Materials Sciences and Applicatio n, 2011, 2, 964-970
doi:10.4236/msa.2011.28129 Published Online August 2011 (
Copyright © 2011 SciRes. MSA
Hydrothermal Synthesis of V3O7·H2O Nanobelts
and Study of Their Electrochemical Properties
Mohamed Kamel Chine1, Faouzi Sediri1,2*, Neji Gharbi1
1Laboratoire de Chimie de la Matière Condensée IPEIT, Université de Tunis, Montfleury Tunis Tunisia, Tunisia; 2Faculté des Sci-
ences de Tunis, Université Tunis El Manar, Tunis, Tunisia.
Email: *,
Received March 15th, 2011; revised April 6th, 2011; accepted May 9th, 2011.
Vanadium oxide hydrate V3O7·H2O (H2V3O8) nanobelts have been synthesized by hydrothermal approach using V2O5 as
vanadium source and phenolphthalein as structure-d irecting agent. Techniques X-ray powder diffraction (XRD), scan-
ning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy and nitrogen adsorp -
tion/desorption isotherms have been used to characterize the structure, morphology and composition of the nanobelts.
The V3O7·H2O nanobelts are up to several hundreds of nanometers, the widths and thicknesses are 90 and 40 nm, re-
spectively. The electroactivity of the nanobelts has been investigated. The as-synthesized material is promising for
chemical and energy-related applications such as catalysts, electrochemical device and it may be applied in recharge-
able lithium-ion batteries.
Keywords: Nanobelts, V3O7·H2O, Phenolphthalein, Hydrothermal Synthesis, Electroactivity
1. Introduction
Among the various candidates for their much important
applications in catalysts [1,2], cathodes materials [3-5]
for rechargeable Li-ion batteries, chemical sensors [6,7],
vanadium oxides have attracted much attention due to
their layered structure and distinctive physicochemical
properties [8-10]. In particular, one-dimensional (1D)
nanostructural vanadium oxides have been successfully
used as electrode materials with greatly enhanced elec-
trochemical properties [11,12]. 1D nanostructural vana-
dium oxides containing either V4+ or V5+ have a large
capacity which corresponds to reduction of the V4+ or
V5+ by the intercalation process in which Li enters the
VOx layers. To best of our knowledge, however, the syn-
thesis and electrochemical properties of 1D nanostruc-
tural vanadium oxide composed of V4+ and V5+ have
rarely been reported [13]. Among them nanostructured
vanadium oxides have been extensively studied since the
discovery of VOx nanotubes by R. Nesper and his group
[14-15]. They exhibit a great variety of nanostructures,
ranging from 1D to 3D [16] and V2O5 has even been
chosen as a model system for the description of nanos-
tructured materials.
As one of the wet chemistry methods, hydrothermal
treatment has been extensively used for the synthesis of
inorganic compounds [12]. Indeed, Sediri et al. [13]
synthesized the nanoneedles, nanorods of B-VO2, and
vanadium oxide nanotubes with high crystallinity via a
one-step hydrothermal treatment using crystalline V2O5
as a precursor and various aromatic amines as struc-
ture-dire-cting templates. V3O7·H2O·(H2V3O8) has been
studied for many years [19-21]. V3O7·H2O nanobres
have been prepared rstly by Theobald [19]. Their struc-
ture was described as layers that contain VO6 octahedra
and VO5 trigonal bipyramids with vanadium oxidation
states of +4 and +5, respectively [20]. Recently, the syn-
thesis of V3O7·H2O nanobelts was reported by Li and
coworkers [22]. In their synthesis, the nanobelts were
hydrothermally grown from V2O5 powder in the presence
of appropriate amount of hydrochloric acid. Shi et al. [23]
obtained single-crystalline vanadium oxide nanobelts
through a surfactant-directed growth process under hydr-
othermal conditions using V2O5 as a precursor.
