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Banerjee et al.
A VO-seeded approach for the growth of star-shaped VO2 and
V2O5 nanocrystals: facile synthesis, structural characterization, and
elucidation of electronic structure
 CrystEngComm Dynamic Article Links < C

Cite this: CrystEngComm, 2011, 13, 5328

www.rsc.org/crystengcomm PAPER
A VO-seeded approach for the growth of star-shaped VO2 and V2O5
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nanocrystals: facile synthesis, structural characterization, and elucidation

of electronic structure
Luisa Whittaker, Jesus M. Velazquez and Sarbajit Banerjee*
Received 9th November 2010, Accepted 31st January 2011
DOI: 10.1039/c0ce00832j

Obtaining shape and size control of strongly correlated materials is imperative to obtain a fundamental
understanding of the influence of finite size and surface restructuring on electronic instabilities in the
proximity of the Fermi level. We present here a novel synthetic approach that takes advantage of the
intrinsic octahedral symmetry of rock-salt-structured VO to facilitate the growth of six-armed
nanocrystallites of related, technologically important binary vanadium oxides VO2 and V2O5. The
prepared nanostructures exhibit clear six-fold symmetry and most notably show remarkable retention
of electronic structure. The latter has been evidenced through extensive X-ray absorption spectroscopy
measurements.

Introduction
Vanadium oxides exhibiting various connectivities of distorted
VO6 polyhedra with the potential for the intercalation of extra-
neous species (metal ions and organic molecules) are character-
ized by tremendous structural diversity, which makes this class of
compounds a veritable playground for solid-state chemists.14
The incredible wealth of available crystal structures in this
system is underscored by the scores of distinctive structure types
that exist even for simple binary vanadium oxides. The
complexity of the binary vanadiumoxygen phase diagram has
its origins in the relatively unhindered access that vanadium has
to oxidation states ranging from 1 to +5, the unparalleled
richness of local coordination environments (tetrahedral, octa-
hedral, square pyramidal, dodecahedral), and the adroitness with
which these systems are able to accommodate point defects via
shearing and slips of lattice planes.1,3 The incredible bounty of
available crystal structures translates to some remarkable new
physics, especially since the spatial extent of vanadium d orbitals
implies that several readily accessible structures hover at the cusp
of facile carrier delocalization.5,6 Binary vanadium oxides and
metal vanadates have already proven to be happy hunting
grounds for the discovery of phenomena such as superconduc-
tivity at high pressures, low-dimensional quantum spin transi-
tions, and perhaps most famously, strikingly large metal
insulator phase transitions.7,8 Other layered systems based on the
characteristic V2O5 motif have been of great interest as host
Department of Chemistry, University at Buffalo, The State University of
New York, Buffalo, NY, 14260-3000, USA. E-mail: sb244@buffalo.edu
Electronic supplementary information (ESI) available. See DOI:
10.1039/c0ce00832j
These authors contributed equally to this work.
lattices for the intercalation of species ranging from Li-ions for
electrochromics and rechargeable Li-ion batteries to solvent
molecules and polymers for sensing and actuator applica-
tions.1,4,912 The profusion of geometric and electronic structures
available for vanadium oxides has inspired numerous techno-
logical applications such as for flat-panel displays, thermo-
chromic windows, Mott field-effect transistors,13 infrared
modulators, and optical switching constructs.1416
Over the last decade, the ability to scale materials to finite
dimensions has emerged as an incredibly powerful tool to further
expand the repertoire of available functionality in these mate-
rials.4,9,10 Amongst a few notable examples, Cui and colleagues
have demonstrated the complete conversion of 740 nm wide
V2O5 nanorods to u-LixV2O5 within 10 s upon chemical
lithiation, suggesting a Li-ion diffusion constant that is three
orders of magnitude faster than in the bulk.17 These authors
suggest that the accommodation of Li-ions requires puckering
and transformation of the V2O5 lattice in all three dimensions,
which generates substantial strain and gives rise to a significant
activation energy barrier. In contrast, the nanowires are better
able to relax strains generated upon lattice distortion, enabling
a much quicker transformation to the lithiated u-LixV2O5
phase.17 Analogously, Whittinghams group has systematically
compared the capacity and cycling stabilities of a series of
nanocrystalline and microcrystalline V2O5 samples;1 nanowires
prepared by annealing HxV4O10$nH2O fibers grown by a solgel
process show by far the best performance.18,19 Martin and co-
workers have also demonstrated a two-fold improvement in the
high-rate capabilities of polycrystalline 115 nm diameter V2O5
nanorods grown by templated growth methods as compared to
a 250 nm thin film.9
Pronounced finite size effects have also been noted on the
