Temperature Based Investigation on Structure and Optical Properties of Bi2S3 Nanoflowers

Mechanics, Materials Science & Engineering, April 2017 – ISSN 2412-5954

Temperature Based Investigation on Structure and Optical Properties of Bi2S3 Nanoflowers by Solvothermal Approach43 J. Arumugam1, A. Dhayal Raj1, a, A. Albert Irudayaraj1, T. Pazhanivel2 1 – Department of Physics, Sacred Heart College, Tirupattur, Vellore Dist, Tamilnadu, India 2 – Department of Physics, Periyar University, Salem, Tamilnadu, India a – dhayalraj03@gmail.com DOI 10.2412/mmse.73.16.231 provided by Seo4U.link

Keywords: Bi2S3 nanostructures, XRD, SEM, UV-Vis, FTIR.

ABSTRACT. A solvothermal process has been employed to synthesis Bi2S3 nanostructures which has a wide spread applications in photodiode, hydrogen storage, high energy batteries, as well as luminescence and catalytic fields. Bismuth nitrate, thiourea and PolyVinyPyrrolidene (PVP), used as the starting materials are dissolved in ethylene glycol for different reaction times. It was found that the temperature plays a key role in determining the shape of the products. The crystalline phase and structure of the Bi2S3 nanostructures were investigated by power X-ray diffraction (XRD). The surface morphology has been analyzed by Scanning electron microscopy (SEM), the optical properties of the Bi2S3 nanoparticles were analyzed using UV-Vis spectroscopy. The functional groups present in the Bi2S3 nanoparticles were characterized by FT-IR spectroscopy. The novel Bi2S3 nanoparticles will be exploited for its application as photocatalyst.

Introduction. Recently, nanostructured materials have gained their importance in science and technology due to their novel optical, electric, magnetic and catalytic properties as compared to the corresponding bulk counter parts due to their large surface areas, smaller size, reduced numbers of free electrons and possible quantum confinement effects [1]. The integration of one-dimensional nanoscale building blocks into two-and three-dimensional ordered superstructures or complex functional architectures, which not only open up possibilities for advanced nanodevices but also offers opportunities to explore their novel collective properties, has recently been proposed [2]. In particular, nanostructures like nanopariticles and nanoflowers of semiconductor materials have attracted much attention due to their possible applications in nanoscale electronic and optoelectronic devices. Nanowiskers so called by reason off their appearance have become the subject of intensive study in recent years because of their remarkable characteristics [3]. However, the organization of building blocks into ordered patterns through direct manipulation receives increasing research interest in the synthesis of nanomaterials.

Bismuth sulfide (Bi2S3) is one of the most studied semiconductors with Eg of 1.3eV [4] owing to its wide spread applications, such as photodiode arrays, photovoltaic converters, photodetectors, thermoelectric and electrochemical hydrogen storage as an imaging agent in X-ray computed tomography, in biomolecules detection, H2 sensing and so on. Extensive research has been focused on the synthesis of one dimensional Bi2S3 nanostructures in a controlled fashion by various methods [5]. Qiaofeng Han et al., have reported the Orthorhombic Bi2S3 nanorods with diameters in the ranging of 20-35 nm and with lengths of hundreds of nanometers by hydrothermal treatment [6].

Xuefeng Qian et al., have reported Bi2S3 naniwiskers through microwave method and influence of PVP and sulfur sources on the morphology of the prepared Bi2S3 have also been reported [3].

Yonghong Ni et al., have reported flowerlike Bi2S3 microspheres and have studied catalytic activity 43

© 2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license http://creativecommons.org/licenses/by-nc-nd/4.0/

MMSE Journal. Open Access www.mmse.xyz 181

Mechanics, Materials Science & Engineering, April 2017 – ISSN 2412-5954

[7]. Anukorn Phuruangrat et al., have reported the Influence of PVP on the Morphologies of Bi2S3 Nanostructures synthesized by Solvothermal Method [8], K. Kavi rasu et al., have reported the structural and optical properties of PVP/Bi2S3 nanoparticles by chemical method [9]. Ding et al., have synthesized the 3D Hierarchical Bi2S3 nanostructures through PolyVinylPyrrolidone (PVP) and Chloride Ion-assisted synthesis [10]. However, most of the techniques mentioned above are of higher temperature and pressure, or the preparation procedures are complex. Therefore, it remains a challenge to develop a facile route to fabrication of Bi2S3 nanomaterials in order to investigate its unusual properties [11].