While many methods have been developed to elabo-
rate nanostructured vanadium oxides, to the best of our
knowledge, it is the first time to report the optimization
of reaction conditions of the synthesis of V3O7·H2O
nanobelts using phenolphthalein as structure-directing
template by hydrothermal self-assembling process. The
Hydrothermal Synthesis of VO·H O Nanobelts and Study of Their Electrochemical Properties965
3 72
electrochemical properties of V3O7·H2O nanobelts were
also studied.
2. Experimental Section
2.1. Hydrothermal Synthesis
All of the chemical reagents were purchased from Across
and used without further purification. V2O5 was used as
vanadium source and phenolphthalein was used as struc-
ture-directing template for the first time.
The detailed synthesizing process was as follows. In a
typical synthesis, the preparation was made from a mix-
ture of V2O5 (0.079 g), phenolphthalein (0.46 g) and dis-
tilled water (10 mL). After 2 hours of stirring, the mix-
ture was transferred into a Teflon lined steel autoclave
with a capacity of 23 ml, and maintained at 180˚C for 4
days under autogenous pression. The pH of the reaction
mixture remains close to pH 7. After hydrothermal
treatment, the pH of the solution was equal to 4.3. The
resulting green powder was washed with water and
ethanol to remove the organics residues and then dried at
80˚C for 4 hours. The green color of the powder sug-
gested the presence of the V4+ ions [24].
2.2. Characterization Techniques
X-ray powder diffraction data (XRD) were obtained on a
X`Pert Pro Panalytical diffractometer with CoKα radia-
tion (λ = 1.78901 Å) and graphite monochromator. The
XRD measurements were carried out by a step scanning
method (2θ range from 2˚ to 50˚), the scanning rate is
0.03˚ s–1 and the step time is 3 s.
Scanning electron microscopy (SEM) images were
obtained with a Cambridge Instruments Stereoscan 120.
Transmission electron microscopy (TEM) was carried
out with a Philips G20 Ultra-Twin Microscope at an ac-
celerating voltage of 200 kV. One droplet of the powder
dispersed in CH3CH2OH was deposited onto a car-
bon-coated copper grid and left to dry in air.
Fourier transform infrared spectra (FTIR) were re-
corded with a Nicolet 380 Spectrometer.
The electrochemical measurements were performed
using a potentiostat (Organic-Logic SA) workshop with
Hg/HgCl2/KCl as reference electrode and a stainless grid
as the counter electrode. The working electrode is a film
of V3O7·H2O deposited on a plate of indium tin oxide
(ITO). The operating voltage was controlled between
–1.0 and 2.5 V at a scan rate of 50 mVs1. The electrolyte
was the lithium perchlorate 1M (LiClO4) dissolving in
propylene carbonate (PC). All measurements were per-
formed at room temperature.
3. Results and Discussion
3.1. X-ray Diffraction
The structural properties of the prepared samples were
studied by using the X-ray diffraction (XRD). The X-ray
diffraction (XRD) pattern of the as-obtained powder after
hydrothermal treatment is shown in Figure 1. All of dif-
fraction peaks can be perfectly indexed to orthorhombic
vanadium oxide crystalline phase V3O7·H2O·(H2V3O8)
with lattice constants of a = 16.847 Å, b = 9.362 Å and c
= 3.634 Å (JCPDS 85-2401). No peaks of any other
phases or impurities were observed from the XRD pat-
terns, indicating that V3O7·H2O crystalline phase with
high purity could be obtained using the present synthetic
3.2. Scanning and Transmission Electron
The surface morphology and size of the as-prepared
samples were studied by using the scanning and trans-
mission electron microscopes (SEM and MET). The ob-
servation by scanning electronic microscopy of the sam-
ple (Figure 2) shows that the as-obtained V3O7·H2O is
made of a homogenous phase with particles uniformly
sized which display belt-like morphology, with a smooth
Figure 1. XRD pattern of the as- synthe sized V3O7·H2O nanobelts.
Copyright © 2011 SciRes. MSA
Hydrothermal Synthesis of VO·H O Nanobelts and Study of Their Electrochemical Properties
966 3 72
Figure 2. SEM micrographs (a and b) of the as-synthesized material.
surface and a rectangular cross-section, 2 - 10 min length.