metalinsulator transition behaviour of VO2 and metal

5328 | CrystEngComm, 2011, 13, 53285336 This journal is The Royal Society of Chemistry 2011
 vanadates. In particular, scaling to nanoscale dimensions offers
the possibility of tantalizing new physics and chemistry since the
characteristic behaviour of single electronic domains can be
examined without modification by grain boundaries and the
nucleation of interphase domain walls.2022 Some unique and
intriguing aspects of the influence of finite size on the metal
insulator transitions of VO2 include a pronounced depression of
the phase transition temperature, massively enhanced hystereses,
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supercooling of the metallic phase, observation of the axial
motion of a single metal/insulator domain wall, and evidence for
a unique coexistence regime wherein metallic and insulating
domains are present within a single nanobeam with proportions
dependent on the subtle interplay between temperature and
strain.2026
In recent years, attention has focused on further refining
control over finite size effects via establishing morphology
control over the growth of nanostructures.2729 Several different
synthetic strategies have been attempted with various degrees of
success including solvothermal methods,21,23,24 templated elec-
trodeposition,4,30 vapor transport,31,32 ion beam sputtering,16,25,27
solgel processes,33 and template-based synthesis.34 However,
even the most generous evaluation of this arsenal of available
techniques leads to the conclusion that current synthetic methods
remain far from being optimal in terms of establishing rational
and predictive control. In this submission, we report a novel
seeded growth strategy that takes advantage of the intrinsic
octahedral symmetry of vanadium(II) oxide, VO, to obtain
nanostars of VO2 and V2O5. The synthetic strategy offers
a reproducible alternative to previous approaches for growing
octahedral microcrystallites and nanostars with star, snowflake,
and asterisk geometries that seem for the most part to be plagued
by poor monodispersity and extreme sensitivity to reaction pH,
and that even under the best conditions yields stars only as one
component of a mixture of different morphologies.3537 The
results also suggest a generalizable approach for using the
intrinsic crystal symmetry of one phase to control the crystal
growth of a second related phase under solvothermal conditions.
To the best of our knowledge, there have been no reports thus far
of V2O5 nanostars with well-defined morphologies.
Experimental section
VO2 nanostars
Hydrothermal synthesis. Nanostructured VO2 nanostars were
synthesized by a solution-based approach using bulk VO2 and
bulk VO as the precursors. Small molecule alcohols and ketones
were used as structure-directing agents and were purchased from
Fisher Scientific. Deionized water from a Barnstead Interna-
tional NANOpure Diamond ultrapure water system (r 18.2
MU cm1) was used to prepare all aqueous solutions. Bulk VO2
(260 mg) was placed within a Teflon-lined stainless steel auto-
clave with a capacity of 23 mL and dispersed with 15 mL of
deionized water and 1 mL of methanol. Subsequently, an
appropriate amount of bulk VO (ranging from 80260 mg) was
added to the mixture to seed the growth of star-shaped nano-
structures. The autoclave was then sealed and maintained at
210  C under hydrothermal conditions for 72 h. The resulting
dark blue precipitates were collected and washed with distilled
This journal is The Royal Society of Chemistry 2011
water and acetone, and then dried at 80  C for 10 h. To investigate
the effect of reaction conditions upon the morphology and prop-
erties of the final products, the reaction temperature, duration of
reaction, and concentration of the VO seed used were varied.
V2O5 nanostars
Vanadium oxide films were fabricated on a Si/SiO2 (300 nm)
substrate coated with a 100 nm Fe layer. The Fe metal catalyst
film was evaporated onto the Si/SiO2 wafer using an electron-
beam evaporator at a pressure of 5  106 Torr. The Fe-coated
substrate was then placed inside a chemical vapor deposition
(CVD) reactor at temperatures ranging from 600700  C and
pressures <1  103 Torr. A ceramic boat containing bulk VO
powder (Cerac, >99%) was placed at the center of a 100 quartz
tube and was transported under a mixture of Ar/air at flow rates
ranging from 47200 sccm. A flow control system (Matheson
TriGas) was used to precisely control the mixing of the two gases.
The temperature inside the furnace was subsequently increased
to 900  C to evaporate the VO powder that was placed in the
ceramic boat. The Fe-coated chips recovered after 35 h
reactions showed the formation of a granular faceted V2O5
structure that was then treated hydrothermally in the presence of
small-molecule aliphatic alcohols. Specifically, the Fe-coated
chip was placed in a Teflon-lined stainless steel autoclave with
a capacity of 23 mL along with 5 mL of deionized water and
300 mL of methanol as the structure-directing agent. The auto-
clave was then sealed and maintained at 210  C under hydro-
thermal conditions for 72 h.
