Zirconia nanostructures have been successfully synthesized through sonochemical-assisted rout. Zirconia nanostructures were synthesized by employing of the zirconyl nitrate and tetramethylethylenediamine (TMED) as starting materials. Here, TMED was used not only as precipitator, but also as capping agent to form zirconia nanostructures. The products were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), ultraviolet–visible (UV–vis) spectroscopy and scanning electron microscopy (SEM). The obtained results demonstrated that utilizing of this precipitator is suitable choice for preparation of zirconia nanostructures with very uniform sphere-like morphology

Salavati-Niasari, M.

Zinatloo-Ajabshir, S.

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  
NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 4 No 1, 01NNPT01(3pp) (2015) 
 
2304-1862/2015/4(1)01NNPT01(3) 01NNPT01-1  2015 Kashan University 
Facile Surfactant-Free Preparation, Characterization and Investigation of  
Optical Properties of Zirconia Nanostructures 
 
S. Zinatloo-Ajabshir, M. Salavati-Niasari* 
 
Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P.O. Box 87317-51167, I.R. Iran 
 
(Received 19 March 2015; published online 22 August 2015) 
 
Zirconia nanostructures have been successfully synthesized through sonochemical-assisted rout. Zirco-
nia nanostructures were synthesized by employing of the zirconyl nitrate and tetramethylethylenediamine 
(TMED) as starting materials. Here, TMED was used not only as precipitator, but also as capping agent to 
form zirconia nanostructures. The products were analyzed by X-ray diffraction (XRD), Fourier transform 
infrared spectroscopy (FT-IR), ultraviolet–visible (UV–vis) spectroscopy and scanning electron microscopy 
(SEM). The obtained results demonstrated that utilizing of this precipitator is suitable choice for prepara-
tion of zirconia nanostructures with very uniform sphere-like morphology.  
 
Keywords: Zirconia, Nanostructures, Optical properties. 
 
 PACS numbers: 81.07. – b, 78.67. – n 
 
 
                                                          
*
salavati@kashanu.ac.ir  
1. INTRODUCTION 
 
The preparation of nanomaterials has attracted 
broad scientific attention due to their useful applica-
tions in various areas during the last decades [1,2]. 
Among these nano-scale materials, zirconia as an im-
portant metal oxide has been attracted significant sci-
entific and industrial interest for a long time because of 
its specific optical and electrical properties as well as 
potential applications, including transparent optical 
devices and electrochemical capacitor electrodes, fuel 
cells and catalysts. ZrO2 has three crystal forms that 
are stabilized at different temperature ranges: mono-
clinic (below 1170 °C), tetragonal (1170–2370 °C), and 
cubic (2370–2680 °C). Up to now, several methods have 
been developed to synthesize zirconia, such as sol–gel, 
hydrothermal, thermal decomposition, microwave irra-
diation, precipitation, and sonochemical [3-6]. Recently, 
the ultrasonic rout as a fast, convenient, and economi-
cal method has been widely utilized to prepare new 
nanostructured materials. Ultrasonic irradiations bring 
about cavitation in a liquid medium where the for-
mation, growth and implosive collapse of bubbles take 
place. The collapse of bubbles with short lifetimes (less 
than a nanosecond) generates intense local heating 
and. we report synthesis of zirconia nanostructures via 
surfactant-free sonochemical-assisted rout by employ-
ing zirconyl nitrate and tetramethylethylenediamine 
(TMED). 
 