The transmission electron microscopy photos of the
as-obtained V3O7·H2O shows that the nanobelts are typi-
cally 90 nm wide and 40 nm thick (Figure 3). The high
magnification HRTEM image clearly exhibits high
Figure 3. TEM photos (a and b) of V3O7·H2O nanobelts.
crystallinity (Figure 4).The lattice fringes correspond to
a d spacing of 0.47 nm which is consistent with the dis-
tance between two (020) crystal planes of the ortho-
rhombic V3O7·H2O crystal, according to JCPDS 85 -
2401 [25]. This result is good agreement with X-ray dif-
3.3. Infrared Spectroscopy
The structure information was further provided by FTIR
spectroscopy. Figure 5 displays the infrared spectrum of
as-synthesized V3O7·H2O nanobelts. The bands at 1021
cm–1, 980 cm–1, and 557 cm–1 are attributed to the char-
acteristic of V-O vibration bonds. Indeed, the bands at
1021 cm–1 and 980 cm–1 correspond to the symmetric
stretching of the s (V5+ = O) and s(V4+ = O) bonds,
respectively, which indicates the similarity of the
as-prepared phase with the structure of the layered or-
thorhombic V2O5 [26]. The band at 534 cm–1 corresponds
to the stretching vibrations of the s (V-O-V) bridging
bonds [27]. The bands located at 3407 cm–1 and 1634
cm–1 come from the s (H-O-H) and s(H2O) vibration,
which might indicate that a certain amount of water
molecules is embedded between the layers [23]. The re-
sults demonstrates that the
Figure 4. HRTEM image of V3O7·H2O nanobelts.
1 μm WD = 3.4 mm EHT = 5.00 kV Signal A = InLens200 nmWD = 3.3 mm EHT = 5.00 kV Signal A = InLens
Copyright © 2011 SciRes. MSA
Hydrothermal Synthesis of VO·H O Nanobelts and Study of Their Electrochemical Properties 967
3 72
Figure 5. FTIR spectrum of V3O7·H2O nanobelts.
Figure 6. Cyclic voltammogams of the as-synthesized V3O7·H2O nanobelts.
material consist of mixed valance state vanadium atoms
and water.
3.4. Electrochemical Properties
As an intercalation compound, V3O7·H2O is promising
cathode material in lithium-ion batteries [23]. It was re-
ported that the electrochemical properties of the electrode
materials are influenced by many factors such as instinc-
tive structure, morphology, and preparation processes.
Therefore, in this paper, we also investigated the elec-
trochemical properties of lithium ion intercalation/dein-
tercalation of V3O7·H2O nanobelts. The cyclic voltam-
mogram (CV) curves of V3O7·H2O are shown in Figure
6. This clearly exhibits that there is a broad cathodic re-
duction peak at –0.5 V which result from the lithium ion
intercalation process and anodic oxidation peak at 1.2 V,
which is attributed to lithium ion deintercalation process,
which means that the crystalline structure is reversible.
This is a typical phenomenon of VOx active materials and
is often reported in the literature [28]. The lithium ion
intercalation and deintercalation process can be described
by the following process:
V3O7·H2O +x Li+ + x e- LixV3O7·H2O
3.5. Brunauer-Emmett-Teller (BET)
The specific surface area (SBET), pore volume (Vpor) and
Copyright © 2011 SciRes. MSA
Hydrothermal Synthesis of VO·H O Nanobelts and Study of Their Electrochemical Properties
968 3 72
Figure 7. N2 adsorption/desorption isotherms of V3O7·H2O nanobelts.
average pore size (dpor) of V3O7·H2O nanobelts were
measured by physisorption of nitrogen according to BET.
