See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/263703794

Synthesis and Characterization of SnO2 Nanorods for

Energy Storage Applications
ARTICLE JULY 2014
DOI: 10.1166/asem.2014.1563

READS

178

7 AUTHORS, INCLUDING:
M. Zubair Iqbal

Fengping Wang

Chinese Academy of Sciences

University of Science and Technology Beijing

46 PUBLICATIONS 206 CITATIONS

67 PUBLICATIONS 359 CITATIONS

SEE PROFILE

SEE PROFILE

Riaz Hussain

Muhammad Yasir Rafique

Pakistan Institute of Engineering and Applied Sci

COMSATS Institute of Information Technology

7 PUBLICATIONS 3 CITATIONS

44 PUBLICATIONS 225 CITATIONS

SEE PROFILE

SEE PROFILE

Available from: Riaz Hussain

Retrieved on: 10 April 2016

Article
Advanced Science,
Engineering and Medicine

Copyright 2014 American Scientic Publishers

All rights reserved
Printed in the United States of America

Vol. 6, 16, 2014

www.aspbs.com/asem

Synthesis and Characterization of SnO2 Nanorods for

Energy Storage Applications
M. Zubair Iqbal1
2
, Fengping Wang2
, Riaz Hussain3 , Tahir Iqbal4 , Israt Ali5 ,
M. Yasir Raque2 , and Shujjat Ali2
1

Division of Functional Materials and Nano-Devices, Ningbo Institute of Materials Technology and Engineering,
Chinese Academy of Sciences, Ningbo, Zhejiang, 315201, P. R. China
2
Department of Physics, School of Applied Science, University of Science and Technology Beijing,
Beijing 100083, P. R. China
3
Department of Physics and Applied Mathematics, Pakistan Institute of Engineering and
Applied Sciences, Nilore, Islamabad 45650, Pakistan
4
Department of Physics, University of Gujrat, Gujrat, 50700, Pakistan
5
Department of Chemistry, University of Gujrat, Gujrat, 50700, Pakistan

Tin dioxide (SnO2 ) is a signicant functional material which contributes to a broad range of applications in optoelectronic, gas sensing and energy storage devices because of its high excitation
binding energy ( 130 meV) and good chemical stability. In present work, single crystalline SnO2
bullet-shaped nanorods have been synthesized via hydrothermal growth route by using SnCl2 2H2 O
and N2 H4 2H2 O as raw materials. The morphology, crystalline structure and elemental composition
were characterized by eld emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive X-ray (EDX) respectively.
FESEM results have illustrated that the average size of nanorod-shape structure of SnO2 is about
100 nm. X-ray diffraction (XRD) and selected area electron diffraction (SAED) patterns revealed
that the prepared SnO2 nanorods exist in single-crystalline behavior. Furthermore, X-ray photoelectron spectroscopy (XPS) has been employed to conrm the chemical valence of Sn and relative
atomic composition of as-synthesized SnO2 . The rst ever study on hydrogen absorption characteristics of SnO2 nanostructures performed at 373 K shows good absorption capacity of 1.22 wt.%.
The absorption kinetics is investigated qualitatively with respect to the rate-limiting procedures by
manipulating different kinetic models. Moreover, the electrochemical performance results suggest
that as-synthesized SnO2 nanorods will be a promising anode material for lithium-ion batteries.

Keywords: Nanostructured Materials, Stannic Oxide, Hydrothermal Method, Transmission

Electron Microscopy (TEM), Energy Storage.

1. INTRODUCTION
Modern energy sources such as lithium ion batteries and
H2 fuel cells have attracted great interest of researchers
owing to their environment friendly and promisingly efcient operation. In contrast, combustion of conventional
carbon-based fossil fuels contributes to air pollution,
global warming and environmental contamination. In this
context, hydrogen is an excellent alternative clean energy
carrier which is hazardless, nontoxic, cost effective and

Authors to whom correspondence should be addressed.

