Accepted Manuscript

Synthesis and characterisations of SnO2 nanorods via low temperature hydrothermal

method

Vicinisvarri Inderan, Shin Ye Lim, Teng Sian Ong, Samuel Bastien, Nadi Braidy, Hooi
Ling Lee

PII: S0749-6036(15)30208-1
DOI: 10.1016/j.spmi.2015.09.031
Reference: YSPMI 3995

To appear in: Superlattices and Microstructures

Received Date: 17 August 2015

Accepted Date: 26 September 2015

Please cite this article as: V. Inderan, S.Y. Lim, T.S. Ong, S. Bastien, N. Braidy, H.L. Lee, Synthesis
and characterisations of SnO2 nanorods via low temperature hydrothermal method, Superlattices and
Microstructures (2015), doi: 10.1016/j.spmi.2015.09.031.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT
Synthesis and Characterisations of SnO2 Nanorods via Low Temperature Hydrothermal Method

Vicinisvarri Inderan a, Shin Ye Lim a, Teng Sian Ong b, Samuel Bastien c, Nadi Braidy c, Hooi Ling Lee *a

a
School of Chemical Sciences, Universiti Sains Malaysia, Penang, Malaysia.

PT
b
Faculty of Engineering, Multimedia University, Cyberjaya, Malaysia.
c
Department of Chemical and Biotechnological Engineering, Université de Sherbrooke, Sherbrooke, Quebec,

RI
Canada.

U SC
AN
M
D
TE
C EP
AC

*Corresponding author. +60465333547. Fax. +604-6574854. Email : hllee@usm.my

a
School of Chemical Sciences, Universiti Sains Malaysia, Penang, Malaysia.
 ACCEPTED MANUSCRIPT
Abstract In the present study, tin oxide (SnO2) nanorods were successfully synthesized through hydrothermal

treatment at a relatively low temperature (180 ⁰C) using various concentrations of metal precursor, SnCl4.5H2O

(0.04 M - 0.16 M) in a mixed solution of ethanol and water before bringing the pH to 13 by adding 6 M NaOH.

The effect of concentration on the morphology and structure of SnO2 were comprehensively studied using

scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD),

ultraviolet-visible spectroscopy (UV-Vis) and Fourier Transform Infrared (FTIR). It was found that increasing

PT
the concentration of tin precursor from 0.04 M to 0.16 M leads to a complete conversion from nanospheres to

nanoplates and finally to nanorods. The SEM results confirmed that SnO2 nanorods are obtained for

RI
concentrations up to 0.12 M. At synthesis condition of 0.12 M, SnCl4.5H2O and pH 13, single rutile nanorods

SC
with preferential growth in the [002] direction were obtained. It was found that the diameter of nanorods formed

at 0.12 M is similar to that of nanoplates formed at 0.08 M (20 nm), which suggests that spear-shaped nanorods

might have originated from the primary nanoparticles (the particles grown in lower concentration during

U
hydrothermal treatment). Possible reaction mechanisms are proposed to explain the observed morphologies.
AN
M

Keywords: hydrothermal; tin dioxide; nanorods; SEM; TEM, UV-Vis

D
TE
C EP
AC
 ACCEPTED MANUSCRIPT
1. Introduction

Over the years, metal oxide nanostructures have been extensively explored as catalyst [1], photo-

catalyst [2], semiconductor [3], and gas sensor [4] in various industrial applications. Among them, tin oxide

(SnO2) is considered to be one of the most promising candidate for gas sensor as well as semiconductor due to

their inherent advantages such as a wide band gap (3.6 eV at 300 K), a large exciton binding energy (130 meV)

PT
and a high electron mobility (100-200 cm2 V-1S-1) [5]. It is well understood that the efficiency of SnO2

nanomaterial in various applications largely depends on both their size and shape [6, 7]. Recent efforts have

RI
allowed researchers to control the morphology of SnO2 nanostructures, from nanorods [8], nanowires [9],

nanotubes [10], nanosheets [11], to hollow nanospheres [10]. Some commonly used methods to synthesize SnO2

SC
include thermal evaporation [12], chemical vapour deposition (CVD) [13], sol-gel [14] and co-precipitation

[15]. Although these methods produced SnO2 nanostructures of defined shapes, they involve a high operational

U
temperature and expensive instrumentation. Hence, it is essential to develop a facile method to synthesize SnO2
AN
nanomaterials with well-defined structures desirable for the above-mentioned applications.