2. MATERIALS AND METHOD 
 
All the chemical reagents used in our experiments 
were of analytical grade and were used as received 
without further purification. Zirconyl nitrate, tetra-
methylethylenediamine (TMED), liquor ammonia solu-
tion containing 25% ammonia were obtained from 
Merck Co. Distilled water was used for all the experi-
ments. A multiwave ultrasonic generator (Sonicator 
3000; Bandeline, MS 72, Germany), equipped with a 
converter/transducer and titanium oscillator (horn), 
12.5 mm in diameter, operating at 20 kHz with a max-
imum power output of 80 W, was used for the ultrason-
ic irradiation. Fourier transform infrared (FT-IR) spec-
tra were recorded on Varian 4300 spectrophotometer in 
KBr pellets. Powder X-ray diffraction (XRD) patterns 
were collected from a diffractometer of Philips Compa-
ny with X’PertPro monochromatized Cu Ka radiation 
(k = 1.54 Å). Microscopic morphology of products was 
visualized by a Hitachi s4160 Japan scanning electron 
microscope (SEM). The electronic spectra of the zirco-
nia were obtained on a Scinco UV–vis scanning spec-
trome-ter (Model S-4100). To prepare the zirconia 
nanostructures, 1 mmol of TMED was dissolved in 40 
mL of distilled water and then, added into a solution of 
ZN (1 mmol of ZN dissolved in 40 mL of distilled water) 
drop-wise under ultrasound irradiation. The white gel-
like product obtained 4 was filtered and washed re-
peatedly with distilled water. The final product was 
dried at 80 °C and calcined at 600 °C for 4 h. To study 
the effect of TMED on the morphology of the zirconia 
nanostructures, one experiment was carried out by 
NH4OH instead of TMED (blank test). In the blank test 
1, 8 mmol of ammonia dissolved in 50 mL distilled wa-
ter and was added into a solution including 1 mmol of 
ZN dissolved in 40 mL of distilled water (Table 1). The 
as-prepared nanostructures were characterized by 
(SEM), (UV–vis) spectroscopy, (FT-IR) and (XRD) tech-
niques. 
 
Table 1 – Preparation conditions for samples. 
 
Sample No Ultrasonic irradiation Morphology 
1 TMED 
Homogeneous sponge-
like 
2
a 
NH4OH 
Agglomerated particle-
like 
a
 Blank test, in the absence of TMED. 
 
 S. ZINATLOO-AJABSHIR, M. SALAVATI-NIASARI PROC. NAP 4, 01NNPT01 (2015) 
 
 
01NNPT01-2 
3. RESULTS AND DISCUSSION 
 
In the present study, zirconia nanostructures were 
prepared by using zirconyl nitrate and TMED as starting 
reagents via a surfactant-free sonochemical-assisted rout.  
The XRD pattern of the sample 1 has been shown in 
Fig. 1. All of the diffraction peaks of the product in Fig. 
1 can be indexed to tetragonal zirconium dioxide (space 
group P42/nmc, JCPDS card 88-1007). The average 
crystal size of the as-prepared product was calculated 
from Debeys–Scherrer formula [7] given by the follow-
ing formula:  
 
 τ = kλ/βcosϴ (1) 
 
where, τ is the crystal size, β is the breadth of the ob-
served diffraction line at its half intensity maximum, k 
is the so-called shape factor and λ is the wavelength of 
X-ray source used in XRD. The average crystal size of 
the as-prepared product was about 15 nm. 
 
 
 
Fig. 1 – XRD patterns of sample 1. 
 
Fig. 2a and 2b show FT-IR spectra of sample 1 after 
washing steps and after calcination, respectively. The 
weak (C-N) stretching vibration band at 1340 cm-1 and 
(C- H) bending vibration band 1382 cm-1 indicates the 
presence of TMED in the pores after washing steps (Fig. 
2a). They completely disappear after calcination at 
600°C. The absorption band centered at 3447 cm-1 and a 
weak peak at 1631 cm-1 are ascribed to the v(OH) 
stretching and bending vibrations, respectively, which 
indicates the presence of physisorbed water molecules 
linked to zirconium dioxide sample. 
SEM images of the samples 1 and 2 have been shown 
in Fig. 3a and 3b. As seen in Fig.3a, by using of the 
TMED, homogeneous sponge-like zirconia nanos-
?ructures obtained. In the absence of TMED, the parti-
cles coalesced and turn into agglomerated particle-like 
structures. It seems that when TMED utilized as precip-
itator (Fig. 3a), the chance of collision between ZrO(OH)2 
nanoparticles decreased because of steric hindrance ef-
fect of TMED, and therefore homogeneous sponge-like 
zirconia nanostructures formed. The bifunctional TMED 
can act as both precipitator for ZrO(NO3)2 to ZrO(OH)2 
and capping agent for the ZrO(OH)2 nanoparticles by 
hindering the aggregation of nanoparticles. 
The optical characteristics of the zirconia 
nanostructures with sphere-like morphology were ex-
amined by UV–vis absorbance analysis. Fig. 3a shows 
the UV–vis absorbance spectrum of the sample 1. 
 
 
Fig. 2 – FT-IR spectra of sample 1 after washing (a), and after 
calcinacion (b). 
 
 
 
Fig. 3 – SEM images of (a) sample 1, (b) sample 2. 
 