Characterization
Phase identification and evaluation of the crystallinity of the as-
prepared samples were performed by X-ray diffraction using
a Siemens D-500 X-ray diffractometer at a scanning rate of 0.04
degree per second in the 2q range between 10 and 90 using
graphite-monochromated CuKa radiation (l 1.5418 A). 
The morphologies of the nanostructures were analyzed by
scanning electron microscopy (SEM, JEOL JSM-5610LV and
Hitachi SU-70 operated at 20 keV and equipped with an energy
dispersive X-ray analysis detector), high-resolution transmission
electron microscopy (HRTEM, JEOL 2010 operated at an
accelerating voltage of 200 keV), and selected-area electron
diffraction (SAED). Copper grids (300 mesh) coated with an
amorphous carbon film were used for the TEM measurements.
Samples were prepared by placing 2-propanol dispersions of the
nanostars on the grids and allowing them to dry under ambient
conditions.
The metalinsulator phase transitions for the as-prepared VO2
nanostars was analyzed using differential scanning calorimetry
(DSC Q200, TA Instruments) under a flowing high-purity N2
atmosphere in the temperature range between 10 and 150  C.
The electrical properties of the VO2 nanostars were examined
using a homebuilt transport measurement setup based on
a Keithley 6517A electrometer/high-resistance meter and
a Keithley 220 current supply unit. Four-point probe resistivity
measurements were acquired for pressed pellets of the samples
using patterned silver contacts.
The electronic structure of the VO2 and V2O5 nanostars was
analyzed by X-ray absorption spectroscopy performed at the V
CrystEngComm, 2011, 13, 53285336 | 5329
 L-edge, V K-edge, and the O K-edge at National Institute of
Standards and Technology (NIST) beamlines U7A and X23A2
of the National Synchrotron Light Source of Brookhaven
National Laboratory. For near-edge X-ray absorption fine
structure (NEXAFS) spectroscopy experiments at the V L-edge
and O K-edge, a toroidal mirror spherical grating mono-
chromator was used with a 1200 lines per mm grating with
a nominal energy resolution of 0.1 eV. The spectra were acquired
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in partial electron yield mode using a channeltron electron
multiplier located near the sample with the detector at an
entrance grid bias of 200 V to enhance surface sensitivity. A
charge compensation gun was used to avoid sample charging. A
vanadium mesh was used as a reference standard for calibration
of the energy scale for all spectra. To eliminate the effects of
incident beam intensity fluctuations and monochromator
absorption features, the partial electron yield signals were
normalized using the drain current of a freshly evaporated gold
mesh with 90% transmittance located along the path of the
incident X-rays. The soft X-ray data presented here have been
acquired at magic angle (q 54.7  C) incidence of the X-ray
beam to preclude observation of effects due to preferential
alignment within the samples. Pre- and post edge normalization
of the data were performed using the Athena suite of programs.
For transmission XANES experiments at the V K-edge, a Si
(311) channel-cut monochromator was used to select the X-ray
energy. Higher harmonic oscillations were eliminated by a pair of
grazing-incidence mirrors. All XANES spectra at the V K-edge
were collected at room temperature in transmission mode for
powder samples mixed with non-absorbing BN powder and
mounted between two layers of kapton tape. To achieve
approximately 15% absorption, the transmission chamber was
filled with 100% N2, whereas the ionization chamber was filled
with a 60 : 40 mixture of N2 and He. Data were recorded at an
energy resolution of 0.03k in the near-edge region. The obtained
spectra were processed using the Athena and Artemis suite of
software tools. The XANES and NEXAFS data for the nano-
structures were compared to data acquired for bulk binary
vanadium oxide standards (VO 99.5% pure CERAC, VO2 99.5%
pure CERAC, V2O3 99.99% Sigma Aldrich, and V2O5 99.6%
Sigma Aldrich).
Results and discussion
Despite the abundant bounty of crystal structures available for
binary vanadium oxides, relatively few of the structures belong to
high-symmetry space groups. A notable exception is
vanadium(II) oxide VO that crystallizes in the cubic rock salt
structure and exhibits octahedral symmetry (lithiated u-LixV2O5
also adopts a defective rock-salt structure) (Fig. 1A).1,38 The
intrinsic symmetry of VO is further more closely related to that of
tetragonal VO2 (the high-temperature metallic polymorph) than
to the dimerized monoclinic insulating phase of VO2. Conse-
quently, our hope has been not only to use the intrinsic octahe-
dral symmetry of VO to template the growth of star-shaped
nanostructures but to also nudge the system to stabilize the
tetragonal rutile phase of VO2 over other metastable VO2 phases
(VO2(A) and VO2(B)) that are frequently the kinetically trapped
products obtained under solvothermal conditions. Fig. 1 depicts
the crystal structures of various binary vanadium oxide phases
5330 | CrystEngComm, 2011, 13, 53285336
Fig. 1 Schematic depiction of the crystal structures of single-valence
binary vanadium oxides. (A) Cubic rocksalt structure of VO (JCPDS 77-
2173) formed by octahedrally coordinated VO6 units. (B) The high-
temperature metallic rutile phase of VO2 (JCPDS 43-1051), VO2(R). (C)
Low-temperature insulating antiferromagnetic M1 monoclinic phase of
VO2 (M). (D) Orthorhombic V2O5 (JCPDS 41-1426) showing the layered
structure of V2O5 based on zigzag double chains separated by
a pronounced gap.