The hydrothermal method has been considered as a versatile route for the synthesis of homogenous SnO2
M

nanostructures with controlled size and shape [16]. This technique is classified as a soft chemical process, where

a solvent (usually water) and a precursor are sealed in a reaction vessel and heated at a temperature above 100
D

°C [17]. Studies show that tuning the experimental parameters (e.g. solvent [18], pH [19], concentration [20],

temperature [21], template [7], surfactant [22] and time [21]) influences the morphology and structure of the
TE

final product. Supothina et al [20] reported the synthesis of SnO2 nanorod clusters via hydrothermal route using

different concentrations of precursor, Na2SnO3·3H2O and NaOH at 200 °C for 48 hours. It was found that the
EP

precursor concentration and the pH affected the morphology of the SnO2 nanostructures. Furthermore, a number

of studies report on the synthesis of SnO2 nanostructures using surfactants. Recently, Cao et al [22] produced
C

SnO2 nanocubes and nanospheres using Sodium Dodecyl Sulphate (SDS) as a surfactant via hydrothermal route
AC

at a temperature of 180 °C. However, the usage of surfactants can represent environmental risks, especially to

aquatic species [23]. In another study, Matin et al [24] successfully prepared SnO2 nanoparticles without the use

of any alkaline solution and template; however, the samples required further calcination at a high temperature of

350 °C following the hydrothermal process at 130 °C.

In this study, SnO2 nanorods are synthesized via a simple hydrothermal route at a low temperature of 180

°C using a mixture of water/ethanol as a solvent. This method does not need any surfactant, template or

calcination to control the shape and the size of particles. In contrast, a concentrated sodium hydroxide solution
 ACCEPTED MANUSCRIPT
was used to control the hydrolysis degree during the formation of SnO2 nanorods. The effect of precursor

concentration on morphology of SnO2 was investigated and possible growth mechanisms were proposed and

discussed based on the results obtained.

2. Material and methods

PT
2.1. Synthesis of SnO2 nanostructures

All the chemicals were analytical grade reagents and were used without any further purification. Tin

RI
(IV) chloride hydrate (SnCl4·5H2O) was purchased from Gene Chemicals and absolute ethanol was obtained

from QRec Chemical Co. Ltd., Thailand. Sodium Hydroxide (NaOH) was procured from Unilab Chemicals and

SC
Pharmaceuticals Pvt Ltd, India. In a typical synthesis to prepare SnO2 with 0.12 M metal precursor, 1.6838 g

SnCl4.5H2O was dissolved in 20 mL mixed solution of absolute ethanol and distilled water (1:1, v/v) at room

U
temperature with vigorous stirring to obtain a homogeneous solution. The pH of the solution was adjusted to pH
AN
13 by adding in same volume of 6 M NaOH aqueous solution and absolute ethanol simultaneously. The final

volume of the reaction mixture was completed to 40 mL by adding ethanol-distilled water (1:1 v/v) mixture. A
M

white translucent suspension was obtained, which was then transferred into a 50 mL Teflon-lined stainless steel

autoclave. The sample was subsequently heated in an oven at 180 °C for 24 h and was allowed to cool down to
D

room temperature. The resulting white precipitates were washed and centrifuged several times with distilled
TE

water and absolute ethanol, respectively. Finally, the precipitate was dried in an oven, at 100 °C for 2 hours. To

investigate the effect of metal precursor concentration on the morphology and structure of the SnO2
EP

nanoparticles, the samples were prepared with various concentrations of SnCl4.5H2O (0.04 M - 0.16 M) in total

volume of 40 mL solution.
C

2.2. Characterization
AC

The morphology, size distribution and composition of the product were determined using SEM (Leo

