Journal of Wuhan University of Technology-Mater. Sci. Ed. Apr.

2009 245

OI 10.1007/s11595-009-2245-7

Morphological Evolution of Nb2O5 in a Solvothermal

Reaction: From Nb2O5 Grains to Nb2O5 Nanorods and
Hexagonal Nb2O5 Nanoplatelets

HU Weibing1,3, LIU Zuli3, TIAN Dating1, ZHANG Shengmin3, ZHAO Yimin2, YAO Kailun3
(1. School of Chemical and Environmental Engineering, Hubei Institute for Nationalities, Enshi 445000, China;
2. School of Materials, Mechanical and Manufacturing Engineering, the University of Nottingham, University Park, Nottingham NG7 2RD, UK;
3. Department of Physics, Huazhong University of Science and Technology, Wuhan 430074, China)

Abstract: Novel Nb2O5 nanorods and polygonal Nb2O5 platelets were generated by a simple
solvothermal technique. The geometry evolution of the resultant Nb2O5 from amorphous nanoparticles
to crystallized particles, from polygonal platelets to well-elongated nanorods was been studied in detail.
The processing parameters, including the reaction temperature, reaction time, concentration of the
precursors, and pH value of the solution, which affect the shape and size of the nanorods, were inves-
tigated. The Nb2O5 nanorods with different aspect ratios were examined by XRD, SEM and TEM. The
experimental results show that Nb2O5 nanorod is the orthorhombic structure and well-crystallized. The
growth of the nanorods follows their [001] direction. The successful generation of high quality Nb2O5
nanorods is not only important for transition metal oxide research, but also potentially important for
further formation of new Nb-based 1-D nanostructures, such as NbS2 and NbN.
Keywords: solvothermal; morphological evolution; Nb2O5 nanomateraials

1 Introduction tate with H2O2 aqueous solutions after heating at 348 K

One-dimensional (1-D) transition metal oxide
structures have recently attracted considerable research
interests because of their many promising applications in
various areas[1]. Typical examples include the ZnO[2],
WO3 and Fe2O3 nanowires and nanorods[3,4], which can
be used as sensor materials, catalyst carriers, and in
nanodevice constructions. In particular, niobium oxides
are considered a valuable candidate for biomaterial ap-
plications[5], which is partly due to their chemical inert-
ness[6], thermodynamic stability and low cytotoxicity[7].
However, compared with other transition metal oxides,
niobium oxide nanostructures have been proved some-
how difficult to generate and there are only very few
reports concerning the synthesis of Nb-related 1-D
nanomaterials. Shortly after Feldmann and his
co-workers reported the manufacture of Nb2O5 nanopar-
ticles using Nb(OC2H5)2[8], Pinna et al have employed a
nonaqueous route to synthesize Nb2O5 polyhedral
nanocrystals[9]. The peptization of a niobic acid precipi-
(Received: Jan.12, 2008; Accepted: Apr.9, 2008)
HU Weibing(胡卫兵): Prof.; E-mail: w.hu@tom.com
Funded by the International Cooperation Project of Hubei Province (2006
CA014)
for one week resulted in the formation of poorly crystal-
line Nb2O5 nanoparticles of 4.5 nm in diameter[10]. Re-
cently, Sunkara et al have successfully produced Nb2O5
nanowires at low temperature by utilising an oxygen
assisted plasma technique[11]. We have generated the
NbS2/Nb2O5 nanocables using Nb2O5 nanorods reaction
with H2S[12]. In this report, we described a facile
soft-chemistry approach to synthesize high quality Nb2O5
nanorods, and then discussed the effects of reaction time
and temperatures, and the concentrations of the solvents
on formation of Nb2O5 nanorods.
2 Experimental
A 120 mL PTFE lined autoclave was used in the
solvothermal synthesis. During the experiments, 0.050 g
NbCl5 (0.185 mmol) was dissolved in 2 mL ethanol in a
beaker, and stirred to obtain a thoroughly clear solution.
40 mL cyclohexanol was then added to the solution,
which was then transferred to and sealed in the autoclave,
subsequently heated at 200-240 ℃ in a muffle furnace
for 8-90 h. The autoclave was cooled down to room
temperature naturally after the heating process. The re-
sultant products were thoroughly washed with acetone
for several times to remove any organic by-products, and
246 Vol.24 No.2 HU Weibing et al: Morphological Evolution of Nb2O5 in a…