featured in this submission. The low-temperature insulating
phase of VO2 is characterized by dimerized VV clusters that are
almost molecular in nature, with short and long VV distances of
 respectively; there is considerable twisting of the
2.65 and 3.12 A,
VV pairs away from the crystallographic c axis to define
a zigzag chain of VO6 octahedra.5 Heating this polymorph across
the characteristic insulatormetal phase transition results in
stabilization of the high-temperature rutile polymorph (Fig. 1B)
with collinear chains of VO6 polyhedra along the a axis. The
structural phase transition is also accompanied by halving of the
unit cell size with a unique VV distance of 2.85 A  replacing
the alternating short and long VV dimers.
In contrast, V2O5 crystallizes in a simple orthorhombic
structure comprising layers of [VO5] square pyramids sharing
edges and corners (Fig. 1D).39,40 The layers themselves are weakly
electrostatically bound along the c-axis and the spacing between
the layers provides sites for the facile intercalation of Li-ions
amongst other species.40,41
As noted above VO is used with the expectation that the
intrinsic octahedral symmetry of this structure will allow the
stabilization of star-shaped nanostructures. Two novel synthetic
approaches have been developed to prepare VO2 and V2O5
nanostars. The first approach is based on the hydrothermal
reaction and recrystallization of bulk VO and V2O4 likely
through exfoliation, dissolution, and recrystallization of
hydrated layered intermediates and yields monoclinic VO2
nanostars.24,42,43 The second approach comprises the catalytic
vapor transport of bulk VO, followed by the hydrothermal
treatment of the resulting polycrystalline V2O5 film to form V2O5
nanostars.
The SEM images presented in Fig. 2AF illustrate the
morphological features of nanostructures synthesized by the
hydrothermal treatment of bulk V2O4 and methanol with
different amounts of the VO seed template after reaction for 72 h.
From Fig. 2 it is observed that the as-synthesized six-armed
This journal is The Royal Society of Chemistry 2011
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Fig. 2 Scanning electron micrographs of VO2 nanostars prepared by the
hydrothermal treatment of bulk VO and V2O4: (A and B) low and high
magnification images of samples prepared using a 23% VO : 77% V2O4
precursor ratio; (C and D) low and high magnification images of samples
prepared using a 37% VO : 63% V2O4 precursor ratio; (E) SEM image of
samples prepared using a 43% VO : 57% V2O4 precursor ratio; (F) SEM
image of samples prepared using a 50% VO : 50% V2O4 precursor ratio.
nanostars are geometrically uniform and range in size from 50 to
500 nm in terms of their end-to-end dimensions. The cross-
section thickness and lateral width of the individual arms are
<100 nm justifying the nanostar moniker. Clearly, the molar
ratio of the added VO seed strongly influences the mono-
dispersity and morphology of the obtained products. Nanostars
with six arms endowed with six-fold rotation axes are observed
for VO ratios as low as 23% (expressed as a function of total
added vanadium content), and represent a vast preponderance of
the synthesized nanostructures up to VO loadings of 37%.
Further, increasing the ratio of VO precursors results in the
formation of poorly defined amorphous nanostructured
powders.
The reaction temperature and duration have also been
screened. Notably, star-shaped structures are far sparser after
solvothermal reaction of the same precursor ratios at 180 and
250  C. At lower temperatures, a metastable VO2(B) phase is
stabilized.23 Further extending the reaction time as presented in
Fig. S1 (ESI) results in degradation of the intricate six-fold
symmetry of the nanostructures evidenced in Fig. 2 and remnant
arms of the nanostars are detected within a matrix of poorly
defined VOx nanostructures.