Supra 50 VP Field Emission SEM) and TEM (FEI Titan Krios FEG at 300 kV). Phase structure and phase purity

of the as-synthesized nanostructures were determined via XRD (X'PERT PRO Multi-Purpose Diffractometer)

from PANalytical equipped with a PIXcel detector using the Bragg-Brentano geometry with a sample spinner

and CuKα1 radiation (1.541 Å), scanning over the 2θ range 13-110°, a step size of 0.003° and a scan time of 20s

per step. Rietveld refinement of each sample was performed using the HighScore plus software (v3.0.5) by
 ACCEPTED MANUSCRIPT
PANanalytical. HighScore Plus was operated in semi-automatic mode to obtain refined values for instrumental

parameters (zero-shift, peak-shape parameter, preferred orientation, etc.) and the important structural parameters

for the rutile phase [25, 26]: the unit cell parameter (a and c) and the oxygen atomic coordinates in the crystal

lattice. Further characterisation was carried out via UV-Vis Spectroscopy (PERKIN ELMER Lambda 35) at 220

-400 nm of wavelength range and Fourier Transform Infrared (FTIR) spectrum of the as-synthesized sample was

recorded by the KBr method on PERKIN ELMER System 2000 FT-IR in the range of 500 – 4000 cm-1.

PT
RI
3. Results and discussion

Fig. 1 shows that the morphology and shape of the synthesized SnO2 nanoparticles are largely

SC
determined by the concentration of the metal precursor. As shown in Fig. 1(a) and (b), at the lowest

concentration of 0.04 M, random clusters of irregular-shaped SnO2 nanospheres were obtained. On the other

U
hand, Fig. 1(c) and (d) show that nanoplates were obtained at a concentration of 0.08 M. When the
AN
concentration of metal precursor was raised to 0.12 M, nanorods growing in random direction were clearly

observed (Fig. 1(e) and (f)). A further increase in the concentration to 0.16 M decreased the size of the nanorods
M

which grew into more closely packed flower-like bunches (Fig. 1(g) and (h)). Overall, these results confirmed

that, as the concentration of precursor increased, a morphological evolution of SnO2 nanoparticle occur.
D

XRD analysis combined with Rietveld refinement was carried out on two selected samples prepared
TE

from 0.08 M and 0.12 M precursor. The XRD result showed that both samples are only composed of a single

rutile-type tetragonal SnO2 phase (Fig. 2), despite their difference in morphology. There were no traces of other
EP

phases detected. The calculated lattice constants and the position of oxygen within the crystal lattice (Table 1)

are in good agreements with literature data [26, 27]. The 0.08 M sample has a smaller calculated crystallite size
C

compared to the 0.12 M sample, as exemplified by its broader diffraction peaks.

AC

Fig. 1. Secondary electrons SEM images of SnO2 nanoparticles synthesized at the concentration of SnCl4.5H2O

(a and b) 0.04 M, (c and d) 0.08 M (e and f) 0.12 M (g and h) 0.16 M

Fig. 2. Experimental XRD spectra (black line), spectra calculated by Rietveld refinement (red line) and

difference plot (pink line) of SnO2 produced at a concentration of (a) 0.08 M and (b) 0.12 M. The stick patterns

(blue line) represent the reference pattern calculated by Rietveld refinement for the SnO2 rutile phase.
 ACCEPTED MANUSCRIPT
Table 1. Crystallographic parameters calculated by Rietveld refinement for samples produced at 0.08 M and

0.12 M. Values in parentheses are the standard deviation calculated from the Rietveld refinement for the last

digit of this parameter. GOF = Goodness of Fit.

