Journal of the Iranian Chemical Society

Synthesis of ZnO Nanocrystal via Sol-Gel method

--Manuscript Draft-Manuscript Number: Full Title: Article Type: Corresponding Author: Synthesis of ZnO Nanocrystal via Sol-Gel method Original Paper Abdollah Javidan, Ph.D IHU TEHRAN, TEHRAN IRAN (ISLAMIC REPUBLIC OF)

Corresponding Author Secondary Information: Corresponding Author's Institution: Corresponding Author's Secondary Institution: First Author: First Author Secondary Information: Order of Authors: Abdollah Javidan, Ph.D Abolghasem Moghimi, Ph.D Hossein Fakhraeian, Ph.D Ebrahim Mehraban Order of Authors Secondary Information: Abstract: Abstract Nanostructure zinc oxide was synthesized by sol-gel method from Zn (II) Sulphate heptahydrate (ZnSO4.7H2O), potassium hydroxide as the starting materials in water as solvent, in the presence of either triethanol amine (TEA) or ethylene glycol (EG) as organic capping agent. The synthesized nanomaterials were identified by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis and IR spectroscopy. Experimental results showed that pore size of the nanocrystals was 45-75 nm when calcinated at 900 C. Suggested Reviewers: Abdollah Javidan, Ph.D IHU

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Synthesis of ZnO Nanocrystal via Sol-Gel method A. Moghimi, A. Javidan*, E. Mehraban, H. Fakhraeian Department of Chemistry Imam Hossien University of Tehran, Iran
POBOX 16575-347 Tel/fax: +98 21 77104930 Email: ajvidan@ihu.ac.ir

Abstract Nanostructure zinc oxide was synthesized by sol-gel method from Zn (II) Sulphate heptahydrate (ZnSO4.7H2O), potassium hydroxide as the starting materials in water as solvent, in the presence of either triethanol amine (TEA) or ethylene glycol (EG) as organic capping agent. The synthesized nanomaterials were identified by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis and IR spectroscopy. Experimental results showed that pore size of the nanocrystals was 45-75 nm when calcinated at 900 C. Keyword: nanocrystal, nanostructure, ZnO, scanning electron microscopy, and Xray diffraction

1. INTRODUCTION Metal nanoparticles research has very rapid growth during the last decades, because of their vast applications. Among m Metal nanoparticles, zinc oxide has attracted much attention because of their catalytic and optical activities. ZnO is an important semiconductor, which has direct band gap (3.37 eV at room temperature), large bond strength, large excitation binding energy ( Eb=60 meV) and high melting temperature (2248 K) [1]. ZnO is widely used in many field such as catalysts for organic reaction, pigment, rubber additive, gas sensor (Example H2, H2S, NH3, LPG and EtOH) [2], optical devices [3], luminescent materials [4], transparent
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conductor, heat mirrors, coating. It is also used in the fabrication of solar cells [5], a hexagonal wurtzite crystal of Zinc oxide (ZnO) is a promising material for manufacturing photo detector, blue and violet laser diodes [6a].It also has attracted interest in the application in biosensors [6b]. Quantum mechanical calculations and experimental observations suggest that the energy level of the first excited state of the excitation increase with decreasing particle size thus leading to a blue shift in the absorption spectrum [7]. Nana-size ZnO has been Prepared by different methods like aerosol, ultrasonic, evaporation of solution and suspensions, evaporative decomposition of solution (EDS), solid state reaction, wet chemical

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synthesis, spray pyrolysis method, chemical vapor deposition, hydrothermal synthesis, Recently, synthesis of ZnO in the form of nanopowder using metal organic chemical vapor deposition (MOCVD), vapor-solid (VS), and sol-gel method [8-17] have also been reported.

Today, Sol-gel method is one of the known procedures for the preparation of metal oxide nanoparticles [13]. To the best of our knowledge, there has no report on the synthesis of ZnO nanoparticles starting from the Zinc sulphate and potassium hydroxide although there are several report in which used sodium hydroxide. Herein we wish to report such a synthesis method. 2. MATERIAL AND METHOD 2.1. MATERIALS All materials were purchased from Merck chemical company and used without further purification. Also, A furnace (Qamato Model FM21), X-ray diffraction (XRD) patterns of prepared ZnO were recorded by diffractometer (SEIFERT PTS 3003) using a Cu K radiation (= 1.54 ),The morphology was examined by a (Philips XL30) scanning electron microscope (SEM) .

ZnSO4 was added to 100 ml aqueous solution 0.2 M potassium hydroxide. After stirring for 10 minute, 4.0 ml triethanol amine (or 4.0 ml ethylene glycol) was slowly added to the reaction mixture. It was then stirred for 24 h at room temperature. The solution product was filtered by vacuum, washed with distilled water and acetone for two times, and dried in air at room temperature. It was calcinated at 900 C for 1h in furnace to give the White powders of nano zinc oxide. 3. RESULT AND DISCUSSION 3.1. REACTIONS ZnO nanocrystals prepared in two steps can be presented as follows: a) ZnSO4 + 2KOH Zn(OH)2+ K2SO4 b) Zn(OH)2 ZnO + H2O In this method , Zinc () sulphate heptahydrate was mixed with aqueous solution of potassium hydroixe after constantly stirring. Generally, zinc hydroxide was formed. The possible formation of Zn(OH)4(2-) is reported elsewhere[14]. To avoid the agglomeration, triethanol amine or ethylen glycol was slowly added to was introduced as a capping agentThe subsequent decomposition of zinc hydroxide particles result in formation of nanometric particles of nano oxide (reaction b: Gf {100 C} =-2.79 Kj/mol) [15]. 3.2. XRD ANALYSIS