Fig. 3 (and the graphical abstract) shows V2O5 nanostars
formed by the combined vapor transport/hydrothermal dissolu-
tion route from an initial granular and faceted V2O5 thin film
(Fig. 3A). Individual granules in the deposited polycrystalline
V2O5 layer have pseudocubic morphologies perhaps due to the
intrinsic crystal symmetry of the VO precursor. Dissolution of
high-energy surface planes likely promotes the stabilization of
the octahedral geometries. Indeed, consistent with this broad
idea of selective hydrothermal dissolution along specific crystal
growth directions, Fig. 3D shows the incomplete separation of
the six arms indicating unfinished reshaping of the surface-
This journal is The Royal Society of Chemistry 2011
Fig. 3 SEM images of the deposited V2O5 layers and nanostars. (A)
Polycrystalline V2O5 film prepared by the catalytic vapor transport of
bulk VO. (B) V2O5 nanostars formed by the combined vapor transport/
hydrothermal dissolution of vapor-deposited V2O5 layers. (C) High-
magnification of an as-synthesized V2O5 nanostar; inset shows a cross-
sectional image. (D) Incomplete separation of the six arms indicating and
unfinished reshaping of the surface-tethered V2O5 grains.
tethered V2O5 grains. The lateral width of the individual arms is
defined by the extent of dissolution. An alternative scenario may
involve coordination of the added structure-directing agents
(typically 2-propanol or methanol) to specific facets, which are
passivated and protected from hydrothermal dissolution.
Definitive phase identification of the structures is obtained
from XRD measurements. Fig. 4A depicts the corresponding
XRD patterns of the VO2 samples synthesized with different VO
precursor ratios presented in Fig. 2. As corroborated by the SEM
images, the sample prepared with 37% VO appears to be the most
phase pure and all the observed reflections can be indexed to
monoclinic VO2 (Joint Committee of Powder Diffraction
Standards (JCPDS) 43-1051). The strong intensity of the (011)
reflection denotes the preferential growth direction of the stars.
The diffraction peaks are shifted to higher d-spacings likely as
a result of tensile strain originating from scaling to finite size.
Similar size-dependent lattice expansion has also been observed
(in fact to a greater extent) for VO2 nanobelts synthesized by an
analogous synthetic procedure.24
In contrast, below a concentration of 37% VO, a mixture of
a vanadium oxide hydrate V3O7$H2O (JCPDS 85-2401) and pure
monoclinic VO2 is obtained, whereas at higher VO precursor
loadings, unreacted VO is found to be remnant in the reaction
products after 72 h. These results suggest that, as is generally true
of solvothermal reactions, reaction temperature, precursor ratio,
reaction time, and the structure-directing agent must be carefully
optimized to enable VO to serve as an efficacious template for the
formation of phase-pure monoclinic VO2 nanostars.
Fig. 4B shows the XRD patterns obtained for the V2O5 layers
prepared by vapor transport and subsequent hydrothermal
treatment to form V2O5 nanostars. Upon the vapor transport of
a VO layer onto a 100 nm Fe thin film, VO is oxidized to
a granular densely packed V2O5 film with pseudocubic grains
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Fig. 4 XRD patterns for VO2 and V2O5 stars. (A) Diffraction patterns
obtained for samples prepared using varying VO precursor ratios. (B)
XRD patterns of the precursor V2O5 film and the V2O5 nanostars
obtained by hydrothermal treatment of the V2O5 films.
that perhaps result from the intrinsic symmetry of the precursor,
as well as the influence of the metallic substrate. During the
oxidation/deposition process, the underlying metal layer is
oxidized and reflections that can be attributed to iron oxides of
varying stoichiometry (FeO JCPDS 86-2316; Fe2O3 JCPDS 87-
1166; and Fe3O4 JCPDS 19-0629) are clearly observed.
Furthermore, the diffraction pattern for the faceted granular film
can be readily indexed to orthorhombic V2O5 (JCPDS# 41-
1426). Remarkably, after hydrothermal dissolution, the charac-
teristic (00l) reflections of orthorhombic V2O5 strongly dominate
the diffraction pattern suggesting dramatic restructuring and
reshaping of the grains and a strong preferred growth direction
for the nanostars. The almost exclusive observation of (00l)
reflections further lends credence to the idea of dissolution of
higher energy surface planes with greater reticular density. The
orthorhombic structure of the nanostars has further been
confirmed by Raman microprobe measurements (Fig. S2, ESI)
under 514.5 nm laser excitation. The Raman band at 145 cm1
corresponds to external [VO5][VO5] modes and indicates the
retention of long-range crystalline order in the nanostars. The
phonon modes of the antiphase bridging VO are observed at
528 cm1. The higher frequency modes originating from chaining
VO stretching modes are observed at 703 cm1, whereas strong
V]O vanadyl stretching modes are observed at 999 cm1.44
Further structural studies of the VO2 nanostars have been
undertaken using HRTEM and SAED. Fig. 5 shows overview
TEM and lattice-resolved HRTEM images and the SAED
pattern for an individual VO2 star, which reveals the perfect six-
fold symmetry of the stars and indicates that these remarkable
nanostructures are grown along the [011] direction. The SAED
pattern is uniform along the entire core and spicular regions of
5332 | CrystEngComm, 2011, 13, 53285336
Fig. 5 (A) HRTEM image of VO2 nanostars. (B) Lattice-resolved
HRTEM image of one arm of the star showing the separation between
(011) planes. (C) SAED pattern acquired for the same star. (D) Low
magnification TEM image of two superimposed VO2 stars.
the nanostars, indicating that the obtained structures are single-
crystalline objects.
