ARTICLE IN PRESS

Journal of Crystal Growth 291 (2006) 320–324

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Synthesis and characterization of single-crystal MnV2O6 nanobelts

Yi Liua,b, Yuanguang Zhanga,c, Jin Dua, Weichao Yua, Yitai Qiana,
a
Hefei National Laboratory for Physical Sciences at Microscale, Department of Chemistry, University of Science and Technology of China,
Hefei 230026, PR China
b
Department of Chemistry, Zaozhuang University, Zaozhuang 277100, PR China
c
Department of Chemistry, Anqing Normal College, Anqing 246011, PR China
Received 13 October 2005; received in revised form 1 March 2006; accepted 26 March 2006
Communicated by J.M. Redwing
Available online 12 May 2006

Abstract

MnV2O6 nanobelts were prepared from the reaction between MnCl2
4H2O and NH4VO3 solutions under hydrothermal conditions in
the presence of nitric acid (1%, v/v) as an acidifying agent. The synthesized products were characterized by XRD, FESEM, TEM,
SAED, HRTEM and XPS analytical techniques. SAED and HRTEM confirm the single-crystalline nature of MnV2O6 nanobelts. The
nanobelts of MnV2O6 are obvious, with an average diameter of 110 nm, 10 nm in thickness and several tens of micrometers in length. The
effect of pH, reaction time, and temperature on the morphologies of the resulting products has been investigated. The key factors to
control the morphology and a possible formation mechanism were discussed.
r 2006 Elsevier B.V. All rights reserved.

PACS: 61.82.Rx; 81.07.Bc; 81.10.Aj; 81.10.Dn; 82.47.Aa; 82.80.Ej

Keywords: A1. Crystal morphology; A1. One-dimensional structures; A2. Hydrothermal crystal growth; B1. Manganese vanadate (brannerite) nanobelts;
B1. Nanomaterials

1. Introduction Nowadays, vanadates have generated a new interest as

Nanostructured materials, especially one-dimensional
systems have attracted intense interest because of their
distinctive geometries, novel physical and chemical proper-
ties, and potential applications in electronics, optoelec-
tronics, and memory devices [1,2]. By virtue of the
promising building-block function for nanoelectronics
and optoelectronics, the belt-shaped one-dimensional
nanostructures for efficient transport of electrons have
been intensively investigated [3]. In recent years, much
effort has been devoted to developing new approaches to
the syntheses of 1D nanostructrual vanadium oxides
materials [4]. For example, the syntheses of metal and
vanadium oxides (MVO) were respectively reported by our
group [5] and Yu et al. [6].
Corresponding author. Fax: +86 551 3631760.
E-mail addresses: liuyi67@mail.ustc.edu.cn, ytqian@ustc.edu.cn
(Y. Qian).
an electrode material [7,8]. Research has shown that
transition metal vanadates may be promising anode
materials due to their high-specific capacity and layered
crystal structure. In addition to those carbon materials
(such as graphite, etc.), the compound MnV2O6 hydrous
and anhydrous ones, were also proposed to be used as the
anode [9,10]. Just like other various oxides of manganese
and vanadium, MnV2O6 is a typical promising battery
material, and these divalent metal vanadates are of interest
because of their structural relationship to g-MnO2 and the
non-stoichiometric form of manganese dioxides used in the
battery industry. Its electrochemical property highly
depends on the synthetic and processing methods [11,12].
Up to the present; several methods have been reported
about the synthesis of MnV2O6 such as precipitations,
solid-state reactions [11], and wet chemical reactions at low
temperature [12].
Previously, for the convenience of controlling the
composition, crystalline manganese vanadium MnV2O6

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doi:10.1016/j.jcrysgro.2006.03.028
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Y. Liu et al. / Journal of Crystal Growth 291 (2006) 320–324 321