Adv. Sci. Eng. Med. 2014, Vol. 6, No. xx

greatly reduces ecological pollution.1 However, challenge

to synthesize the advanced hydrogen storage materials
with high volumetric and gravimetric density is still out
there. Recently, one and two dimensional nanostructured
materials (about less than 80 nm) have acquired a considerable attention thanks to their interesting electrical, magnetic, catalytical and optical properties in comparison to
their bulk state.2
3 Nano architectures of transition semiconductor oxides are getting immense importance because
of their excellent properties and potential applications
in energy storage devices. Among them, stannic oxide

2164-6627/2014/6/001/006

doi:10.1166/asem.2014.1563

Synthesis and Characterization of SnO2 Nanorods for Energy Storage Applications

Iqbal et al.

(SnO2 ), as an important n-type semiconductor with wide

optical band gap of 3.6 eV, has been extensively studied
due to its high excitation binding energy ( 130 meV),
high chemical stability and interesting electrochemical/optical properties. SnO2 has potential applications in
various elds such as solar cells, catalysts, gas sensors,
eld emitters and optical devices. SnO2 is a promising electrode material for lithium ion rechargeable batteries because of its higher theoretical storage capacity
(781 mA h g1 ) compared to graphite (372 mA h g1 ).46
It is well known that the dimension and morphology
of materials have signicant inuence on their physical/chemical properties. To date, nanostructures of SnO2
have been successfully synthesized by various techniques
such as solgel route,7 thermal evaporation method,5
chemical vapor deposition (CVD),8 aqueous phase process, pulsed laser deposition and solution methods.9
10
A wide range of SnO2 micro/nanostructures including nanocrytalline,11 pompon-like,6 nanosheets,12 hollow
spheres,13 spirals, nanorings,14 nanobelts and nanowires,5
nanobox,15 meshes,16 nanoowers,17 and mesoporous
structures18 were synthesized. However, the preparation of
SnO2 nanostructures with well-controlled morphology and
dimension by facile synthesis is still a challenge.
During this study, bullet-shaped stannic oxide nanorods
with an average length and diameter about less than
100 nm were synthesized by a simple template/catalystfree hydrothermal process using novel precursor hydrazine
hydrate. To demonstrate the promising applications, hydrogen absorption, kinetics of absorption and electrochemical
properties of as-synthesized SnO2 nanomaterial were evaluated. The electrochemical results exhibit that synthesized
SnO2 nanorods deliver a high initial discharge capacity
about 2207 mA h g1 comparatively higher than several
earlier reported gures.

2.2. Characterization
The as-synthesized nanomaterial was investigated by
X-ray diffraction (XRD) using a Rigaku D/MAX-RB
diffractometer equipped with Cu K radiation ( =
154056 ). The morphological information of prepared
SnO2 was characterized by eld-emission scanning electron microscopy (FESEM, SUPRA55) combined with
energy dispersive spectra (EDS) analysis, transmission
electron microscopy (TEM), HRTEM and selected area
electron diffraction pattern (SAED). X-ray photoelectron
spectroscopy (XPS) analysis and hydrogen storage properties of the sample were studied by AXIS ULTRADLD
(Al K, h = 14866 eV, Kratos) and Sieverts-type Gas
Reaction Controller, respectively.
Electrochemical characterization of bullet-shaped SnO2
nanorods were executed by using Swagelok-type cells
which is assembled under Ar atmosphere, in a
MIKROUNA glove box with oxygen and water vapor concentrations were less than 1 ppm. The working electrode
was formed as a thin lm by spreading slurry out on a copper foil. The slurry was a mixture composed of 80 wt.%
synthesized active materials, 10 wt.% PVDF as binder
dissolved in N -methyl pyrrolidone (NMP), and 10 wt.%
acetylene black as conductive agent. After NMP evaporation, the mixture was spread uniformly onto a copper foil
with a diameter of 8 mm and dried at 120  C under vacuum for 24 h. The disk was used as the positive electrode
and a lithium foil as the counter electrode. The electrolyte
was made of 1 M LiPF6 dissolved in the mixture of methyl
ethylene carbonate (MEC), ethylene carbonate (EC), and
dimethyl carbonate (DMC) (1:1:1 by volume) soaked on a
Celgard 2400 polypropylene separator. The galvanostatic
cycling tests were performed within a 0.012.0 V cut-off
voltage limit, using a LAND BT-10 battery test system
(Wuhan, China).