The origin of the strong observed preference for octahedral
symmetry is not yet clear, although several scenarios can be
envisioned including templated growth on VO seeds that have
octahedral symmetry arising from their rocksalt structure38 or
the oriented attachment of crystalline arms grown along the [011]
direction with the elimination of water at the interfaces.45 Cao
et al. have reported the growth of rutile WxV1xO2 snowflake
architectures reflecting the intrinsic symmetry of the rutile
polymorph with a growth axis along the [110] direction.37 These
authors described these structures as growing from nuclei bound
by the six low-index (20 1) facets.37 Regardless of whether a VO
seed grows along six specific crystalline facets or whether
distinctive nanostructures are fused together through aggregative
growth mechanisms, preferential crystal growth must be
invoked. It is likely that upon hydration, exfoliation, dissolution
and recrystallization of tetragonal VO2 (the high temperature
phase that yields monoclinic VO2 upon cooling), the z-potential
of the reaction solution, the intrinsic surface energies of different
exposed crystalline facets, and interactions with the structure-
directing agent (methanol) all have an influence on the relative
growth rates of different crystalline facets.35,36 Consequently,
despite seeding with VO, phase-pure VO2 nanostars are obtained
only within a relatively narrow window of reaction conditions.
Further characterization of the geometric and electronic
structure of VO2 and V2O5 nanostars comes from X-ray
absorption near-edge structure measurements acquired at the V
K-edge, V L-edge, and O K-edge. XANES lineshapes, peak
positions, and intensities at metal K and LIII,II edges yield
valuable information about local electronic structure, the tran-
sition metal oxidation state, ligand type, and site symmetry (in
This journal is The Royal Society of Chemistry 2011
 conjunction with measurements of standards).46 Fig. 6A shows
the XANES absorption spectra for the VO2 and V2O5 nanostars
alongside data acquired for the bulk standard samples. Several
distinctive absorption features are labeled in the spectra and have
been assigned based on dipole selection rules (Dl 1) and
ground-state electronic structure calculations previously repor-
ted in the literature.47,48
The first absorption feature, within 5.0 eV of the absorption
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edge of vanadium metal at 5465.0 eV, is assigned to dipole-dis-

allowed transitions from 1s core states to V 3d levels. This pre-
edge absorption feature is prominently absent from the XANES
spectrum of rock-salt structured VO with perfectly symmetric
VO6 octahedra, further corroborating the high intrinsic
symmetry of this phase.38,47 However, with the progressive
reduction of symmetry in going from VO to VO2 and V2O5,
a finite transition probability exists for the 1s / 3d transition
and a prominent pre-edge absorption feature is discernible in the
transmission spectrum due to greater mixing (hybridization) of
the 3d and 4p states as well as contributions from quadrupolar
transitions.40,47 The pre-edge absorption feature is especially
pronounced for V2O5, as shown in Fig. 6A, and the strong
polarization dependence of this absorption has been used as
a measure of the intrinsic asymmetry and 2D layered nature of
this structure.40,47
For binary vanadium oxides and metal vanadates, the peak
positions, lineshapes, and intensities of the pre-edge absorption
feature strongly depend on the formal vanadium oxidation state,
local coordination geometry (extent to which the structure is
distorted from the perfectly octahedral symmetry of VO), and the
cage size defined by the bond lengths between vanadium and
the nearest-neighbor ligand atoms.4749 Several researchers have
developed semi-empirical methodologies to relate the integrated
peak intensity and the peak position, as determined from deriv-
ative spectra or the centroid of the spectral feature, to the local
coordination environment and formal vanadium oxidation
state.47,48,50
In Fig. 6B, the peak position of the V K-edge pre-edge
absorption feature is plotted as a function of the formal vana-
dium oxidation state based on data acquired for different binary
vanadium oxide standards. A clear linear correlation is observed,
consistent with Kunzls law, since more energy is required to
excite a tightly bound core electron with an increase in the
oxidation state.47 The VO2 nanostar samples have been located
within this plot and corroborate the approx. +4 formal oxidation
state of vanadium even in the samples prepared with high VO
precursor loadings. A more detailed picture of the vanadium Fig. 6 V K-edge XAFS spectra obtained at room temperature for the as-
geometric and electronic structure emerges from the 2D plot of prepared VO2 and V2O5 nanostars. (A) V K-edge spectra clearly showing
the area and the peak position of pre-edge absorption feature the pre-edge feature; note the absence of the pre-edge peak in the VO data
presented in Fig. 6C based on a method developed by Chaurand due to its high symmetry and cubic structure. (B) Plots of the different
et al. for identification of vanadium phases in steel slag.48,51 The spectral features observed in the XANES spectra for different single-
2D plot has distinctive regions that have been correlated to valence vanadium oxide standards plotted as a function of the formal
oxidation state; the peak positions derived from spectra of the
specific vanadium oxidation states and local coordination
as-prepared VO2 nanostars have been located within these plots to
geometries based on the ideas developed above that the peak
determine the average vanadium oxidation state. (C) 2D plot of the
position strongly depends upon the formal vanadium oxidation normalized area and the peak position of pre-edge absorption feature
state and that the intensity of this dipole-disallowed transition is based on a method developed by Chaurand et al. for identification of
a convolved function of the distortion from perfectly octahedral specific vanadium oxidation states and local coordination geometries. (i)
symmetry and the nearest-neighbor bond lengths. The peak V2O5 nanostars, (iiv) VO2 nanostars prepared using the following
positions (derived from the centroids of the spectral features) and precursor ratios: (ii) VO 23% : VO2 77%, (iii) VO 37% : VO2 63%, (iv) VO
the integrated intensities extracted from the XANES spectra of 43% : VO2 57%, (v) VO 50% : VO2 50%.