The nanostructures show the absorption spectrum 
with an absorption band at 226 nm. Utilizing Tauc's 
formula, the band gap can be obtained from the absorp-
tion data. The energy gap (Eg) of the as-obtained zirco-
nia has been calculated by extrapolating the linear por-
tion of the plot of (αhν)2 against hν to the energy axis 
(Fig. 4). The Eg value of the zirconia nanostructures 
(sample 1) is calculated to be 4.6 eV, which has a red 
shift of about 0.4 eV compared with the band gap value 
of bulk zirconium dioxide (5 eV). The red shift of the 
absorption band can be originated from the various 
 FACILE SURFACTANT-FREE PREPARATION, CHARACTERIZATION… PROC. NAP 4, 01NNPT01 (2015) 
 
 
01NNPT01-3 
structural defects [8]. The obtained data are in good 
agreement with previous report [9]. 
 
 
 
Fig. 4 – UV–vis absorbance spectrum of the sample 1 (inset: 
the curve of (αhν)2 against hν). 
4. CONCLUSIONS 
 
Shortly, homogeneous sponge-like zirconia 
nanostructures were successfully prepared by using 
zirconyl nitrate and tetramethylethylenediamine as 
starting agents in the presence of ultrasound irradia-
tion. Here, TMED was used not only as precipitator, 
but also as capping agent to form zirconia nanostruc-
tures. Here, TMED was used not only as precipitator, 
but also as capping agent to form zirconia nanostruc-
tures. High purity of the as-obtained zirconia 
nanostructures was confirmed by XRD and FT-IR 
analyses. The optical characteristics of the obtained 
zirconia nanostructures were also examined.  
 
AKNOWLEDGEMENTS 
 
Authors are grateful to the council of Council of 
University of Kashan on this work by Grant number 
(22134324/45). 
 
 
REFERENCES 
 
1. E.P. Marray, T. Tsai, S.A. Barnett, Nature 400, 649 
(1999).  
2. A.V. Chadwich, Nature 408, 925 (2000).  
3. J. Liang, Zh. Deng, X. Jiang, F. Li, Y. Li, Inorg. Chem. 41, 
3602 (2002).  
4. C.C. Coterillo, T. Yokoo, T. Yoshioka, T. Tsuru, M. Asaeda, 
Sep. Sci. Technol. 46, 1224 (2011).  
5. F. Sayılkan, M. Asiltu¨rk, E. Burunkaya, E. Arpac, J. Sol-
Gel Sci. Technol. 51, 1049 (2009).  
6. S.R.M. Feng, X.J. Yang, W.J. Ji, and Ch.T. Aua, Chemistry 
and Physics 107, 132 (2008).  
7. R.L. Snyder Jenkins, Chemical Analysis: Introduction to 
X-ray Powder Diffractometry (New York: John Wiley & 
Sons, Inc.: 1996). 
8. A. Sobhani, M. Salavati-Niasari, M. Sobhani, Mater. Sci. 
Semicond. Process. 16, 410 (2013).  
9. N. Clament Sagaya Selvam, A. Manikandan, L. John 
Kennedy, and J. Judith Vijaya, J. Colloid Interface Sci. 
389, 91 (2013). 
 


English

Facile Surfactant-Free Preparation, Characterization and Investigation of Optical Properties of Zirconia Nanostructures