2. EXPERIMENTAL DETAILS

3. RESULTS AND DISCUSSION

2.1. Sample Preparation

Commercially available reagents stannous chloride dehydrate ( 95%) and hydrazine hydrate (80% aqueous
solution) were used to synthesize SnO2 nanomaterial. At
starting procedure, 0.55 M of SnCl2 2H2 O dissolved into
20 ml de-ionized water by stirring for 20 minutes to obtain
SnCl2 homogeneous solution. Subsequently, the quantity
of 30 ml of H4 N2 H2 O (80% aqueous solution) was
added in the obtained homogeneous solution and mixed
by magnetic stirrer for 40 minutes at maintained temperature 50  C. Later on, the reaction mixture was sealed in a
40 ml Teon-lined stainless steel autoclave and kept within
a microwave oven at 180  C for 24 hrs. Once hydrothermal process completed, the precipitates were collected by
centrifugation, washed several times with absolute ethanol
and dried under vacuum at 70  C for over a night. Finally,
the obtained powder annealed at 700  C and collected for
characterization.

The crystalline structure of the prepared material is characterized by x-ray diffraction. Figure 1 shows the typical
XRD pattern of as-synthesized product. All the diffraction peaks of XRD pattern are in accordance with the
tetragonal cassiterite SnO2 (JCPDS le No. 41-1445).
Dominant sharp diffraction peaks (110), (101) and (211)
indicate the good crystallinity of the synthesized material. The lattice parameters measurements of the sample
were computed according to the equation 1/d 2 = h2 /a2 +
k2 /a2 +l2 /c 2 based on the crystallographic planes of (200)
and (101). The acquired values a = b = 4751 and
c = 3190 which are consistent with the standard card
(JCPDS le No. 41-1445).
Furthermore, peak sharpness reects the size for SnO2
particles and the average crystallite size of SnO2 nanoparticles is calculated to be about 9 nm from the fullwidth at half-maximum of XRD using the Debye Scherrer
equation.19 The EDS analysis spectra are shown in the

Adv. Sci. Eng. Med. 6, 16, 2014

Iqbal et al.

Synthesis and Characterization of SnO2 Nanorods for Energy Storage Applications

Figure 1. (a) X-ray diffraction pattern (XRD), the inset shows an EDS spectrum and (b) XPS analysis of as-prepared SnO2 nanostructures.

inset of Figure 1. The nal precipitation contains only Sn

and O elements, which suggests that synthesized nanostructures are made of Sn and O and no other contamination was observed. The chemical states and compositions
of the SnO2 nanorods are acquired by XPS analysis and the
corresponding spectrum is manifested in Figure 1(b). XPS
contains only Sn and O elements and the SnO2 appears
as a spin-orbit doublet at 486.7 (3d5/2) and 495.1 eV
(3d3/2).20 The obtained information from XPS analysis is

consistent with XRD, EDS results and as well as reported

literature.
The morphological characterization of the assynthesized tin dioxide material was initially determined
by FE-SEM. Figure 2 shows the typical FE-SEM micrographs at low magnication which exhibits that these
SnO2 nanoparticles are agglomerated and randomly distributed above a carbon tape. The high magnication
image of these agglomerated SnO2 nanorods is shows in

Figure 2. (a), (b) FESEM images, (c) TEM image of a single bullet shaped SnO2 nanorod, (d) HRTEM image and inset shows the corresponding
SAED pattern of the SnO2 product.

Adv. Sci. Eng. Med. 6, 16, 2014

Synthesis and Characterization of SnO2 Nanorods for Energy Storage Applications

Iqbal et al.

Figure 3. (a) Hydrogen absorption curve of SnO2 nanorods and (b) curves measured from various kinetic models applied to absorption value.