Fig. 3 shows typical agglomeration found in specimen produced using concentrations of 0.08 M (a) and

PT
(b) and 0.12 M (c) and (d). The TEM images exhibit the detail of the morphology of platelets at 0.08 M and of

the spear shaped nanorods at 0.12 M, respectively. The platelets typically have a thickness of 5 nm and a

RI
diameter of about 20 nm (aspect ratio of ~4) and rods were found with a diameter of 20 nm and a length of 100

nm (aspect ratio of ~5). From the analysis of the lattice planes and the Fourier transform (insert, Fig. 3b), it is

SC
established that the platelet grows in directions perpendicular to {101] planes. Here, the ℎ ] and {ℎ

nomenclature are often used for denoting Miller index of directions and planes, respectively, in the tetragonal

U
lattice; it implies that ℎ and are interchangeable but not with . Similarly, inspection of the lattice found at the
AN
tip of the spear shaped nanorods indicates that the preferential growth direction is [002].
M

Fig. 3. TEM images of SnO2 nanostructures prepared with different concentrations of precursor: a) and b) 0.08
D

M and c) and d) 0.12 M. Regions in b) and d) are taken from the regions marked by boxes in a) and c),
TE

respectively. Fourier transforms of the regions of interest are shown in inset in b) and d) in which the

corresponding planes are indexed.

EP

The band gap of SnO2 nanorods was obtained from UV-Vis adsorption spectrum. Fig. 4 shows the high
C

intake around 350 nm is very close to that of bulk SnO2 [14,15].The band gap of SnO2 nanorods prepared with
AC

0.12 M precursor was calculated using the absorbance data by plotting (αhv)2 versus photon energy (hv). As

observed in Fig. 4, the estimated band gap of the SnO2 nanorods obtained is 3.88 eV, which is slightly higher

than bulk SnO2 (Eg = 3.62 eV). This can be explained as the size of particle decrease the band gap increases,

and the absorption edge is blue shifted.

Fig. 4. UV absorbance spectrum and band gap calculations for SnO2 nanorods prepared with 0.12 M of

precursor.
 ACCEPTED MANUSCRIPT

3.1. The Formation Mechanism

The FTIR spectra of SnO2 sample prepared with 0.12 M SnCl4.5H2O before the hydrothermal treatment

and after the treatment are shown in Fig 5. Based on the obtained results, we propose a possible formation

mechanism for SnO2 nanoparticles: SnO2 nanoparticles are formed in two steps, namely dissolution and

PT
nucleation. At the early stage of the procedure, the precursor is dissolved in solvent and produced tin ions, Sn4+.

When the concentrated NaOH is partly added into the solution, a white slurry was observed, showed the

RI
formation of Sn(OH)4 (equation 1). But then, as the pH reached pH 13, the white precipitate (Sn(OH)4)

dissolved immediately by reacting with abundant hydroxide ions and a transparent solution,

SC
Sn(OH)2-
6
was formed (equation 2).

Sn4+ + 4OH- → Sn(OH)4

U
AN (1)

Sn(OH)4 + 2OH- → Sn(OH)2-

6
(2)
M

This can be explained by the FTIR spectrum in Fig. 5(a) where a strong broad band around 3440 cm-1 and a

sharp peak at 1642 cm-1 attributed to the stretching and the bending of hydroxide group in Sn(OH)2-
D

6
were

observed clearly. Another broad band at the wave number of 611 cm-1 assigned to Sn-O bond in Sn(OH)2-
TE

complex.
EP

Fig. 5. FTIR Spectra of SnO2 sample prepared with 0.12 M metal precursor (a) before heating, and (b) after
C

hydrothermal treatment.
AC

On the other hand, in the hydrothermal treatment as the concentration of Sn(OH)2-

6
complex increases with

time, it eventually reaches a critical concentration where SnO2 nuclei are formed spontaneously through the

condensation reaction. (Equation 3)[28].

Sn(OH)62- SnO2 + 2H2O + 2OH- (3)

 ACCEPTED MANUSCRIPT
This finding is confirmed by the two main peaks in Fig. 5(b) at 611 cm-1 and 483 cm-1 which are attributed

to antisymmetric and symmetric stretches of O-Sn-O, respectively. The broad band at 3311 cm-1 and a weak

peak at 1639 cm-1 are assigned to O – H stretching vibrations and O – H bending vibrations, which most

probably come from water molecules absorbed on SnO2 surface. Similar patterns were also obtained in previous

literature [28, 29].