In this study, we report the facile route to synthesize flower-like Bi2S3 nanostructures via a solvothermal approach with different reaction temperature.

Experimental Procedure: Bismuth Nitrate, Thiourea, Polyvinylpyrrolidone (PVP) and ethylene glycol (EG) were purchased from merck without further purification. In a typical procedure required amount of bismuth nitrate, thiourea and PVP were successively mixed in 40 ml of ethylene glycol.

The resulting mixtures were sonicated to obtain a clear yellow solution, which was then transferred in to 40 mL Stainless steel Teflon-lined autoclave. The autoclaved was maintained for different temperatures (60°C, 100°C, 120°C, 160°C and 200°C). Finally, the sample was collected, washed with double distilled water and ethanol for few times and then dried at 60°C in hot air oven. Further the sample was characterized byXRD, HR-SEM, EDAX, UV-Vis and FTIR. Result and discussion Structural analysis. Fig.1 shows the XRD pattern of the Bi2S3 nanostructures obtained via a one-pot Solvothermal method. All the peaks can be indexed to the orthorhombic Bi2S3 phase (JCPDS no. 170320), with lattice constants a=11.15Å, b=11.30Å and c= 3.981Å and no characteristic peaks of any other phases or impurities are observed. Furthermore, the intense and sharp peaks indicate the product is well crystallized. In another investigation, the average crystalline size was derived from DyeScherrer formula as shown below:

=

,

where D is the average crystalline size, k is a constant whose value is typically 0.9 of non-spherical crystals, β is the full width at half maximum (FWHM) of the diffraction peak (in radians) that has the maximum intensity in the diffraction pattern, λ is the wavelength of incident X-ray beam (0.154184 nm) and θ is diffraction angle or Bragg angle.

From this formula, the average crystalline size of Bi2S3 was calculated as 17 nm, 21nm, 28 nm, 30 nm and 32nm for samples prepared at 60°C, 100°C, 120°C, 160°C and 200°C respectively. When the reaction temperature is increased up to 200°C, the diffraction peaks become stronger gradually. When reaction temperature is reached at 200°C, the diffraction peaks are narrow and strong, indicating that the improvement in crystallinity.

MMSE Journal. Open Access www.mmse.xyz 182

Mechanics, Materials Science & Engineering, April 2017 – ISSN 2412-5954

Fig. 1. XRD Pattern of Bi2S3 nanoparticles prepared for 24 hours at (a) 60°C (b) 100°C (c) 120°C (d) 160°C (e) 200°C.

Morphological analysis: Fig.2 Shows the HR-SEM image of Bi2S3 nanoparticles obtained at different temperatures by solvothermal approach. The SEM image in Fig.2 (a) corresponding to the sample prepared at 60°C, shows numerous well-distributed flower-like nanostructures formed from the reactant Bi2S3 powder.

Inset the Fig.2 (a) shows a single flower-like structure. The flowers are approximately of 1µm in size and composed of tens of petals. The petals of these Bi2S3 nanoflowers are smooth flaks-structures and approximately 250 nm in width and 166 nm in thickness as shown in Fig.2 (a). As the reaction temperature is increased the nanoflowers turn up to nanoparticles with some agglomeration. The average particle size has been calculated as 166nm, 180 nm, 249nm and 250nm for sales prepared at 100°C, 120°C, 160°C and 200°C respectively. When the reaction temperature is increased the particle size also increased. The composition of the nanoflowers as extracted from the energy dispersive spectroscopy (EDAX) spectrum and are presented in Fig. 2 (f) which confirms the presence of Bi and S atoms. The deficiency of S with respect to stoichiometry in the nanoflowers can be attributed to the vapour pressure of S higher than that of Bi. Little evidence of O was detected in this spectrum.