The obtained results are SBET = 13 m2·g–1, Vpor = 47.10–3
cm3·g–1 and dpor = 141 Ǻ. Furthermore, the analysis of the
N2 adsorption and desorption isotherms of the sample
leads to identification of the isotherm profiles, as type IV
in the BDDT system [29] as shown in Figure 7. This
profile is typical of mesoporous materials having pore
diameter between 2.0 and 50.0 nm. A hysteresis loop is
apparent identified as H3 type (IUPAC), which is char-
acteristic of cylindrical pores [29]. H3-type hysteresis
loops are usually observed with rigid bulk particles hav-
ing a uniform sizes [30]. This result is confirmed by the
specific surface area and the average pore size values.
These materials are promising for chemical and en-
ergy-related applications such as catalysts, and electro-
chemical device.
Although the formation mechanism of V3O7·H2O
nanobelts remains an open question, experimental data
and close investigation of intermediate compounds make
it possible to propose a model for the belt formation. To
the best of our knowledge and experiments, the whole
formation process of V3O7·H2O nanobelts under hydro-
thermal conditions can be described as follows.
To explain the mechanism which controls the mor-
phology of the material after hydrothermal treatment, a
possible intermediate process was suggested on the basis
of the layered structure of the precursors [31]. Whereas
this structure is stabilized by the phenolphthalein mole-
cules, it is sensible that the lamellate structure would
break down after displacement of the organic com-
Through the hydrothermal treatment, it is plausible
that the layered precursors would split into nanobelts,
and the products obtained would show striated mor-
phologies. However, in the hydrothermal synthesis, the
lamellar intermediate product would split later in small
stems because of the loss of organic molecules. Indeed,
the phenolphthalein molecules make the immobilization
of this lamellar structure difficult, resulting in the col-
lapse of the final lamellar precursor, supporting the exfo-
liation of the precursor and the formation of vanadium
oxide belts. We think that the phenolphthalein played a
double role of reducing and structuring agent in the for-
mation of V3O7·H2O nanobelts.
4. Conclusions
In summary, a facile synthetic route to monodisperse
crystalline vanadium oxide hydrate (V3O7·H2O) nano-
belts has been developed. Indeed, the synthesized
V3O7·H2O nanobelts were reported for the first time us-
ing phenolphthalein as structure-directing template. The
lengths of nanobelts up to several hundreds of nanome-
ters, the widths and thicknesses are 90 and 40 nm, re-
spectively. The phenolphthalein molecules were mainly
as reactants in the development of the formation of
V3O7·H2O nanobelts. The formation mechanism of
V3O7·H2O nanobelts was clearly explained. Finally, the
as-obtained V3O7·H2O nanobelts are promising cathode
materials in lithium-ion batteries
[1] M. Cozzolino, R. Tesser, M. D. Serio, P. D’Onofrio and
E. Santacesaria, “Kinetics of the Oxidative Dehydrogena-
Copyright © 2011 SciRes. MSA
Hydrothermal Synthesis of VO·H O Nanobelts and Study of Their Electrochemical Properties969
3 72
tion (Odh) of Methanol to Formaldehyde by Supported
Vanadium-Based Nanocatalysts,” Catalysis Today, Vol.
128, No. 3-4, August 2007, pp. 191-200.
[2] B. Huang, R. Huang, D. Jin and D. Ye, “Low Tempera-
ture SCR of NO with NH3 over Carbon Nanotubes Sup-
ported Vanadium Oxides,” Catalysis Today, Vol. 126,
No. 3-4, August 2007, pp. 279-283.
[3] D. Muñoz-Rojas and E. Baudrin, “Synthesis and Electro-
activity of Hydrated and Monoclinic Rutile-Type Nanosi-
zed VO2,” Solid State Ionics, Vol. 178, July 2007, pp.
[4] K. Lee, Y. Wang and G. Cao, “Dependence of Electro-
chemical Properties of Vanadium Oxide Films on Their
nano- and Microstructures,” Journal Physics Chemical B,
Vol. 109, No. 35, 2005, pp. 16700-16704.