PT
3.2. Effect of concentration of metal precursor

RI
The morphology of SnO2 can be varied by changing the concentration of metal precursor. It is

noteworthy that the diameter of nanorods formed at 0.12 M metal precursor is similar to that diameter of

SC
nanoplates (20 nm) formed at 0.08 M metal precursor, which suggests that spear-shaped nanorods might have

been produced from the primary nanoparticles. At higher concentration (>0.08 M) the nucleation density is

U
higher and thus, the probability of the primary particles (nanoplates) to meet with neighbour particles is high.
AN
Subsequently, these primary particles grow into nanorods. On the other hand, at lower concentration (<0.12 M),

the nucleation density is low. Hence, the probability of running into neighbours decreases and hence, nanoplates
M

are formed [31]

D

Fig. 6. Possible formation processes for SnO2 nanoparticles at different concentrations (a) 0.08 M and (b) 0.12
TE

M (adapted from Ref [32]).

EP

4. Conclusions
C

In this study, SnO2 spear-shaped nanorods have been successfully synthesized through a hydrothermal
AC

reaction of 0.12 M SnCl4.5H2O at pH 13 in water and ethanol (1:1 v/v) ratio solvent. The average diameter of

nanorods obtained under these conditions is ~20 nm. The absence of other phases detected with XRD confirms

that this method has high potential in producing homogeneous single phased nanostructures. TEM revealed the

formation of different nanostructures, at 0.08 M nanoplates and 0.12 M spear shaped nanorods. The above

findings lead to the conclusion that the nanoparticles in higher concentration of SnCl4.5H2O might have

originated from the primary nanoparticles (the particles grown in lower concentration during hydrothermal
 ACCEPTED MANUSCRIPT
treatment). The results also demonstrated that the morphology and structure of SnO2 nanostructures are largely

determined by the concentration of metal precursor.

Acknowledgements

This work is supported by Fundamental Research Grant Scheme (203/PKimia/6711363) and USM Short Term

Grant (304/PKIMIA/6313032). The authors also wish to thank Dr. Rohana Adnan from School of Chemical

PT
Sciences, USM and Dr. Khairudin Bin Mohamed from School of Mechanical Engineering, USM for their help

in this project. NB acknowledge the Natural Sciences and Engineering Council of Canada and the Canada

RI
Research Chair program for funding.

SC
References

U
[1] C. Karami, H. Ahmadian, M. Nouri, F. Jamshidi, H. Mohammadi, K. Ghodrati, et al., A novel method
AN
for synthesis of cobalt manganese oxide nano catalysts as a recyclable catalyst for the synthesis of some

bis (indolyl) methane derivatives, Catal. Commun. 27 (2012) 92–96.

M

[2] H.N. Tien, V.H. Luan, L.T. Hoa, N.T. Khoa, S.H. Hahn, J.S. Chung, et al., One-pot synthesis of a

reduced graphene oxide–zinc oxide sphere composite and its use as a visible light photocatalyst, Chem.
D

Eng. J. 229 (2013) 126–133.

TE

[3] G. Thennarasu, A. Sivasamy, S. Kavithaa, Synthesis, characterization and catalytic activity of nano size
EP

semiconductor metal oxide in a visible light batch slurry photoreactor, J. Mol. Liq. 179 (2013) 18–26.

[4] D. Wang, X. Chu, M. Gong, Gas-sensing properties of sensors based on single-crystalline SnO2
C

nanorods prepared by a simple molten-salt method, Sensors Actuators B Chem. 117 (2006) 183–187.
AC

[5] M. BATZILL, U. DIEBOLD, The surface and materials science of tin oxide, 2005.