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 4 No 1, 01NNPT01(3pp) (2015)  2304-1862/2015/4(1)01NNPT01(3) 01NNPT01-1  2015 Kashan University Facile Surfactant-Free Preparation, Characterization and Investigation of  Optical Properties of Zirconia Nanostructures  S. Zinatloo-Ajabshir, M. Salavati-Niasari*  Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P.O. Box 87317-51167, I.R. Iran  (Received 19 March 2015; published online 22 August 2015)  Zirconia nanostructures have been successfully synthesized through sonochemical-assisted rout. Zirco-nia nanostructures were synthesized by employing of the zirconyl nitrate and tetramethylethylenediamine (TMED) as starting materials. Here, TMED was used not only as precipitator, but also as capping agent to form zirconia nanostructures. The products were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), ultraviolet–visible (UV–vis) spectroscopy and scanning electron microscopy (SEM). The obtained results demonstrated that utilizing of this precipitator is suitable choice for prepara-tion of zirconia nanostructures with very uniform sphere-like morphology.   Keywords: Zirconia, Nanostructures, Optical properties.   PACS numbers: 81.07. – b, 78.67. – n                                                             *salavati@kashanu.ac.ir  1. INTRODUCTION  The preparation of nanomaterials has attracted broad scientific attention due to their useful applica-tions in various areas during the last decades [1,2]. Among these nano-scale materials, zirconia as an im-portant metal oxide has been attracted significant sci-entific and industrial interest for a long time because of its specific optical and electrical properties as well as potential applications, including transparent optical devices and electrochemical capacitor electrodes, fuel cells and catalysts. ZrO2 has three crystal forms that are stabilized at different temperature ranges: mono-clinic (below 1170 °C), tetragonal (1170–2370 °C), and cubic (2370–2680 °C). Up to now, several methods have been developed to synthesize zirconia, such as sol–gel, hydrothermal, thermal decomposition, microwave irra-diation, precipitation, and sonochemical [3-6]. Recently, the ultrasonic rout as a fast, convenient, and economi-cal method has been widely utilized to prepare new nanostructured materials. Ultrasonic irradiations bring about cavitation in a liquid medium where the for-mation, growth and implosive collapse of bubbles take place. The collapse of bubbles with short lifetimes (less than a nanosecond) generates intense local heating and. we report synthesis of zirconia nanostructures via surfactant-free sonochemical-assisted rout by employ-ing zirconyl nitrate and tetramethylethylenediamine (TMED).  2. MATERIALS AND METHOD  All the chemical reagents used in our experiments were of analytical grade and were used as received without further purification. Zirconyl nitrate, tetra-methylethylenediamine (TMED), liquor ammonia solu-tion containing 25% ammonia were obtained from Merck Co. Distilled water was used for all the experi-ments. A multiwave ultrasonic generator (Sonicator 3000; Bandeline, MS 72, Germany), equipped with a converter/transducer and titanium oscillator (horn), 12.5 mm in diameter, operating at 20 kHz with a max-imum power output of 80 W, was used for the ultrason-ic irradiation. Fourier transform infrared (FT-IR) spec-tra were recorded on Varian 4300 spectrophotometer in KBr pellets. Powder X-ray diffraction (XRD) patterns were collected from a diffractometer of Philips Compa-ny with X’PertPro monochromatized Cu Ka radiation (k = 1.54 Å). Microscopic morphology of products was visualized by a Hitachi s4160 Japan scanning electron microscope (SEM). The electronic spectra of the zirco-nia were obtained on a Scinco UV–vis scanning spec-trome-ter (Model S-4100). To prepare the zirconia nanostructures, 1 mmol of TMED was dissolved in 40 mL of distilled water and then, added into a solution of ZN (1 mmol of ZN dissolved in 40 mL of distilled water) drop-wise under ultrasound irradiation. The white gel-like product obtained 4 was filtered and washed re-peatedly with distilled water. The final product was dried at 80 °C and calcined at 600 °C for 4 h. To study the effect of TMED on the morphology of the zirconia nanostructures, one experiment was carried out by NH4OH instead of TMED (blank test). In the blank test 1, 8 mmol of ammonia dissolved in 50 mL distilled wa-ter and was added into a solution including 1 mmol of ZN dissolved in 40 mL of distilled water (Table 1). The as-prepared nanostructures were characterized by (SEM), (UV–vis) spectroscopy, (FT-IR) and (XRD) tech-niques.  Table 1 – Preparation conditions for samples.  Sample No Ultrasonic irradiation Morphology 1 TMED Homogeneous sponge-like 2a NH4OH Agglomerated particle-like a Blank test, in the absence of TMED.   S. ZINATLOO-AJABSHIR, M. SALAVATI-NIASARI PROC. NAP 4, 01NNPT01 (2015)   01NNPT01-2 3. RESULTS AND DISCUSSION  In the present study, zirconia nanostructures were prepared by using zirconyl nitrate and TMED as starting reagents via a surfactant-free sonochemical-assisted rout.  