[5] Y. Wang, K. Takahashi, K. Lee and G. Cao, “Nanostruc-
tured Vanadium Oxide Electrodes for Enhanced Lith-
ium-Ion Intercalation,” Advanced Functional Materials,
Vol. 16, No. 9, 2006, pp. 1133-1144.
[6] M. S. Whittingham, Y. N. Song, S. Lutta, P. Y. Zavalij
and N. A. Chernova, “Some Transition Metal (Oxy)
Phosphates and Vanadium Oxides for Lithium Batteries”,
Journal of Materials Chemistry, Vol. 15, No. 33, April
2005, pp. 3362-3379. doi:10.1039/b501961c
[7] J. Liu, X. Wang, Q. Peng and Y. Li, “Vanadium Pentox-
ide Nanobelts: Highly Selective and Stable Ethanol Sen-
sor Materials,” Advanced Materials, Vol. 17, No. 6,
March 2005, pp. 764-766.
[8] B. X. Li, Y. Xu, G. X. Rong, M. Jing and Y. Xie, “Vana-
dium Pentoxide Nanobelts and Nanorolls: from Control-
lable Synthesis to Investigation of Their Electrochemical
Properties and Photocatalytic Activities,” Nanotechnol-
ogy, Vol. 17, No. 10, April 2006, pp. 2560-2566.
[9] M. A. Gimenes, L. P. R. Profeti, T. A. F. Lassali, C. F. O.
Graeff and H. P. Oliveira, “Synthesis Characterization,
Electrochemical, and Spectroelectrochemical Studies of
an N-Cetyl-Trimethylammonium Bromide/V2O5 Nano-
composite,” Langmuir, Vol. 17, No. 6, March 2001, pp.
[10] F. Huguenin, M. Ferreira, V. Zucolotto, F. C. Nart, R. M.
Torresi and O. N. Oliveira Jr, “Molecular-Level Manipu-
lation of V2O5/Polyaniline Layer-by-Layer Films to Con-
trol Electrochromogenic and Electrochemical Properties,”
Chemistry of Materials, Vol. 16, No. 11, April 2004, pp.
[11] Y. Wang and G. Z. Cao, “Synthesis and Enhanced Inter-
calation Properties of Nanostructured Vanadium Oxides”
Chemistry of Materials, Vol. 18, No. 12, May 2006, pp.
[12] Y. Wang, K. Takahashi, K. Lee and G. Z. Cao, “Nanos-
tructured Vanadium Oxide Electrodes for Enhanced Lith-
ium-Ion Intercalation,” Advanced Functional Materials,
Vol. 16, No. 9, June 2006, pp. 1133-1144.
[13] H. Qiao, X. J. Zhu, Z. Zheng, L. Liu and L. Z. Zhang,
“Synthesis of V3O7·H2O Nanobelts as Cathode Materials
for Lithium-Ion Batteries,” Electrochemistry Communica-
tions, Vol. 8, No. 1, January 2006, pp. 21-26.
[14] M. E. Spahr, P. Bitterli, R. Nesper, M. Muller, F. Kru-
meich and H. U. Nissen, “Redox Active Nanotubes of
Vanadium Oxide,” Angewandte Chemie International
Edition, Vol. 37, No. 9, 1998, pp. 1263-1265.
[15] R. Nesper and H. J. Muhr, “Nanotubes-an Outstanding
Set of Nano Particles,” Chemical, Vol. 52, 1998, pp. 571-
[16] J. Schoiswohl, S. Surnev, F. P. Netzer and G. Kresse,
“Vanadium Oxide Nanostructure: from Zero to Three-
Dimensional,” Journal Physical-Condemns Matter, Vol.
18, No. 4, 2006, pp. R1-R14.
[17] H. Y. Xu, H. Wang, Z. Q. Song, Y. W. Wang, H. Yan and
M. Yoshimura, “Novel Chemical Method for Synthesis of
LiV3O8 Nanorods as Cathode Materials for Lithium-Ion
Batteries,” Electrochimica Acta, Vol. 49, No. 2, January
2004, pp. 349-353.
