV at pH 12, which indicates its stability. This property is quite suitable for photodegradation application of the nanoparticles synthesized. Band gap energy of modied neodymium-doped TiO2 hybrid nanoparticles The effect of doping was studied by UV-vis spectroscopy in the range of 200600 nm. Figure 6 shows that pure TiO2 had no absorption in the visible light region ( > 400 nm). The modied neodymium doped TiO2 hybrid nanoparticles

20 10

Zeta Potential (meV)

0 -10 -20 -30 -40 2 4 6 8 10 12

pH

Fig. 5. Zeta potential of TiO2 nanoparticles modied with nbuytlamine as surfactant.

Fig. 6. UV-Vis absorbance spectra of a) pure TiO2 , b) surface modied 2% Nd3+ -doped TiO2 nanoparticles and c) surface modied 5% Nd3+ -doped TiO2 nanoparticles.

Photocatalytic treatment of municipal wastewater

showed a remarkable absorption band shift toward a longer wavelength region, which indicates a decrease of the band gap energy. In addition, according to the band edges of the samples determined from differentiation of the three curves, the band gap of the three samples were calculated according to the equation EG = hc/, where EG is the band gap energy (eV), h is Plancks constant, c is the speed of light (m/s), and is the wavelength (nm). The EG of pure TiO2 , neodymium doped TiO2 (2M% Nd2 O3 ) hybrid nanoparticles and neodymium doped TiO2 (5 M% Nd2 O3 ) hybrid nanoparticles were 3.23, 3.18 and 3.11, respectively. Photocatalytic treatment studies

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Photocatalytic activity of pure TiO2 , neodymium-doped TiO2 nanoparticles with and without surface modier was studied using municipal wastewater sample containing various organic compounds. The detention time was up to 3 hrs and concentration of photocatalyst was varied to nd out the optimum amount of photocatalyst required to achieve the highest photocatalytic efciency. Figure 7 shows that neodymium doped TiO2 nanoparticles exhibiting much greater activity than pure and neodymium doped TiO2 without modier in the visible region under UV and sunlight, respectively. The best result for COD reduction was achieved at 1.2 g/L of 5% modied neodymium-doped TiO2 nanoparticles under sunlight and after 3 hrs contact

Fig. 7. Effect of catalyst dosage on the photodegradation efciency: a) under sunlight, and b) under UV light irradiation: ) 5%Nd3+ -doped TiO2 nanoparticles and ) 2% Nd3+ -doped TiO2 nanoparticles modied with 1.0 M n-butylamine; ) reagent grade TiO2 .

Fig. 8. Effect of irradiation time under: a) sunlight and b) under UV light on photodegradation of municipal wastewater: ) 5% Nd3+ -doped TiO2 nanoparticles and ) 2% Nd3+ -doped TiO2 nanoparticles modied with 1.0 M n-butylamine; ) reagent grade TiO2 .

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low toxicity, eco-friendly, low density and low melting temperature. Application of suitable surface modier not only reduced the agglomeration and particle size but also made them highly hydrophilic, which is required for achieving higher photodegradation efciency. The strategy adopted for these surface modied hybrid nanomaterials is costeffective and ecofriendly. The concenteration of surfactant should be optimized; the reason is if the concentration of surfactant was high, it will bring about heavy coverage the surface of the fabricated TiO2 nanoparticles, which can prevent photodegradation of the wastewater or other pollutants though it decreases agglomeration and control the morphology and size of the synthesized particles. The initial concentration and type of pollutant is also one of the important factors, which may affect on the photodegradation. Doping the TiO2 naoparticles with a suitable metal oxide such as neodymium, tungsten, molybdenum, etc. can reduce band gap energy and hence feasibility of the photodegradation in the visible light. Some researchers have synthesized such small particles using supercritical hydrothermal, which needs higher temperature (i.e., above 373 C) but we achieved this in the present work under mild hydrothermal conditions.

85

80

(%)

75

70

65

60 0.8 1.0 1.2 1.4 1.6

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Surfactant Concentration (Molar)

Fig. 9. Relationship between concentrations of surfactant applied to modify surface of doped TiO2 nanoparticles and photodegradation efciency.

time resulting in 95% degradation of wastewater sample. Figure 8 shows the effect of detention time on photodegradation of the municipal wastewater sample using modied neodymium-doped TiO2 hybrid nanoparticles(1.2 g/L) under sun light. Neodymium doping leads to the partial reduction of Ti4+ to Ti3+ , which could improve the photocatalytic activity of TiO2 . Since Ti3+ sites could act as the photogenerated electron traps and thus facilitate the charge separation[22] . Effect of surfactant concentration on photocatalytic degradation There are a variety of organic ligands, which can be applied for surface modication of TiO2 , ZnO, CdS and other particles. We found that despite non-toxicity, ecofriendly, suitable melting point, etc., density, pKa, and its concentration play a critical role in its suitability. The density of surfactant should be less than water and the precursors otherwise while its removal from the prepared nanoparticles will be very difcult and bring about the catalyst contamination so that the density of surfactant should be less than 1 g/L. It was also found that the concentration of the applied surfactant for modication of the TiO2 nanoparticles make effect on the photodegradation. Figure 9 shows effect of surfactant concentration on photodegradation of efuents. As it indicates the optimum concentration was found to be 1.0 M n-butylamine as surfactant for in-situ modication of the Nd3+ doped TiO2 hybrid nanoparticles.

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Conclusion
Neodymium doped TiO2 hybrid nanoparticles were successfully modied under hydrothermal conditions. nbutylamine was used as surface modier because it has

Photocatalytic treatment of municipal wastewater

[11] Han, C.H.; Lee, H.S.; Han, S.D. Synthesis of nanocrystalline TiO2 by sol-gel combustion hybrid method and its application to dye solar cells Bull. Kor. Chem. Soc. 2008, 29(8), 1495 1498. [12] Wu, C.I.; Huang, J.W.; Wen, Y.-L.; Wen, S.B.; Shen, Y.H. Preparation of TiO2 nanoparticles by supercritical carbon dioxide. Mater. Lett. 2008, 62(1213), 19231926. [13] Byrappa, K.; Sunitha, M.H.; Subramani, A.K.; Ananda, S.; Rai, K.M.L.; Basavalingu, B.; Yoshimura, M. Hydrothermal preparation of neodymium oxide coated titania composite designer particulates and its application in the photocatalytic degradation of Procion Red dye. J. Mater Sci. 2006, 41, 1369 1375. [14] Adschiri, T.; Byrappa, K. Supercritical hydrothermal synthesis of organicinorganic hybrid nanoparticles. In Nano-hybridization of organic-inorganic Materials. A. Muramatsu, Ed. Springer-Verlag, Germany, 2008. [15] Clescerl, S. L.; Greenberg, A.E.; Eaton, A.D. Standard Methods for Examination of Water and Wastewater. (21st Ed.). American Water Works Association, 2005.

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