Figure 2(b). Furthermore, depth structural characterizations of the as-synthesized stannic oxide were investigated
by TEM, HRTEM and SAED. Figure 2(c) is the TEM
image of one dimensional bullet-shaped single nanorod
structure. TEM result shows that the typical length of
as grown single nanorod is about 70 nm and the width
is 15 nm. The lattice fringes in the HRTEM image
[Fig. 2(d)] provide strong evidence about the single
crystal nature of the SnS nanostructure. The spacing
between adjacent lattice planes is 0.336 nm corresponding
to (110). Furthermore, selected area electron diffraction
(SAED) pattern from an individual nanorod conrms that
the as-synthesized cassiterite SnO2 nanorods are singlecrystalline in nature and the preferential growth along the
[110] direction (inset of (d)). Generally, 1D nanostructures
have signicant inuence on their applications because of
effective way to trap photons due to special geometrical
architecture in the exciton generation step and their physical dimensions which are the main source of increase in
the energy conversion efciency.
Hydrogen storage in semiconductor materials is a key
challenge in developing hydrogen economy. Hydrogen
adsorption of as-synthesized bullet shaped SnO2 nanorods
has been investigated by Sieverts-type Gas Reaction Controller.
Hydrogen storage experiment was performed for 3 hrs
at 373 K with 4 Mp pressure in one cycle and the absorption characteristic curve was indicated in Figure 3(a).
From results it is obvious that the hydrogen absorption
increases slowly with the passage of time. The maximum hydrogen absorption in SnO2 nanorods was observed
1.22 wt.% after 3 hrs. The hydrogen absorption capability
of the as-synthesized bullet shaped stannic oxide nanorods
may be associated with the spacing between agglomerated
nanorods or surface defects of nanocrystalline material and
this capacity can be increases by increasing by creating
more defects in nanostructured material.2124 This attained
hydrogen absorption capacity is greater than other reported
compounds given in Table I.
A qualitative technique is adopted for examination
of the rate-limiting mechanisms during decomposition
4

reactions by comparing the measured reaction kinetics

with calculated values of known rate-limiting processes.
For this purpose, various solid-state reaction mechanism
models have been proposed such as the geometrical contraction, one-two-three dimensional diffusion, Random
nucleation, 3D growth with constant interface velocity and
3D growth with constant interface velocity. Table II summarizes several important theoretical kinetic equations34
related to different rate-limiting steps.
In above mentioned equations,  is transformed fraction
in time t with the reaction constant k. All the models,
listed in Table II, have been applied to the absorption
characteristic curve achieved in Figure 3(a). The resultant curves are shown in Figure 3(b). In Figure 3(b), the
excellent correlation coefcient value corresponds to the
D2 model which is the function of a two-dimensional
diffusion. In-depth, hydrogen atoms are embedded two
dimensionally on the surface of single crystalline SnO2
nanorods. Initially, the diffusion rate is high and the
observed capacity is rapidly increasing during rst hour,
later this diffusion rate is decreased because the majority
spacing between agglomerated nanorods or surface defects
of nanocrystalline material occupied by hydrogen atom
Table I. Comparison of hydrogen absorption capacity of as-synthesized
SnO2 nanorods with various reported nanostructure materials.
Materials
ZnO nanowires
Pure ZnO Powder
ZnO microspheres
SnO nano-square sheets
Cd/CdO shelled hollow
microspheres
NiO nanorods
SnO clinopinacoid
SWNTS soot
N -doped microporous carbon
Bulk BN powder
SnS nanorods
SnO2 nanorods

Hydrogen Temperature
absorption %
(K)

Ref.

0.83
1.05
1.179
1.194
1.09

300
373
373
373
373

[25]
[24]
[24]
[26]
[27]

0.71
0.96
0.40.7
0.45
0.20
0.73
1.22

300
373
253
298
293
373
373

[28]
[29]
[30]
[31]
[32]
[33]
Present work

Adv. Sci. Eng. Med. 6, 16, 2014

Iqbal et al.