This journal is The Royal Society of Chemistry 2011 CrystEngComm, 2011, 13, 53285336 | 5333
 the VO2 and V2O5 nanostars have been located on this 2D plot.
The data points corresponding to the VO2 nanostars are clus-
tered around the V4+ distorted octahedral region. Interestingly,
somewhat greater octahedral distortion is evidenced for the
nanostars as compared to bulk monoclinic VO2, which may be
related to the tensile strain evidenced in the XRD measurements
and the effects of surface reconstruction. The datum for the V2O5
nanostars is clearly in the V5+ pyramidal regime again with slight
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distortions from the bulk that could perhaps result from
substrate induced strain-effects.
The other spectral features observed in the V K-edge XANES
spectra further corroborate the arguments presented above based
on the pre-edge absorption feature. The most prominent spectral
feature visible in Fig. 6A corresponds to the transition of a core
photoelectron into the continuum. Due to pronounced oscilla-
tions in the spectra, it can be ambiguous and difficult to precisely
locate the exact position of the absorption edge, and conse-
quently we have used derivative spectra to make this determi-
nation. An additional spectral feature appears 26 eV above the
pre-edge peak, and can be attributed to the dipole-allowed
excitation of a V core 1s electron to a localized 4p state.47 Fig. 6B
indicates that the threshold absorption, absorption-edge, and 1s
/ 4p transitions exhibit a monotonic dependence of their peak
positions with respect to the oxidation state according to Kunzls
law.47 Locating the peak positions of the VO2 nanostars on these
plots further corroborates the V4+ assignment of the oxidation
state of vanadium in these nanostructures.
In contrast to V K-edge measurements that provide insight
into energy band dispersion arising from solid-state effects by
probing the more delocalized levels that are derived from metal p
orbitals, V L-edge (and indirectly O K-edge) measurements
primarily probe V 3d states that are more atomic (localized) in
character.40,52 NEXAFS data acquired at the V L- and O K-edges
serve as a sensitive probe of the unoccupied density of states
above the Fermi level. Fig. 7 shows NEXAFS data acquired at
the V L- and O K-edges for the as-synthesized VO2 and V2O5
nanostars. The two broad resonances centered at 517 and 524
eV correspond to V 2p3/2 / V 3d and V 2p1/2 / V 3d, respec-
tively.53,54 The O K-edge resonances, corresponding to
Fig. 7 NEXAFS data acquired at the V L edge (2p3/2, 2p1/2) and O K
edge (p*, s*) for the as-synthesized VO2 and V2O5 nanostars.