[18] F. Sediri and N. Gharbi, “From Crystalline V2O5 to
Nanostructured Vanadium Oxides Using Aromatic Amines
as Templates,” Journal of Physics and Chemistry of Sol-
ids, Vol. 68, No. 10, October 2007, pp.1821-1829.
[19] F. Théobald, “Etude Hydrothermale du Système VO2-
VO2,5-H2O,” Journal of the Less-Common Metals, Vol.
53, September 1977, pp. 55-71.
[20] Y. Oka, T. Yao and N. Yamamoto, “Structure Determina-
tion of H2V3O8 by Powder X-ray Diffraction,” Journal of
Solid State Chemistry, Vol. 89, No. 2, December 1990,
pp. 372-377.
[21] T. Chirayil, P. Y. Zavalij and M. S. Whittingham, “Hy-
drothermal Synthesis of Vanadium Oxides,” Chemistry of
Materials, Vol. 10, No. 10, September 1998, pp. 2629-
[22] G. C. Li, S. P. Pang, Z. B. Wang, H. R. Peng and Z. K.
Zhang, “Synthesis of H2V3O8 Single-Crystal Nanobelts”,
European Journal of Inorganic Chemistry, Vol. 11, No.
5, June 2005, pp. 2060-2063.
[23] S. F. Shi, M. H. Cao, X. Y. He and H. M. Xie, “Surfac-
tant-Assisted Hydrothermal Growth of Single-Crystalline
Ultrahigh-Aspect-Ratio Vanadium Oxide Nanobelts,” Crys-
tal Growth & Design, Vol. 7, No. 9, July 2007, pp. 1893-
[24] J. Livage, “Vanadium Pentoxide Gels,” Chemistry of
Materials, Vol. 3, No. 4, July 1991, pp. 578-593.
[25] S. Gao, Z. Chen, M. Wei, K. Wie and H. Zhou, “Single
crystal Nanobelts of V3O7. H2O: A Lithium Intercalation
host with a Large Capacity,” Electrochimica Acta, Vol.
54, No. 3, January 2009, pp. 1115-1118.
[26] T. R. Gilson, O. F. Bizri and N. Cheetham, “Dalton
Transaction,” Journal of the Chemical Society, Vol. 33,
No. 3, 1973, pp. 291-294.
[27] J.-C. Valmalette and J.-R. Gavarri, “High efficiency
Thermochromic VO2(R) Resulting from the Irreversible
Transformation of VO2(B),” Materials Science and En-
Copyright © 2011 SciRes. MSA
Hydrothermal Synthesis of V3O7·H2O Nanobelts and Study of Their Electrochemical Properties
Copyright © 2011 SciRes. MSA
gineering B, Vol. 54, No. 3, June 1998, pp. 168-173.
[28] C. Delmas, H. Cognac-Auradou, J. M. Cocciantelli, M.
Ménétrier and J. P. Doumerc, “The LixV2O5 System: An
overview of the Structure Modifications Induced by the
Lithium Intercalation,” Solid State Ionics, Vol. 69, No.
3-4, August 1994, pp. 257-264.
[29] K. S. W. Sing, D. H. Everett, R. A. W. Haul, L. Moscou,
R. A. Pierotti, J. Rouquerol and T. Siemieniewska, “Re-
porting Physisorption Data for Gas/Solid Systems with
Special Reference to the Determination of Surface Area
and Porosity,” Pure and Applied Chemistry, Vol. 57, No.
4, 1985, pp. 603-619.
[30] M. Toba, F. Mizukami, S. Niwa, T. Sano, K. Maeda, A.
Annila and V. Komppa, “The Effect of Preparation
Methods on the Properties of Zirconia/Silicas,” Journal of
Molecular Catalysis, Vol. 94, No. 1, 1994, pp. 85-96.
[31] F. Sediri and N. Gharbi, “Controlled Hydrothermal Syn-
thesis of VO2(B) Nanobelts,Materials Letters, Vol. 63,
No. 1, January 2009, pp. 15-18.