Synthesis and Characterization of SnO2 Nanorods for Energy Storage Applications

Table II. Kinetic equations measured for the absorption of as-prepared

SnO2 nanorods.
Symbol
A1
R2
A2
F1
A3
D3
R3
D2
D1

Reaction model description

Branching nuclei, prout tompkins
equation
2D growth with constant
interface velocity
Random nucleation: Avrami equation
First-order kinetic
Random nucleation: Erofeev equation
Jander equation, three-dimensional
diffusion
3D growth with constant
interface velocity
Two-dimensional diffusion
One-dimensional diffusion

Table III. Performance comparisons of different LIB SnO and SnO2

electrodes constructed based on various nanomaterials.

Integral f  form

ln/1 
1 1 1/2
 ln1  1/2
ln1 
 ln1  1/3
1 1 1/3 2
1 ln1 1/3
 + 1  ln1 
2

and the value of observed hydrogen absorption is increasing slowly. This rst ever study on hydrogen absorption
characteristics of SnO2 indicated that as-synthesized SnO2
nanorods are the promising material for hydrogen storage
applications.
Furthermore, galvanostatical charge (Li+ extraction) and
discharge (Li+ insertion) experiments were performed
to investigate the electrochemical behavior of asprepared SnO2 nanorods. The characteristic curves of discharge/charge and cyclic performance of bullet-shaped
nanorods are shown in Figure 4. The discharge plateaus
observed at 0.91.1 V in the rst cycle which corresponds to the conversion reaction between Li and SnO2 ,
and formation of Sn/Li2 O nanocomposites.6 The electrochemical results illustrate that the rst discharge capacity reaches a very high value of 2207 mA h g1 and
remains about 990 mA h g1 during the rst delithiation process with 45% columbic efciency. Interestingly, this rst charge and discharge capacities are greater
than other Sn based anode materials as illustrated in
Table III. A small difference between the rst and
all following cycles is observed. The substantial difference of reversible and irreversible capacity of the

Electrode materials
SnO2 /ZnO composite
SnO2 powered

SnO2 nanospheres
Pristine SnO
Nest-like SnO
Layer-plate-like SnO
Stepwise-bipyramidlike SnO
Nanosized SnO2
SnO2 /MWCNTs
SnO2 /SWCNTs
SnO2 /CNSs
SnO2 nanorods

Applied
potential
range (V)

1 cycle charge
discharge capacity
(mA h g1 )

Ref.

0.022.0
0.02.0
0.02.0
0.02.0
0.02.0
0.02.5
0.10.3
0.023.0
0.023.0
0.023.0

1540620
1015472
1312820
1369846
1331840
1520724
1215.5675.1
960460
1000535.3
830342

[36]
[37]
[37]
[37]
[37]
[38]
[39]
[40]
[40]
[40]

0.042.0
0.0012.5
0.0012.5
0.0012.5
0.012.0

1518916
985755
867652
914375
2207990

[41]
[42]
[42]
[42]
Present work

rst cycle due to the following processes: formation

of irreversible Li2 O, irreversible reactions and volume
expansion when SnO2 became Lix Sn (0 x 44) alloy
in the electrochemical process.
4Li+ + SnO2 + 4e Sn + 2Li2 O
+

xLi + Sn + xe Lix Sn

0 x 44

(1)
(2)

The second charge and discharge capacity were

905 mA h g1 and 1143 mA h g1 , respectively with
coulombic efciency of 79.2% as shown in Figure 4(a).
This coulombic efciency increases to 81% at third
charge/discharge capacity and so on. The cycling performance of as-synthesized bullet-shaped SnO2 nanorods
is shown in Figure 4(b). The discharge capacity after
25 cycles retains about 290 mA h g1 , which is comparatively larger than that of many reported values.
The coulombic efciency is above 87% after 25 cycles.
The high energy storage capacity of as-synthesized

Figure 4. (a) Initial discharge and charge curves and (b) Cycle performance of bullet-shaped SnO2 nanorods.