The XRD pattern of the sample 1 has been shown in Fig. 1. All of the diffraction peaks of the product in Fig. 1 can be indexed to tetragonal zirconium dioxide (space group P42/nmc, JCPDS card 88-1007). The average crystal size of the as-prepared product was calculated from Debeys–Scherrer formula [7] given by the follow-ing formula:    τ = kλ/βcosϴ (1)  where, τ is the crystal size, β is the breadth of the ob-served diffraction line at its half intensity maximum, k is the so-called shape factor and λ is the wavelength of X-ray source used in XRD. The average crystal size of the as-prepared product was about 15 nm.    Fig. 1 – XRD patterns of sample 1.  Fig. 2a and 2b show FT-IR spectra of sample 1 after washing steps and after calcination, respectively. The weak (C-N) stretching vibration band at 1340 cm-1 and (C- H) bending vibration band 1382 cm-1 indicates the presence of TMED in the pores after washing steps (Fig. 2a). They completely disappear after calcination at 600°C. The absorption band centered at 3447 cm-1 and a weak peak at 1631 cm-1 are ascribed to the v(OH) stretching and bending vibrations, respectively, which indicates the presence of physisorbed water molecules linked to zirconium dioxide sample. SEM images of the samples 1 and 2 have been shown in Fig. 3a and 3b. As seen in Fig.3a, by using of the TMED, homogeneous sponge-like zirconia nanos-?ructures obtained. In the absence of TMED, the parti-cles coalesced and turn into agglomerated particle-like structures. It seems that when TMED utilized as precip-itator (Fig. 3a), the chance of collision between ZrO(OH)2 nanoparticles decreased because of steric hindrance ef-fect of TMED, and therefore homogeneous sponge-like zirconia nanostructures formed. The bifunctional TMED can act as both precipitator for ZrO(NO3)2 to ZrO(OH)2 and capping agent for the ZrO(OH)2 nanoparticles by hindering the aggregation of nanoparticles. The optical characteristics of the zirconia nanostructures with sphere-like morphology were ex-amined by UV–vis absorbance analysis. Fig. 3a shows the UV–vis absorbance spectrum of the sample 1.   Fig. 2 – FT-IR spectra of sample 1 after washing (a), and after calcinacion (b).    Fig. 3 – SEM images of (a) sample 1, (b) sample 2.  The nanostructures show the absorption spectrum with an absorption band at 226 nm. Utilizing Tauc's formula, the band gap can be obtained from the absorp-tion data. The energy gap (Eg) of the as-obtained zirco-nia has been calculated by extrapolating the linear por-tion of the plot of (αhν)2 against hν to the energy axis (Fig. 4). The Eg value of the zirconia nanostructures (sample 1) is calculated to be 4.6 eV, which has a red shift of about 0.4 eV compared with the band gap value of bulk zirconium dioxide (5 eV). The red shift of the absorption band can be originated from the various  FACILE SURFACTANT-FREE PREPARATION, CHARACTERIZATION… PROC. NAP 4, 01NNPT01 (2015)   01NNPT01-3 structural defects [8]. The obtained data are in good agreement with previous report [9].    Fig. 4 – UV–vis absorbance spectrum of the sample 1 (inset: the curve of (αhν)2 against hν). 4. CONCLUSIONS  Shortly, homogeneous sponge-like zirconia nanostructures were successfully prepared by using zirconyl nitrate and tetramethylethylenediamine as starting agents in the presence of ultrasound irradia-tion. Here, TMED was used not only as precipitator, but also as capping agent to form zirconia nanostruc-tures. Here, TMED was used not only as precipitator, but also as capping agent to form zirconia nanostruc-tures. High purity of the as-obtained zirconia nanostructures was confirmed by XRD and FT-IR analyses. The optical characteristics of the obtained zirconia nanostructures were also examined.   AKNOWLEDGEMENTS  Authors are grateful to the council of Council of University of Kashan on this work by Grant number (22134324/45).   REFERENCES  1. E.P. Marray, T. Tsai, S.A. Barnett, Nature 400, 649 (1999).  2. A.V. Chadwich, Nature 408, 925 (2000).  3. J. Liang, Zh. Deng, X. Jiang, F. Li, Y. Li, Inorg. Chem. 41, 3602 (2002).  4. C.C. Coterillo, T. Yokoo, T. Yoshioka, T. Tsuru, M. Asaeda, Sep. Sci. Technol. 46, 1224 (2011).  5. F. Sayılkan, M. Asiltu¨rk, E. Burunkaya, E. Arpac, J. Sol-Gel Sci. Technol. 51, 1049 (2009).  6. S.R.M. Feng, X.J. Yang, W.J. Ji, and Ch.T. Aua, Chemistry and Physics 107, 132 (2008).  7. R.L. Snyder Jenkins, Chemical Analysis: Introduction to X-ray Powder Diffractometry (New York: John Wiley & Sons, Inc.: 1996). 8. A. Sobhani, M. Salavati-Niasari, M. Sobhani, Mater. Sci. Semicond. Process. 16, 410 (2013).  9. N. Clament Sagaya Selvam, A. Manikandan, L. John Kennedy, and J. Judith Vijaya, J. Colloid Interface Sci. 389, 91 (2013).  

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Facile Surfactant-Free Preparation, Characterization and Investigation of Optical Properties of Zirconia Nanostructures

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