2.2. Preparation of sample Initially, in a typical procedure, 100 ml aqueous solution of 0.1 M
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Figure 1 shows the X-ray diffraction pattern of ZnO nanocrystals prepared in aqueous solvent. It was shows a hexagonal wurtzite structure. The diffraction peaks indicate the nanocrystaline nature (JCDPS card No 36-1451). These peaks at scattering angles (2) of 31.1659, 33.8236, 35.6564, 46.9859, 56.0657, 62.3597, 67.4630 and 68.6192 correspond to the reflection from: 100, 002, 101, 102, 110, 103, 200 and 112 crystal planes, respectively [12]. The XRD patterns is identical to the hexagonal phase with wurtzite structure with space group (C6V=P63 mc) and unit cell parameters a=b=0.3249 nm and c=0.5206 nm, indicating that it was a single crystal. The particle size was calculated using the Scherer Formula, equation (I) (I)

from the extrapolation of the plot shown in figure 2 [16], 1/=2.9 109, which yields = 34.2 10-9 or 34.2 nm. The size from XRD analysis is much smaller than real image. There might be a few factors for this mismatch, for example; crystallinity or distortion. Therefore, 34.2 nm is the average size for crystallinity of the ZnO nanocrystaline. .

3.3. SEM CHARACTERIZATION The SEM of ZnO nanocrystaline particles produced with ZnSO4, 7 H2O, by Sol-gel method is shown in figure 3(or figure 4). As seen as single phase primary particle is spherical in shape with the average diameter of about 45-75 nm. 3.4. EDX ANALYSIS

D
Where K is unit cell cubic system (it is 0.899), is the X-ray diffraction wave length (in this case, it is 1.5406 ), is the measured FWHM (fullwith at half maximum), is the Bragg peak angle of the peak. The lattice strain and crystalline size was calculated from the following equation (II) [15]. Cos 1 Sin (II) Where is the effective particle size and is the effective strain, the average particle size can be estimated
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K Cos

The EDX elemental analysis of ZnO nanocrystal showed at Fig 5. The result indicated that calcinated ZnO nanoparticles containing 100% ZnO template.

3.5. IR SPECTROSCOPY The IR spectrum of ZnO is shown in Figure7.The sharp peak at -600 -1 cm is belong to bonding between zink and oxygen atom. There is a broad band with very low intensity at 3493 cm-1 corresponding to the

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vibration mode of water OH group indicating the presence of small amount of water adsorbed on the ZnO nanocrystal.

CONCLUSIONS A new approach to the synthesis of nanosize ZnO powder via sol-gel method using Zinc (II) sulphate heptahydrate and potassium hydroxide in aqueous solvent was reported. The XRD results confirmed the hexagonal crystals structure of ZnO, and showed the complete conversion of Zinc hydroxide to Zinc oxide at 900 C. The SEM micrographs clearly showed nanostructure homogeneities.

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[3] Z.W. Pan, Z.R. Dai, Z.L. Wang, Science 291 (2001) 1947. [4] J. Zang, W. Yu, and L. Zang, Phys. Lett. A. 299 (2002) 276. [5] K. Matsubara, P. Fons, K. Iwata, A. Yamad, K. Sakurrai, H. Tampo, and S. Niki. Thin Solid Films 431 (2003) 369. [6] a).T. Soki, Y. Hatanaka, and D.C. look, Appl. Phys. Lett 76 (2000) 3257 b).A. Fulati and et al. Sensors and Actuators B Chemical.150 (2011) 673 680. [7] D.W. Bahnemann, C. Kormann, and M.R. Hoffmann. J.Phys.Chem 91 (1987) 3789. [8] R. Okuyama, J. Aerosol. Sci 22 (1998) 5. [9] K.G. Kanade, B.B.Kale, R.C. Aiyer, and B.K. Das, Materials Research Bulletin 41 (2006) 590. [10] Y.Ohya, T. Niwa, T. Ban, Y. Takahashi. Jpn.J.Appl.Phys. 40 (2001) 297. [11] Y.Gui, C.Xie, Q. Zhang, M.Hu, J.Yu, and Z. Weng. Journal of Crystal Growth (2006) [12] L. Spanhal, M.A. anderson. J.Am.Chem.Soc 113 (1991)2826. [13] W.l. Dai, Y. Cao, P.L. Ren, X.L. Yang, J.H. Xu, H.X. Li, H.Y. He, and K.N. Fan. J.Catal 229 (2004) 80.

[16] F.Gu, S.F. Wang, M.K. Lu, G.J. Zhou, D.Xu, and D.R. Yuan. Langmuir 20 (2004) 3528. [17] N.F.Hamedani, and F.Farzaneh J.of. Sci.I.R.of.Iran 17 (3) (2006)231.

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Figure1. The XRD pattern of ZnO nanocrystals from ZnSO4,7 H2O

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0.35 0.3 0.25 0.2 0.15 0.1 0.05 0 0 0.1 0.2 0.3 0.4

Figure 2. Cos/ vs. Sin/ for ZnO nanocrystals from ZnSO4,7 H2O

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Fig 3. SEM image of ZnO nanocrystal calcined at 900 C for 1h(TEA as organic capping).

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Fig 4. SEM image of ZnO nanocrystaline calcined at 900 C for 1h(EG as organic capping).

Fig 5.The EDX analysis of ZnO nanocrystal

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Fig 6.IR spectrum of ZnO nanocrystaline

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