Adv. Sci. Eng. Med. 6, 16, 2014

Synthesis and Characterization of SnO2 Nanorods for Energy Storage Applications

nanomaterial might be related with high surface to volume ratio and the one dimensional architecture, which can
accommodate more storage sites in the prepared bulletshaped SnO2 nanorods.35

4. CONCLUSIONS
In summary, a simple hydrothermal growth method has
been employed for the synthesis of single crystalline
bullet-shaped stannic oxide nanorods. Structural characterizations results show that the length of prepared SnO2
nanorods was less than 80 nm and diameter was about
few nanometers. The novel studies on hydrogen storage
capability of synthesized nanomaterial examined at 373 K
indicate an absorption capacity of 1.22 wt.%. Furthermore, as anode material for LIB, SnO2 nanorods exhibits
a high initial discharge capacity about 2207 mA h g1 ,
which might be related with the high surface-to-volume
ratio and the unique one dimensional nanostructures. The
hydrogen absorption and electrochemical results demonstrated that the synthesized bullet-shaped SnO2 architectures are the promising candidate for energy storage
devices.
Acknowledgments: This research work has been performed with the nancial support of National Key Scientic Instruments and Equipment Development Special
Fund (2011YQ14014506 and 2011YQ14014507), the Oriented Award Foundation for Science and Technological
Innovation, Inner Mongolia Autonomous Region, China
(2012) and Chancellor Scholarship program of University
of Science and Technology Beijing, China.

References and Notes

1. J. Jiang, Q. Gao, Z. Zheng, K. Xia, and J. Hu, Int. J. Hydrogen
Energy 35, 210 (2010).
2. C. H. Shek, J. K. L. Lai, and G. M. Lin, Nanostructured Materials
11, 887 (1999).
3. L. I. Popova, V. K. Georgiev, D. I. Kolev, and J. Lutzkanov, Mater.
Lett. 7, 271 (1988).
4. M. S. Kim, H. K. Lee, and J. S. Yu, Mater. Lett. 80, 13 (2012).
5. X. Xie, Z. Shao, Q. Yang, X. Shen, W. Zhu, X. Hong, and G. Wang,
Journal of Solid State Chemistry 191, 46 (2012).
6. X. Sun, X. Wang, Y. Qin, X. Li, L. Qiao, N. Feng, D. Hu, and D. He,
Mater. Lett. 66, 193 (2012).
7. L. Korosi, S. Papp, V. Meynen, P. Cool, E. F. Vansant, and I. Dekany,
Colloids Surf. A: Physicochem. Eng. Asp. 268, 147 (2005).
8. Z. R. Dai, Z. W. Pan, and Z. L. Wang, 118, 351 (2001).
9. J. Q. Hu, Y. Bando, Q. L. Liu, and D. Golberg, Adv. Funct. Mater.
13, 493 (2003).
10. L. Wang, J. Ren, X. Liu, G. Lu, and Y. Wang, Materials Chemistry
and Physics 127, 114 (2011).

Iqbal et al.