[6] L.X. Yin, F.F. Wang, J.F. Huang, D. Wang, J.Y. Li, Influences of reaction temperature on structure and

Performances of SnO2 nanocrystals prepared by microwave hydrothermal method, Mater. Sci. Forum.

809-810 (2014) 122–127.

 ACCEPTED MANUSCRIPT
[7] B. Liu, L. Zhang, H. Zhao, Y. Chen, H. Yang, Synthesis and sensing properties of spherical flowerlike

architectures assembled with SnO2 submicron rods, Sensors Actuators B Chem. 173 (2012) 643–651.

[8] B. Mehrabi Matin, Y. Mortazavi, A.A. Khodadadi, A. Abbasi, A. Anaraki Firooz, Alkaline- and

template-free hydrothermal synthesis of stable SnO2 nanoparticles and nanorods for CO and ethanol gas

sensing, Sensors Actuators B Chem. 151 (2010) 140–145.

PT
[9] L. Qin, J. Xu, X. Dong, Q. Pan, Z. Cheng, Q. Xiang, et al., The template-free synthesis of square-shaped

RI
SnO2 nanowires: the temperature effect and acetone gas sensors., Nanotechnology. 19 (2008) 185705.

[10] J.L. Haizhen Wang Hai Fan, Baojuan Xi, Maofeng Zhang, Shenglin Xiong, Yongchun Zhu, Yitai Qian,

SC
Synthesis and gas sensitivities of SnO2 nanorods and hollow microspheres, J. Solid State Chem. 181

(2007) 122–129.

U
AN
[11] C. Wang, Y. Zhou, M. Ge, X. Xu, Z. Zhang, J.Z. Jiang, Large-scale synthesis of SnO2 nanosheets with

high lithium storage capacity., J. Am. Chem. Soc. 132 (2010) 46–7.
M

[12] S.H. Luo, Q. Wan, W.L. Liu, M. Zhang, Z.F. Di, S.Y. Wang, et al., Vacuum electron field emission

from SnO2 nanowhiskers synthesized by thermal evaporation, Nanotechnology. 15 (2004) 1424–1427.

D
TE

[13] M. Kwoka, L. Ottaviano, M. Passacantando, S. Santucci, G. Czempik, J. Szuber, XPS study of the

surface chemistry of L-CVD SnO2 thin films after oxidation, Thin Solid Films. 490 (2005) 36–42.
EP

[14] F. Gu, S.F. Wang, M.K. Lu, Photoluminescence properties of SnO2 nanoparticles synthesized by sol -

gel method, J. Phys. Chem. B. (2004) 8119–8123.

C
AC

[15] Maolin Zhang, Guoying Sheng, Jiamo Fu, Taicheng An, Xinming Wang, Xiaohong Hu, Novel

preparation of nanosized ZnO–SnO2 with high photocatalytic activity by homogeneous co-precipitation

method, Mater. Lett. 59 (2005) 3641–3644.

[16] H. Hayashi, Y. Hakuta, Hydrothermal synthesis of metal oxide nanoparticles in supercritical water,

Materials (Basel). 3 (2010) 3794–3817.

 ACCEPTED MANUSCRIPT
[17] M. Adachi, D.J. Lockwood, Self-Organized nanoscale materials, Springer Science & Business Media,

United States of America, 2006.

[18] I.H. Pressions, E.N. Supe, Solvothermal processes: a route to the stabilization of new materials† ´, J.

Mater. Chem. (1999) 15–18.

PT
[19] L.Z. Liu, X.X. Li, X.L. Wu, X.T. Chen, P.K. Chu, Growth of tin oxide nanorods induced by nanocube-

oriented coalescence mechanism, Appl. Phys. Lett. 98 (2011) 133102.

RI
[20] S. Supothina, R. Rattanakam, S. Vichaphund, P. Thavorniti, Effect of synthesis condition on

morphology and yield of hydrothermally grown SnO2 nanorod clusters, J. Eur. Ceram. Soc. 31 (2011)

SC
2453–2458.

