International Journal of Materials Science ISSN 0973-4589 Volume 13, Number 1 (2018), pp. 15-22 © Research India Publications http://www.ripublication.com

Biosyntesis of Titanium Oxide nanoparticles and photodegradation of dye by nanoparticles

Tukaram R. Gaje1, Goraksh J. Hase2, Narendra D. Phatanaga re3, Shubhangi Fargade4, Ghule Rohini5 1. Assistant Professor 2. Assistant Professor 3. Assistant Professor 4.P.G.Student 5.P.G.Student, Department of Chemistry, S. N. Art’s, D.J. Malpani Commerce and B. N. Sarada Science College, Sangamner, Ahmednagar, Maharashtra, India. 1. Corresponding Author

Abstract

The intimate study, anatase phase of TiO2 nanoparticles with the size of about 11.38 nm were biosynthesized using Ti (OCH (CH3)2)4 (titanium tetra- isopropoxide) as titanium source. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) with energy dispersive X-ray microanalysis (EDXMA) and ultraviolet-visible near absorption spectroscopy (UV-VIS). XRD analysis shows that the phase of the sample is anatase TiO2. Experimental results have shown that the prepared white color powder have wholly consisted with anatase crystalline phase. Only powder acquired from an acidic solution has fine particle size with spherical morphology.

Key words: TiO2 NPs, Oscimum tenufluorum L., XRD, FT-IR, UV-VIS, FESEM, EDX.

1. INTRODUCTION In the ago two decades, titanium dioxide has wide applications on multidisciplinary areas due to its exquisite properties such as nontoxic, ultraviolet (UV) blocking and protection, antibacterial, photocatalytic, self-cleaning, etc. In spite of the excellent photo catalyst and antibacterial properties, the problems of recycling and agglomeration of the nano-scaled particles have projected limitations of the applications of nanoparticles. [9] Titania (TiO2) powders possess interesting optical, dielectric, and catalytic properties, which leads to industrial applications such as pigments, fillers, catalyst supports, and photo-catalysts. [8]

TiO2 is a non-toxic white pigment for use in manufacture of paints, plastics, paper, ink, rubber, textile, cosmetics, leather, and ceramics. Photo catalytic degradation of 16 Tukaram R. Gaje et al pesticides with TiO2 and other catalyst has shown promise as a potential water remediation method. It has also been noted that titanium dioxide breaks down the ethylene gas produced in storage rooms into carbon-dioxide and water, thus it is also used to treat the air in fruit, vegetable, and cut flower storage areas to prevent spoilage and increase the product’s shelf life. TiO2 NPs are promising as efficient nutrient source for plants to increase biomass production due to enhanced metabolic activities, and utilization of native nutrients by promoting microbial activities. [4]

2. MATERIALS AND METHODS 2.1: Collection and Preparation of plant leaves extract: The leaves of plant were collected at karule, near canal area, Sangamner, Ahmednagar Maharashtra. The taxonomic identification was made by BSI pune. (No.BSI/WRC/IDEN.CER./2016/489). The leaves were washed thoroughly in running tap water to remove adhere soil particles and clung debris and finally washed with sterile distilled water. After that the leaves are dried in 15 days at room temperature (28 °C) and then the leaves grained into a fine powder using mortar. The Oscimum tenufluorum L. leaf powder of 5g was taken for synthesis purpose. The weighed of 5g leaf powder were boiled with 500 ml of distilled water for 3 hour at 80 °C until the colour of the aqueous solution changes from watery to green. The extract was cooled at room temperature and filtered by Whatman No1 filter paper, stored at room temperature in order to use for further studies.

2.2. Preparation of Titanium Oxide NPs

The synthesis of TiO2 NPs, 500 mL of Oscimum tenufluorum L. leaves extract was taken and boiled at 80 °C with a magnetic stirrer. When the temperature of the solution was reached at 80 °C, 5 ml titanium tetra-isopropoxide solution was added. The mixture was boiled until it changed to a brown colour paste. Then the paste was collected in a ceramic crucible and heated using muffle furnace at 500 °C for 3 hrs. Thereafter we obtained white color powder, it was stored in properly labeled containers and used for further Characterization.[1]

3: RESULT AND DISCUSSION 3.1: Fourier transform infrared spectroscopy (FTIR):

The FTIR spectrum of prepared TiO2 nanoparticles recorded in the range of 400 cm-1 to 4000 cm-1 is shown in fig.1. A peak appearing at 663 cm-1 is due to broad stretching vibration of Ti-O. The peak at 1392.4 cm-1 and 1634.1 cm-1 corresponds to C-H and - NO3 ion respectively. The absorption range around 3428.6 cm-1 indicates the broad [2] - stretching of hydroxyl (O-H), which is due to bending vibrations of H2O . 1116.2 cm 1 and 2245.3 corresponds to R-O –R’ and –C≡N.