has been synthesized by a polymer gelation method and
investigated for its physical and electrochemical properties
as an anode material for Li secondary battery [8]. The
synthesis of MnV2O6 was also carried out through solid
state reaction between Mn2O3 and V2O5 [11], and
calcinations of hydrous compound above 500 1C which
were precipitated from the solution of NaVO3 and
Mn(NO3)2 [9,10]. Inagaki et al. have reported rod-like
anhydrous crystalline powders of MnV2O6 (brannerite)
successfully precipitated from mixed aqueous solution of
Mn(CH3COO)2 and V2O5 under autogenous hydrothermal
condition [12].
The hydrothermal synthetic route has advantages in
obtaining high-crystallized powders with narrow grain size-
distribution and high purity without heat treatment at high
temperature. Therefore, this method has also been used in
1D nanostructure single-crystal growth. Up to now,
transition metal vanadates with layered structures obtained
through these approaches tend to be composed of various
hydrate vanadium oxides, and there are few reports on the
fabrication of 1D nanostructures via hydrothermal proces-
sion. Especially, the synthesis of MnV2O6 nanobelts has
never been reported. In this paper, we reported a low
temperature process without using any templates or
surfactants to prepare MnV2O6 nanobelts with a high
aspect ratio. In addition, the effect of the solution pH value
to its 1D structure morphology has also been discussed.
2. Experimental section
All the reagents used in the experiment were of analytical
purity and were purchased from Shanghai Chemical
Reagent Company and used without further purification.
In a typical procedure, 1 mmol MnCl2
4H2O and 2 mmol
NH4VO3 powders were put into beakers with 20mL
distilled water separately, and magnetically stirred for
15 min at 80 1C. After that, the solution of MnCl2
4H2O
was added slowly to the NH4VO3 solution to form a
homogeneous solution, in which a small amount of nitric
acid(1%, v/v) was added drop by drop to promote solution
characterized by Hitachi H-800 TEM with a tungsten
filament and an accelerating voltage of 200 kV. High
resolution transmission electron microscope (HRTEM)
image was recorded on a JEOL 2010 microscope. The
chemical composition of the nanobelts was obtained by
X-ray photoelectron spectroscopy (XPS) on a VGESCA-
LAB MKII X-ray photoelectronic spectrometer, using
non-monochromated Mg Ka radiation as the excitation.
The samples used for TEM and HRTEM characterization
were dispersed in absolute ethanol and were ultrasonicated
before observation.
3. Results and discussion
Under present hydrothermal conditions, a series of
different hydrothermal temperature and reaction time were
investigated and it was determined that reaction tempera-
ture of 180 1C and reaction time of 14 h are optimal. In the
meantime, it is necessary that pH value of solution was
controlled between 6.0 and 6.2 in order to obtain the as-
prepared MnV2O6 nanobelts.
The XRD patterns of the products are shown in Fig. 1.
The primary diffraction peaks in Fig. 1 can be readily
indexed to a monoclinic phase, end-centered lattice [space
group: C2/m (12)] of MnV2O6 with the calculated lattice
constants a ¼ 9.3287 Å, b ¼ 3.536 Å, c ¼ 6.765 Å, b ¼ 112.
291, which are in good agreement with the literature results
(JCPDS no.35-0139.). The minor peaks of impurity phases
are present in Fig. 1 (as shown by asterisk). All those peaks
of impurity phase almost accord with the XRD patterns of
manifold oxides. Hence, it is difficult to index peaks of
impurity phase.
Fig. 2(a) is the low magnification FESEM image of the
as-prepared MnV2O6 single-crystal nanobelts. It shows
that the products of MnV2O6 consisted of a large quantity
of nanobelts, with diameters of 110 nm, thickness of 10 nm
(202)

gel till the pH value of the solution was 6.0–6.2. The slurry
-

solution was transferred into a 50 mL stainless autoclave

with a Teflon-liner. The autoclave was sealed and main-
(110)
(201)

tained at 180 1C for 14 h, then air cooled to room

(311) (203)

temperature. The caesious products were filtered off,

(513) (402)
intensity

(111)

washed several times with distilled water and absolute

ethanol, and then dried in a vacuum at 60 1C for 5 h.
(202)

(113)

X-ray powder diffraction (XRD) patterns of the as-

(201)

(023) (205)
(112) -

(510) -
(020)
(001)

(311)
(003)

prepared samples were determined using a Philips X’Pert

-

-
(200)

(402)
-

PRO SUPER X-ray diffractometer equipped with graphite

(312)

(600)

(115)
(204)
(401)

(423)
-

monochromatized Cu Ka radiation (l ¼ 1.541874 Å). The * *

-

*
-

morphology and size of the final products were separately *

characterized by a series of microscopic techniques. Field
scanning electron microscopy (FESEM) images were taken
10 20 30 40 50 60 70 80
with JEOL-6700F scanning electronic microanalyzer.
2θ/degree
Transmission electron microscope (TEM) image and
selected area electron diffraction (SAED) pattern were Fig. 1. Typical XRD pattern of as-prepared MnV2O6 samples.
 ARTICLE IN PRESS
322 Y. Liu et al. / Journal of Crystal Growth 291 (2006) 320–324

Fig. 2. Low magnification FESEM image (a) and high magnification FESEM image (b) of MnV2O6 nanobelts.