MMSE Journal. Open Access www.mmse.xyz 183

Mechanics, Materials Science & Engineering, April 2017 – ISSN 2412-5954

a

b

c

d

cps/eV

e

12

f

10

Counts

8

6

S

S Bi

O

4

2

0 1

2

3

4

5 keV

6

Energy (eV)

Fig. 2. HR-SEM image of Bi2S3 nanoparticles obtained at different temperatures (a) 60°C, (b) 100°C, (c)120°C, (d)160°C, (e)200°C and (f) EDAX spectrum of Bi2S3 nanoflowers prepared by solvothermal approach for 24 hours.

MMSE Journal. Open Access www.mmse.xyz 184

7

Mechanics, Materials Science & Engineering, April 2017 – ISSN 2412-5954

Fig. 3. UV absorption spectra of Bi2S3 nanoparticles prepared for 24 hours at (a)60°C, (b) 100°C, (c)120°C, (d)160°C (e)200°C.

Optical analysis. Fig.3 shows the UV-Vis spectra of Bi2S3 nanoparticles obtained at different temperatures by solvothermal approach. The optical properties of Bi2S3 semiconducting compounds result from band structures of the materials and are very important in a large number of applications.

The (αhυ)2 ~ hυ curve are shown as inset in Fig.3. From the Fig., the band gap of Bi2S3 semiconductor nanoflowers and nanoarticles could be determined to be about 1.70 to 1.82 eV by extrapolating the linear portion of (αhυ)2 Vs hυ curve. The band gap values thus obtained is higher than that of the bulk Bi2S3 (1.3eV). The blue shift might be ascribed to the quantum effect due to the high aspect ratio of the nanoflower and nanoparticles.

Functional group analysis.

Fig. 4. FTIR spectra of Bi2S3 nanoparticles prepared for 24 hours at (a) 60°C by solvothermal approach.

The composition and quality of the product were analyzed by FT-IR spectroscopy. Fig.4 FTIR spectra of Bi2S3 nanoflowers prepared for 24 hours at 60°C by solvothermal approach. The broad absorption MMSE Journal. Open Access www.mmse.xyz 185

Mechanics, Materials Science & Engineering, April 2017 – ISSN 2412-5954

band centered at 3426 cm−1, must be associated with the (OH) stretching vibration. A broad band at 3300 to 3500 cm-1 attributed to the stretching vibration of H2O, while the band centered at 1623cm-1 corresponds to the bending vibrations of H2O. The strong peaks at 1370 cm−1 attributed to C-S stretching vibration [12], indicating the formation the [Bi (Tu)x]3+ complex in the porous nanoflowers, as shown in the Fig. 4. The peaks at 1207 cm-1 could be attributed to the stretching of C–O–C– bonds [13]. The strong absorption band at 428 cm−1 and 478 cm-1 is due to Bi [14]. The peak at 618 cm-1 may be attributed to stretching vibrations of sulphur indicating the formation of Bi2S3.

Summary. Well-crystallined Bi2S3 nanoflowers have been successfully synthesized by solvothermal approach with low reaction temperature. The structure of the Bi2S3 nanoparticles is confirmed to be orthorhombic from the X- ray diffraction patterns. The Vibrational peaks at 423 cm-1and 618 cm-1 confirm the formation of Bi2S3. From the optical absorption spectra, the band gap of Bi2S3 nanostructures were found to be in the range 1.70 to 1.82eV, which are higher than that of bulk Bi2S3 materials. The as-synthesized Bi2S3 nanoflowers, can be potentially applied in the field of photocatalysis.

Acknowledgments The authors would like to acknowledge the management, Sacred Heart College for extending support to complete this work successfully.