were then centrifuged in deionized water. The suspension
was transferred by a pipette to a quartz (or Si) substrate to
form a thin film, for further examinations by X-ray dif-
fraction (XRD) and scanning electron microscopy (SEM),
transmission electron microscopy (TEM) and electron
X-rays dispersive spectrum (EDX). By using the 120 mL
autoclave, the resultant solid product is typically about
25 mg, which could be scaled up by utilizing a larger
reaction vessel.
3 Results and Discussion
3.1 Characterization
Fig.1 shows the overall structures of the resulting
Nb2O5 nanomaterials, and Figs. 1c, 1f and 1h exhibit the
1-D structure of the nanorods. The Nb2O5 nanorods are
geometrically uniform and fairly pure, without inclusion
of particulate impurity. They are typically about 1 μm in
length and 50-80 nm in diameter. In Fig.1(g), found that
the nanorods exhibit a hexagonal cross-section at the
ends as marked. It reveals that the nanorods do not pos-
sess round cross-section. Further ED study during TEM
observation is shown that the Nb2O5 nanorods consist of
well-crystallized single crystals (Fig.2, insets). The
compositions of individual nanorods were also verified
by using EDX, which confirms that the nanorods are
chemically pure, containing Nb and O only, in consistent
with the bulk Nb2O5 structures as verified later by XRD.
Fig.2(d) is TEM image of hexagonal Nb2O5 platelets,
which is shown that the hexagonal Nb2O5 platelets are
indeed well-crystallized, as shown in Fig.2(e).
XRD analyses confirm the orthorhombic structure
of the Nb2O5 nanorods, as shown in Fig.3. It is noted from
the XRD profiles that the features of Nb2O5 nanorods are
quite different from those reported of Nb2O5 nanoparti-
cles with similar diameters ranging from 30-80 nm[7,8]. In
the case of nanoparticles, the reported XRD profiles are
almost identical, similar to those of the bulk materials
(JCPDS 030-0873). In our samples, when the aspect ratio
of the nanorods is small (Fig.1(g)), we obtained similar
XRD pattern (Fig.3(b)). However, when the aspect ratio
is large, >10-20, as the nanorods shown in Fig.1(h), the
XRD pattern changes dramatically in terms of the inten-
sities (Fig.3(a)). The intensity of the (180) peak becomes
dominantly stronger than those of all other peaks. We
believe that this is a good reflection of the pronounced
feature of the 1-D nanostructures.