Biosyntesis of Titanium Oxide nanoparticles and photodegradation of dye… 17

RC SAIF PU, Chandigarh

74.0

70

65 2245.3

60 1392.4 1116.2

1358.2

55 %T 1634.1 50

45 663.0

40

3428.6 35.0 4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0 cm-1 Tukaram-1.sp - 12/11/2017 - OTAF

Fig.1. FTIR of TiO2 NP’S

3.2: Field emission scanning electron microscope (FESEM): FESEM images were measured and topographical analysis was performed based upon the surface study. Synthesized TiO2 NPs were smooth and spherical in shape (Fig.2). The images showed the synthesized nanoparticles in various magnifications 300 nm, 500nm and 200 nm which clearly gives physical morphology, particle size and aspect ratio.

Fig.2. FESEM images of TiO2 NP’S

3.3: The energy dispersive X-ray analysis (EDX) The analysis was performed by EDX instrument make Bucker. The EDX study proves that the particles are crystalline in nature and indeed metallic TiO2 NPs (Fig.3). The presence of calcium, oxygen, magnesium, aluminium and potassium indicate that the extracellular organic moieties are adsorbed on the surface of the metallic nanoparticles. 18 Tukaram R. Gaje et al

The Kα value of Ti metal is observed at 4.5 KeV.

Fig. 3. EDX spectrum of TiO2 NPs

3.4: XRD analysis:

The phase and crystallinity of prepared TiO2 nanoparticles were analysed by X-ray diffractometer. XRD pattern is shown in Fig. [4]. It was obtained in 2θ range of 20- 80°with Cu Kα radiation source (λ = 1.5406 A°) and the X-ray tube was operated at 40 mA and 45 Kv. The Scan Axis is Gonio, Start Position [2θ°]-10.0084 ,End Position [2θ°]-89.9934,Step Size [2θ°]0.0170 Scan Step Time [s]-29.8450, Scan Type-Continuous PSD Mode Scanning, PSD Length [2θ°]- 2.12 Offset [2θ°]-0.0000 , Divergence Slit Type- Fixed, Divergence Slit Size [°]0.4354, Specimen Length [mm]-10.00 , Measurement Temperature [°C]- 25.00, Anode Material-Cu, K-Alpha1 [Å]-1.54060, K-Alpha2 [Å]- 1.54443, K-Beta [Å] -1.39225,K-A2/K-A1 Ratio-0.50000. XRD pattern shows eight peaks at 2θ° = 25.4192, 38.0487, 48.0345, 54.0416, 54.9772, 62.8304, 70.0149, 75.3536. The observed peaks correspond to the anatase crystalline phase of TiO2 at 2θ° =25.32, 37.80, 48.05, 53.89, 55.06, 62.69, 70.31, 75.03 shows good agreement in values with observed peaks. The XRD pattern was compared with standard JCPDS database National Bureau of Standards Monograph 25 Section 7 and [3] good matching with formation of anatase TiO2 was confirmed. The average crystallite size, determined using Debye Scherrer equation from full width half maxima (FWHM) of the distinct peak 2θ° = 25.4192 was 15.39 nm. The average crystallite size of TiO2 nanoparticles can be determined from Debye Scherrer formula, D=Kλ/β cosθ, where, D is the crystallite size, λ is the wavelength of the X-ray radiation, K is the Scherrer constant, and β is the full width at half-maximum height (FWHM), θ is the Bragg’s Biosyntesis of Titanium Oxide nanoparticles and photodegradation of dye… 19 diffraction angle. Average crystallite size of TiO2 nanoparticles was calculated as 11.38 nm by using FWHM of the distinct peaks 2θ° = 25.4192, 38.0487, 48.0345, 54.0416, 54.9772, 62.8304, 70.0149, 75.3536.