References [1] R. Chen, M.H. So, C.M. Che, H. Sun, Controlled synthesis of high crystalline bismuth sulfide nanorods: using bismuth citrate as a precursor, J. Mater. Chem., 15 (2005) 4540-4545. DOI: 10.1039/B510299E [2] J. Ma, J. Yang, L. Jiao, T. Wang, J. Lian, X. Duan, W. Zheng, Bi2S3 nanomaterials: morphology manipulation and related properties, Dalton Trans., 40 (2011) 10100-10109. DOI: 10.1039/C1DT10846H [3] R. He, X. Qian, J. Yin, Z. Zhu, Preparation of Bi2S3 nanowhiskers and their morphologies, J. Cryst growth, 252 (2003) 505-510. DOI:10.1016/S0022-0248 (03)00968-0 [4] X. Yu, C. Cao, Photoresponse and Field-Emission Properties of Bismuth Sulfide Nanoflowers, Cryst. Growth Des., 8 (2008) 3951-3955. DOI: 10.1021/cg701001m [5] J. Ma, Z. Liu,, J. Lian, X. Duan, T. kim, P. Peng, X. Liu, Q. Chen, G. Yao, W. Zheng, Ionic liquids-assisted synthesis and electrochemical properties of Bi2S3 nanostructures, Cryst Eng Comm., 13 (2011) 3072-3079. DOI: 10.1039/C0CE00913J [6] Q. Han, J. Chen, X. Yang, L. Lu, X. Wang, Preparation of Uniform Bi2S3 Nanorods Using Xanthate Complexes of Bismuth (III), J. Phys. Chem. C, 111 (2007) 14072-14077. DOI: 10.1021/jp0742766 [7] F. Guo, Y. Ni, Y. Ma, N. Xiang, C. Liu, Flowerlike Bi2S3 microspheres: facile synthesis and application in the catalytic reduction of 4-nitroaniline, New J. Chem., 38 (2014) 5324-5330. DOI: 10.1039/C4NJ00900B [8] A. Phuruangrat, T. Thongtem, S. Thongtem, Influence of PVP on the Morphologies of Bi2S3 Nanostructures Synthesized by Solvothermal Method, Journal of Nanomaterials, 1155 (2013) 1-6.

DOI:10.1155/2013/314012 [9] K. Kavi Rasu, D.Vishnushankar, V. Veeravazhuthi, Optical and Structural Properties of PVP/Bi2S3 Nanoparticles by Chemical Method, Advanced Materials Research, 678 (2013) 248-252.

DOI:10.4028/www.scientific.net/AMR.678.248 [10] T. Ding, J. Dai, J. Xu, J. Wang, W. Tian, K. Huo, Y. Fang, C. Chen, 3D Hierarchical Bi2S3 Nanostructures by Polyvinylpyrrolidone (PVP) and Chloride Ion-Assisted Synthesis and Their

MMSE Journal. Open Access www.mmse.xyz 186

Mechanics, Materials Science & Engineering, April 2017 – ISSN 2412-5954

Photodetecting Properties, Nanoscale Res. Lett., 10 (2015) 286- 274. DOI 10.1186/s11671-015-09931 [11] X. Zhou, H. Shi, B. Zhang, X. Fu, K. Jiao, Facile synthesis and electrochemical application of surface-modified Bi2S3 urchin-like nano-spheres at room temperature, Mater Lett., 62 (2008) 32013204. DOI:10.1016/j.matlet.2008.02.019 [12] C.Tang, C. Wang, F. Su, C. Zang, Y. Yang, Z. Zong, Y. Zhang, Controlled synthesis of urchinlike Bi2S3 via hydrothermal method, Solid State Sci., 12 (2010) 1352-1356, Doi:10.1016/j.solidstatesciences.2010.05.007 [13] Y.Y Wang, K Feng Cai, Xi Yao, One-pot fabrication and enhanced thermoelectric properties of poly (3, 4-ethylenedioxythiophene)-Bi2S3 nanocomposites, J. Nanopart. Res., 14 (2012) 2-7, 10.1007/s11051-012-0848-y.

[14] M. Salavati-Niasari, Z. Behfard, O. Amiri, E. Khosravifard, S. Mostafa Hosseinpour-Mashkani, Hydrothermal synthesis of Bismuth Sulfide Bi2S3 Nanorods: Bismuth (III) Monosalicylate Precursor in the Presence of Thioglycolic Acid, J. Clust. Sci., 24 (2013) 349–363, DOI 10.1007/s10876-0120520-9.

Cite the paper J. Arumugam, A. Dhayal Raj, A. Albert Irudayaraj, T. Pazhanivel (2017). Temperature Based Investigation on Structure and Optical Properties of Bi2S3 Nanoflowers by Solvothermal Approach. Mechanics, Materials Science & Engineering, Vol 9. doi:10.2412/mmse.73.16.231

MMSE Journal. Open Access www.mmse.xyz 187