Fig. 3. TEM images (a), (b) and SAED pattern (c) of as-prepared single-crystal MnV2O6 nanobelts.

and lengths up to several tens of micrometers. Fig. 2(b) is

the high magnification FESEM image of the as-prepared
MnV2O6 nanobelts. It reveals that the products of MnV2O6
consisted of a large quantity of nanobelts, in which we can
observe obvious features of belt-like structure.
The morphologies and microstructures of the as
prepared MnV2O6 nanobelts were further investigated by
using TEM. Figs. 3(a) and (b) show the low magnification
and high magnification TEM images of as-prepared
MnV2O6 products, respectively. The TEM images also
demonstrate that the obtained products take on uniform
belts bundle array. The microstructures of nanobelts were
consistent with those of FESEM results. SAED analysis of Fig. 4. TEM image of typical MnV2O6 nanobelt (a) and HRTEM image
MnV2O6 taken from some parts of a single nanobelt gave of the single MnV2O6 nanobelt (b).
monoclinic ED pattern, revealing the single crystalline
nature of the nanobelts. The typical SAED pattern of the
single MnV2O6 nanobelt is shown in inset of Fig. 3(c). MnV2O6. The (1 1 0) plane in MnV2O6 is oriented parallel
The TEM image (Fig. 4(a)) of representative single to nanobelt growth direction. These substantiate that the
nanobelts and HRTEM observation for individual nano- nanobelts are single crystalline.
belt provide additional insight into the structure of XPS analysis further confirms the element component of
MnV2O6. Fig. 4(b) displays the HRTEM image taken MnV2O6 nanobelts. As shown in Fig. 5, the survey spectra
from a single nanobelt and recorded from the [1 1 0] zone demonstrate the presence of Mn, V, and O. The high-
axis, which shows the clearly resolved lattice fringes. The resolution XPS spectra from V 2p to O 1 s region of the
lattice fringes in Fig. 4(b) show the integrality of crystal- nanobelts of MnV2O6 show the binding energies (BE) of V
linity of the nanobelt. The inter-planar spacing was 2p3/2(516.85 eV), V 2p1/2 (524.22 eV) and O 1 s (529.80 eV),
measured as 3.2 Å, corresponding to the (1 1 0) plane of As far as Mn2+ ion and Mn3+ are concerned, their ion BE
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Y. Liu et al. / Journal of Crystal Growth 291 (2006) 320–324 323

3000
O1s Mn2p3/2 Mn2p1/2
2300

Relative intensity(cps)
Relative intensity(cps) 2500

V2p3/2 2200
2000

V2p1/2 2100
1500 4+
V
2000
1000
1900
510 515 520 525 530 535 635 640 645 650 655 660
Binding energy (eV) Binding energy (eV)

Fig. 5. XPS spectra of the as-prepared MnV2O6 nanobelts.

of Mn2p3/2 are contiguous and almost cannot to be nanobelts. SAED and HRTEM analyses confirm that the
discerned. The reason of obviating Mn3+ ion in products nanobelts are single crystalline. The key factors to control
is based on the consideration that NH+4 ion in the solution the morphology and a possible formation mechanism were
may block the oxidation reaction process of Mn2+ to discussed. The new synthetic route is also expected to be
Mn3+. The BE of Mn2p3/2 (641.45 eV) display Mn2+ ion applicable to the synthesis of other transition metal
in existence. The high-resolution spectrum of MnV2O6 vanadates nanobelts. The obtained sample might find
nanobelts also shows that V 2p3/2 consists of two possible application as an electrode material in lithium ion
overlapping peaks. The peak at BE ¼ 516.85 eV may be batteries.
assigned to V5+ ions, and the one at BE ¼ 515.50 eV to
V4+ ions. According to the analysis of quantification, the
ratio of V5+ ions to V4+ ions is 1:0.168. Such overlapping Acknowledgements
peaks are usually observed in ternary vanadium oxides
bronzes containing mixed valences of V5+ and V4+ [13]. Financial support from the National Natural Science
The result shows existence of a small quantity of Foundation of China and the 973 Project of China is
quadrivalence vanadium oxides in the as-prepared pro- greatly appreciated.
ducts, which is in agreement with analyses of XRD pattern.
Although the exact mechanism for the formation of
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