Fig.1 SEM images show effects of reaction temperature, reaction time and concentration of precursors on the final morphologies of the
resulting Nb2O5. The applied conditions are: (a) 215 ℃, 90 h, 4.628×10－3 M; (b) 225 ℃, 90 h, 4.628×10－3 M; (c) 235 ℃, 90 h, 4.628
×10－3 M; (d) 20 h, 235 ℃, 6.477×10－3 M; (e) 36 h, 235 ℃, 6.477×10－3 M; (f) 90 h, 235 ℃ , 6.477×10－3 M; (g) 9.253×10－3 M, 235 ℃
90 h; (h) 2.468×10－3 M, 235 ℃, 90 h; (i) Nb2O5 platelet structures produced at pH = 2.1, 235 ℃, 90 h, 3.08×10－3 M
 Journal of Wuhan University of Technology-Mater. Sci. Ed. Apr. 2009
Fig.2 TEM images of the resulting Nb2O5 nanorods. (a) and (b)
showing the Nb2O5 nanorods with different aspect ratios.
The inset ED pattern in (a) reveals the single crystalline
feature of a nanorod and indicates the [001] growth direc-
tion of the nanorods. (c) Lattice fringe image shows the
(001) plane of the nanorods perpendicular to the nanorod
axis, with a lattice separation of 0.39 nm.(d) and (e) TEM
image and HRTEM image of the hexagonal Nb2O5 platelets
Fig.3 XRD patterns of (a) long Nb2O5 nanorods and (b) short
Nb2O5 nanorods with small aspect ratio, exhibiting the
(180) dominant feature of the long nanorods
3.2 Reaction temperature
The final geometry of the oxide was dictated by the
applied solvothermal conditions. We investigated the
247
processing parameters that affect the shape and size of the
nanorods, which include the reaction temperature, reac-
tion time, concentration of the precursors, and pH value
of the solution. Three sets of reaction temperature were
applied while maintaining other parameters constant
during the synthesis of Nb2O5, with a concentration of
4.628×10 3 M of NbCl5 and reaction time of 90 h. At
－
215 ℃, only large amorphous niobium oxide particles
were obtained, as shown in Fig. 1a whose amorphous
structural feature was also verified by XRD. At 225 ℃,
the resulting crystallised products contain very few short
nanorods mixed with polygonal particles (Fig.1(b)); and
at 235 ℃ pure nanorods are resulted (Fig.1(c)).
3.3 Reaction time
Reaction time shows a significant impact on the
morphology of the products. When 6.477 × 10 3 M
－
NbCl5, short reaction time 20 h and heated at 235 ℃, the
products are mainly nanoparticles with non-uniform size
and shape (Fig.1(d)); at prolonged reaction time of 36 h,
elongated structure are observed (Fig.1(e)). Further ex-
tended the reaction time to 90 h, very pure 1-D oxide
nanostructures are obtained at about 100% conversion
rates, as shown in Fig.1(f).
3.4 Concentration of reactant
The concentration of the NbCl5 shows interesting
influence on the geometry of the final products. At high
concentration, 9.253×10 3 M, heated at 235 ℃ for 90 h,
－
the resulting materials are crystallized polyhedral parti-
cles (Fig.1(g)). At a concentration of 6.477×10 3 M, we
－
have obtained nanorods with an average length of 600 nm
(Fig.1(f)). Further reducing the concentrations gradually
down to 2.469×10 3 M, we have achieved longer and
－
longer nanorods up to 1 μm on average. As a result, the
aspect ratios of the nanorods are increased. It is noted that
the pH values have no significant influence on the
product, as there is very little pH variation while modi-
fying the concentrations of the precursor. A constant pH
value about 0.7 was adopted during the experiments for
nanorods generation. However, when adding deionized
water into the cyclohexanol solution, the pH value is
increased to 2.0-2.1, leading to polygonal platelet prod-
ucts rather than nanorods (Fig.1(i)).
3.5 Growth direction
High resolution TEM image shows that the atomic
planes stacked vertically to the nanorod axis exhibite an
atomic lattice separation of 0.39 nm (Fig.2(c)), corre-
sponding to 0.393 nm of the (001) of Nb2O5. According
to analyses based on the ED results and high resolution
lattice fringe images of individual nanorod, the growth
direction of Nb2O5 nanorods is believed to follow [001].
This can also account for the significantly improved (180)
248 Vol.24 No.2 HU Weibing et al: Morphological Evolution of Nb2O5 in a…
intensities of long nanorods compared with standard
XRD patterns obtained from particulate materials (Fig.3).
For quasi-spherical Nb2O5 particulates, the diffraction
intensities of each crystal planes are determined by their
more or less equivalent sizes in the particles. However for
Nb2O5 nanorods, when crystals elongate along one par-
ticular direction and become longer and longer, as along
[001] in present crystals, those crystal planes parallel to
the [001] growth direction of the nanorod would be the
preferential growth planes, resulting in such planes be-
come dominant along the nanorod axis. In the case of
orthorhombic Nb2O5, the [180] planes of the nanorods
that are parallel to the [001] growth axis of the nanorod
are the preferential growth planes. Their stacking along
the entire nanorod body in the nanorods led to the sig-
nificantly intensified [180] peak in the XRD pattern. The
longer the nanorods is, the stronger the intensities of the
[180] peaks are.
4 Conclusion
In summary, we have successfully generated high
quality Nb2O5 nanorods. The simple and effective low
temperature soft-chemistry process was investigated in
order to realize uniform geometry control over the Nb2O5
nanostructures. Well-crystallized Nb2O5 nanorods with
different aspect ratios are achieved. The growth of the
nanorods follows their [001] direction. The successful
generation of high quality Nb2O5 nanorods is not only
important for transition metal oxide research, but also
potentially important for further formation of new
Nb-based 1-D nanostructures, such as NbS2 and NbN.
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