5334 | CrystEngComm, 2011, 13, 53285336
transitions from O 1s core levels to 2p states, are split into p* and
s* components due to strong hybridization of the O 2p states
with V 3d states. The strength of these features further under-
scores the importance of covalent bonding in binary vanadium
oxides.24,55,56 According to Goodenoughs description of the
electronic structure of VO2,5,5557 the V 3d orbitals with t2g
symmetry, dz2 and dx2y2, are pointed towards the ligand giving
rise to s and s* molecular states. Transitions from O 1s to the
latter states of s* symmetry are evidenced in the O K-edge
NEXAFS spectrum as the higher-energy component. In
contrast, the dxz and dyz are oriented to undergo (weaker) side-
ways p interactions with the oxide ligands. Transitions to p*
bands lying just above the Fermi level constitute the low-energy
component of the NEXAFS spectrum at the O K-edge. Finally,
the nonbonding orbital dxy orbital gives rise to a dk band for
tetragonal VO2, which splits into bonding and non-bonding
levels upon the molecular dimerization of adjacent pairs of
vanadium atoms upon undergoing the phase transition to the
low-symmetry monoclinic insulating phase.55,56 The transition to
the dk component is evidenced as a high-energy shoulder to the
p* band. At higher energies, a broader feature is observed that
can be ascribed to transitions from O 1s core levels to O 2p states
hybridized with V 4sp levels. Previous studies on the V L-edge
NEXAFS spectroscopy suggest a 0.8 eV shift in the V 2p3/2 / V
3d and V 2p1/2 / V 3d transitions per oxidation state. Based on
the peak positions and retention of crystal field splitting between
the p* and s* states as well as the constancy of the V LIII and V
LII splitting, it is clear that the essential electronic structure of
monoclinic VO2 and V2O5 has been retained for the nanostars.
Notably, as with most strongly correlated electronic systems, the
orbital, lattice, and spin degrees of freedom in VO2 are closely
related, which gives rise to the incredible sensitivity of the metal
insulator phase transition to external stimuli. On the flip side, the
electronic structure thus exhibits strong sensitivity to the precise
stoichiometry, strain, and incorporation of point defects.
The retention of the electronic structure of VO2 has been
further examined by measuring the metalinsulator phase tran-
sitions of these nanostructures using differential scanning calo-
rimetry and electrical transport measurements. The monoclinic
/ rutile structural phase transformation accompanying the
insulator / metal electronic transition is first order in nature
and thus has a pronounced measurable latent heat.24,58 The DSC
plots shown in Fig. 8 indicate pronounced endothermic and
exothermic features that are retained over scores of cycles
attributed to monoclinic / rutile phase transformations upon
heating and the reverse rutile / monoclinic restoration of
structure upon cooling, respectively. The insulator / metal
phase transformations are observed between 66 and 70  C, fairly
consistent with the temperatures reported for polycrystalline or
single-crystalline VO2.5,59 The restoration of the phase transition
is observed at temperatures between 54 and 58  C. The observed
hysteresis is characteristic of a first-order phase transition and is
known to be especially pronounced upon scaling to finite size
dimensions. Consistent with our previous results for sol-
vothermally grown VO2 nanobelts, the metal / insulator tran-
sition is more affected by scaling to finite size than the insulator
/ metal transitions, perhaps as a result of the ease with which
a percolative threshold can be reached when metallic puddles
coalesce within an insulating matrix. Notably, since the
This journal is The Royal Society of Chemistry 2011

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Fig. 8 (A) DSC curves obtained for VO2 nanostars prepared by the
hydrothermal treatment of bulk V2O4 along with varying (2350%) ratios
of VO as the precursor. (B) Electrical resistivity for a pressed pellet of
VO2 nanostars synthesized at 37% VO precursor loading plotted as
a function of temperature. (C) First derivative (dR/dT) plot showing
a pronounced dip across the metal-to-insulator phase transition of the as-
prepared VO2 nanostars.
nanostars are significantly larger than nanobelts and nanobeams
that have been previously studied, finite size exerts a significantly
smaller impact on the critical temperature and hysteresis.
Fig. 8B plots the electrical resistivity of a pressed pellet of VO2
nanostars plotted as a function of temperature. Although such
a bulk measurement primarily reflects the grain boundary
connectivity between discrete VO2 particles, there is clear
evidence for an insulator / metal transition and the dR/dT plot
in Fig. 8C shows a pronounced dip that establishes a phase
transition temperature of 63  C.
The results noted above thus not only provide a novel
approach for stabilizing star-shaped nanostructures of VO2 and
V2O5 by exploiting the intrinsic symmetry of a closely related VO
phase, but also, of utmost importance to strongly correlated
systems, indicate complete retention of electronic structure in the
obtained crystallites. The overall synthetic strategy may have
broad applicability for the fabrication of nanostructures of other
closely related binary vanadium oxide and metal vanadate pha-
ses and will provide new platforms for elucidating the influence
of shape and size on metalinsulator phase transitions and allied
electronic instabilities.
Acknowledgements
We gratefully acknowledge Dr. Bruce Ravel, Dr. Cherno Jaye,
and Dr. Daniel A. Fischer from NIST for helpful discussions
regarding the XAFS measurements. We are grateful to the
National Science Foundation for support of this work through
DMR 0847169. Acknowledgment is made to the Donors of the
This journal is The Royal Society of Chemistry 2011
American Chemical Society Petroleum Research Fund for
partial support of this research through 50201DNI10. JMV
acknowledges support through a NASA Harriet G. Jenkins pre-
doctoral Fellowship.
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