Counts OTAX

400

200

0 20 30 40 50 60 70 80 Position [°2θ] (Copper (Cu))

Fig. 4: XRD pattern of TiO2 NPs

3.5: UV–Visible characterization: UV–Visible absorption spectroscopy analysis Fig.5. Depicts the UV–Visible spectrum of biosynthesized titanium oxide nano particles using oscimum tenufluorum L. leaf extract. The TiO2 nanoparticles was dispersed in liquid ammonia and distilled water with a concentration of 0.1 wt% respectively, sonicated for uniform dispersion of TiO2 nanoparticles and so subjected for UV – visible spectrophotometric measurements. Figure: 5. and 5.1. is showing absorption peak of TiO2 nanoparticle at 200 nm.

Absorbance Vs Wavelength 0.7 0.6 0.5 0.4 0.3 0.2 Absorbance 0.1 0 0 500 1000 Wavelength in nm

Fig. 5. UV–Vis Spectrum of TiO2 in water iiiNPs 20 Tukaram R. Gaje et al

Absorbance Vs Wavelength 1 0.8 0.6 0.4

Absorbance 0.2 0 0 200 400 600 800 Wavelength in nm

Fig. 5.1. UV–Vis Spectrum of TiO2NPs in NH3

3.6: Photocatalytic activity of TiO2 nanoparticles

The Photocatalytic activity of these synthesized TiO2 nanoparticles was studied by degradation of methylene blue dye under sunlight irradiation with respect to time. Initially, the preparation of dye solution by dissolving 1 mg powder of methylene blue dye in 100 ml of distilled water (w/v). 10 mg of CuO nanoparticles was added with 50 ml dye solution of methylene blue and the mixture was stirred magnetically and exposing to the sunlight at the interval of 60,120,180 mins. A control was prepared and kept under the similar condition for comparing any change in color of the dye solution. The colloidal suspension was then put under sunlight irradiation with constant stirring. The average temperature of the atmosphere during the experiment was found to be around 40 °C with 3.00 hrs. mean sun shine duration. The 5ml clean supernatant soup was then scanned at fixed wavelength 664 nm using the Systronics visible double beam spectrophotometer 1203 to study the dye degradation in presence of TiO2 nanoparticles. [4]

3.6:1: Analysis of Photocatalytic activity:

The Photocatalytic activity of the biosynthesized TiO2 nanoparticles was evaluated by degradation of methylene blue dye under solar irradiation. Dye degradation was visually detected by gradual change in the color of the dye solution from deep blue to colorless. The characteristic absorption peak for methylene blue dye was noticed at 664 nm. The control exhibited no change in coloration during exposure in sunlight. The degradation of the dye in presence of biogenic TiO2 nanoparticles was verified by the decrease of the absorbance at 664 nm during 3.30 hrs. of exposure in sunlight (Fig. 6). Biosyntesis of Titanium Oxide nanoparticles and photodegradation of dye… 21

Absorbance Vs Time 1.2 control (0.9481) 1 pH(2.1) 0.787 0.8 0.5987 0.6 0.3313 0.4 Absorbance 0.2 0.106 0 0 50 100 150 200 250 300 Time in mins

Fig: 6– Methylene blue dye degradation.

CONCLUSION

Structural and morphological properties of TiO2 nanoparticles were studied by UV- Visible, FTIR, FESEM and XRD. FESEM micrographs with EDAX of TiO2 are shown in Fig. 2 & 3. It can be concluded from fig. 2 that prepared TiO2 nanoparticles were spherical. The synthesized TiO2 nanoparticles were in nanometer range with average size of 11.38 nm. The EDAX image confirms the presence of Ti and O element in sample. The Nano-TiO2 powder prepared by biosynthesis method was found to be pure which was confirmed by EDAX and FTIR. Anatase phase of TiO2 was confirmed by XRD and FESEM analysis confirmed the size of TiO2 powder in nanometer range. Powder morphology in these criteria is almost spherical which is due to acidic condition (pH=5.3) that prevents agglomeration.

ACKNOWLEDGEMENT The authors are grateful to the principal of S. N. Arts, D.J. M. Commerce and B. N. S. Science College, Sangamner for providing the laboratory facilities, and also thankful to SAIF & CIL laboratory Punjab National University, Chandigarh, Punjab for providing instrumentation facility.

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