U
[21] N. Talebian, F. Jafarinezhad, Morphology-controlled synthesis of SnO2 nanostructures using
AN
hydrothermal method and their photocatalytic applications, Ceram. Int. 39 (2013) 8311–8317.

[22] S. Cao, W. Zeng, H. Zhang, Y. Li, Hydrothermal synthesis of SnO2 nanocubes and nanospheres and
M

their gas sensing properties, J. Mater. Sci. Mater. Electron. 26 (2015) 2871–2878.
D

[23] X. (2015). Wang, Y, Zhang, Y, Li, X, Sun, M, Wei, Z., Wang, Y, Feng, Exploring the effects of
TE

different types of surfactants on Zebrafish embryos and larvae., Sci. Rep. (2015).

[24] B. Mehrabi Matin, Y. Mortazavi, A.A. Khodadadi, A. Abbasi, A. Anaraki Firooz, Alkaline-and
EP

template-free hydrothermal synthesis of stable SnO2 nanoparticles and nanorods for CO and ethanol gas

sensing, Sensors Actuators B Chem. 151 (2010) 140–145.

C
AC

[25] A.A. Bolzan, C. Fong, B.J. Kennedy, C.J. Howard, Structural studies of rutile-type metal dioxides, Acta

Crystallogr. Sect. B Struct. Sci. 53 (1997) 373–380.

[26] W.H. Baur, A.A. Khan, Rutile-type compounds. IV. SiO2, GeO2 and a comparison with other rutile-type

structures, Acta Crystallogr. Sect. B Struct. Crystallogr. Cryst. Chem. 27 (1971) 2133–2139.

[27] L.Z. Liu, X.L. Wu, T.H. Li, P.K. Chu, Twinning Ge0. 54Si0. 46 nanocrystal growth mechanism in

amorphous SiO2 films, Appl. Phys. Lett. 96 (2010) 173111.

 ACCEPTED MANUSCRIPT
[28] H. Wang, J. Liang, H. Fan, B. Xi, M. Zhang, S. Xiong, et al., Synthesis and gas sensitivities of SnO2

nanorods and hollow microspheres, J. Solid State Chem. 181 (2008) 122–129.

[29] Y. Liang, B. Fang, Hydrothermal synthesis of SnO2 nanorods: Morphology dependence, growth

mechanism and surface properties, Mater. Res. Bull. 48 (2013) 4118–4124.

PT
[30] B. Zhang, Y. Tian, J.X. Zhang, W. Cai, Structural, optical, electrical properties and FTIR studies of

fluorine doped SnO2 films deposited by spray pyrolysis, J. Mater. Sci. 46 (2010) 1884–1889.

RI
[31] B. Liu, E.S. Aydil, Growth of oriented single-crystalline rutile TiO2 nanorods on transparent conducting

substrates for dye-sensitized solar cells, J. Am. Chem. Soc. 131 (2009) 3985–3990.

SC
[32] W. Zeng, H. Zhang, Y. Li, W. Chen, Z. Wang, Hydrothermal synthesis of hierarchical flower-like SnO2

U
nanostructures with enhanced ethanol gas sensing properties, Mater. Res. Bull. 57 (2014) 91–96.
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT
Sample GOF a (Å) c (Å) Oxygen position
(X,Y)

0.08 M 8.25 4.7509 (2) 3.18200 (9) 0.3010 (5)

0.12 M 11.70 4.7501 (1) 3.18317 (9) 0.3069 (7)

PT
RI
U SC
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

a b

PT
RI
c d

U SC
AN
e f
M
D
TE
EP

g h
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT
• The concentration of metal precursor strongly affected the morphology of SnO2 nanostructures.
• Hydrothermal method at low temperature 180 °C without surfactant, template or further calcination
was successfully employed.
• From the XRD measurements, homogeneous single rutile tetragonal phased of SnO2 nanorods were
obtained.
• The formation of SnO2 nanorods could have originated from the primary nanoparticles based on the
TEM results.

PT
RI
U SC
AN
M
D
TE
C EP
AC