11. Y. Chen, J. Zhu, X. Zhu, G. Ma, Z. Liu, and N. Min, Materials

Science and Engineering B 99, 52 (2003).
12. Y. Masuda, Progress in Crystal Growth and Characterization of
Materials 58, 106 (2012).
13. X. W. Lou, Y. Wang, C. Yuan, J. Y. Lee, and L. A. Archer, Adv.
Mater. 18, 2325 (2006).
14. R. S. Yang and Z. L. Wang, J. Am. Chem. Soc. 128/5, 1466 (2006).
15. Y. Liu, H. Dong, and M. L. Liu, Adv. Mater. 16, 353 (2004).
16. H. Uchiyama and H. Imai, Cryst. Growth Des. 7/5, 841 (2007).
17. R. Yang, Y.G. Gu, Y.Q. Li, J. Zheng, and X. G. Li, Acta Mater. 58,
866 (2010).
18. X. Yin, L. Chen, C. Li, Q. Hao, S. Liu, Q. Li, E. Zhang, and T. Wang,
Electrochimica Acta 56, 2358 (2011).
19. M. Z. Iqbal, F. Wang, H. Zhao, M. Y. Raque, J. Wang, and Q. Li,
Scripta Materialia 67, 665 (2012).
20. L. Y. Liang, Z. M. Liu, H. T. Cao, and X. Q. Pan, ACS Applied
Materials and Interfaces 2, 1060 (2010).
21. B. Sakintuna, F. L. Darkrim, and M. Hirscher, Int. J. Hydrogen
Energy 32, 1121 (2007).
22. J. Jiang, Q. Gao, Z. Zheng, K. Xia, and J. Hu, Int. J. Hydrogen
Energy 35, 210 (2010).
23. Z. Yaakob, D. J. Khadem, S. Shahgaldi, W. R. W. Daud, and S. M.
Tasirin, Int. J. Hydrogen Energy 37, 8388 (2012).
24. M. Ahmad, Ra-ud-Din, C. F. Pan, and J. Zhu, J. Phys. Chem. C
114, 2560 (2010).
25. Q. Wan, C. L. Lin, X. B. Yu, and T. H. Wang, App. Phy. Lett. 84, 124
(2004).
26. M. Z. Iqbal, F. Wang, T. Feng, H. Zhao, M. Y. Raque, Ra-udDin, M. H. Farooq, Q. Javed, and D. F. Khan, Materials Research
Bulletin 47, 3902 (2012).
27. W. S. Khan, C. Cao, F. K. Butt, Z. Ali, Z. Usman, G. Nabi, et al.,
Int. J. Hydrogen Energy 38, 2332 (2013).
28. Z. P. Guo, L. Yuan, K. Konstantinov, Z. G. Huang, and H. K. Liu,
Mater. Lett. 60, 3891 (2006).
29. M. Z. Iqbal, F. Wang, Ra-ud-Din, M. Y. Raque, Q. Javed, A.
Ullah, and H. Qiu, Materials Letters 78, 50 (2012).
30. L. David, G. Flamant, E. Bche, J. L. Sans, J. Giral, and V. Goetz,
Int. J. Hydrogen Energy 32, 1016 (2007).
31. L. Wang and R. T. Yang, J. Phys. Chem. C 113, 21883 (2009).
32. R. Z. Ma, Y. Bando, H. W. Zhu, T. Sato, C. L. Xu, and D. H. Wu,
J. Am. Chem. Soc. 124, 7672 (2002).
33. M. Z. Iqbal, F. Wang, M. Y. Raque, S. Ali, M. H. Farooq, and
M. Ellahi, Mater. Lett. 106, 33 (2013).
34. Ra-ud-din, L. Zhang, L. Ping, and Q. Xuanhui, J. Alloys Compds.
508, 119 (2010).
35. X. M. Yin, C. C. Li, M. Zhang, Q. Y. Hao, S. Liu, L. B. Chen, et al.,
J. Phys. Chem. C 114, 8084 (2010).
36. M. Ahmad, S. Y. Ying, H. Y. Sun, W. Shen, and J. Zhu, J. Solid
State Chemistry 196, 326 (2012).
37. R. Zhang, J. Y. Lee, and Z. L. Liu, J. Power Sources 112, 596 (2002).
38. Z. Wen, F. Zheng, and K. Liu, Mater. Lett. 68, 469 (2012).
39. W. Yue, S. Yang, Y. Ren, and X. Yang, Electrochimica Acta 92, 412
(2013).
40. J. J. Ning, T. Jiang, K. K. Men, Q. Q. Dai, D. M. Li, Y. J. Wei,
et al., J. Phys. Chem. C 113, 14140 (2009).
41. G. Xia, N. Li, D. Li, R. Liu, N. Xiao, and D. Tian, Mater. Lett.
65, 3377 (2011).
42. L. L. Xing, C. H. Ma, C. X. Cui, and X. Y. Xue, Solid State Sciences
14, 111 (2012).

Received: 11 November 2013. Accepted: 13 February 2014.

Adv. Sci. Eng. Med. 6, 16, 2014