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Ultrathin tungsten oxide nanowires: oleylamine

assisted nonhydrolytic growth, oxygen vacancies
Cite this: RSC Adv., 2015, 5, 77423
and good photocatalytic properties†
Fenglin Liu,a Xianjie Chen,a Qinghua Xia,a Lihong Tian*ab and Xiaobo Chen*b

Ultrathin tungsten oxide nanowires with diameter of around 1.1 nm have been fabricated through a simple
oleylamine (OA) assisted nonhydrolytic process. In the process, the amount of OA, reaction temperature
and time impacted on controlling the formation of tungsten oxide ultrathin nanowires. At high W/OA
molar ratios (>1 : 1), oriented attachment of OA molecules resulted in the preferential growth of
Received 3rd July 2015
Accepted 7th September 2015
nanowires along the [001] direction. At low W/OA molar ratios, small nanoparticles self-assembled into
ultrathin nanowires. The ultrathin tungsten oxide nanowires exhibited a high photocatalytic activity for
DOI: 10.1039/c5ra12993a
the degradation of Rhodamine B under visible light, likely due to their enhanced visible-light absorption
www.rsc.org/advances and the presence of oxygen vacancies.

modern materials science, chemistry, and physics, due to their

1. Introduction high surface area, reduced grain boundaries, direct charge
Photocatalytic oxidation technology utilizing solar energy has transfer pathways, and strong quantum size effects.8 Espe-
attracted increasing interest in decomposing various envi- cially, the short charge diffusion length and more reactive sites
ronmental contaminants.1 Compared with TiO2, the most in ultrathin nanowires bring in fantastic properties in photo-
popular photocatalyst, tungsten oxide can extend the absor- catalysis.9 Non-hydrolytic approaches have been successfully
bance to the blue region of the solar spectrum, as it has a taken to control the morphology, dimensions and particle size
band gap energy of around 2.4–2.8 eV (ref. 2) and its deep of nanomaterials. Recently, some achievements on ultrathin
valence band edge (3.1 eV) is much more positive than the nonstiochiometric tungsten oxide was also obtained through
H2O/O2 oxidation potential and suitable for photo-oxidising it, particularly, W18O49 nanowires. For instance, Moshofsky
organic pollutants under visible light.3 Nevertheless, et al. synthesized the nonstiochiometric tungsten oxide
conduction band level of WO3 (0.5 eV vs. NHE) is more posi- nanowires with diameter of 1–4 nm by controlling the ratios of
tive than the potential for the single-electron reduction of W(CO)6, octadecanol and octadecene.10 Ye et al. obtained
oxygen, leading to the low light energy conversion efficiency W18O49 nanowires with diameter of 0.9 nm with WCl6
because of high recombination of excited electrons and precursor in ethanol.11 Niederberger and co-workers achieved
holes.4 Up to now, several approaches have been taken to the preferential growth of W18O49 along [010] direction and
solve the problem: such as platinum loading to induce a obtained nanowires with a diameter of 1.3 nm with deferox-
multielectron O2 reduction;5 carbon materials (carbon amine coordinating with tungsten atoms.12 However,
nanotube and graphene) composites to improve the photo- controlled synthesis of ultrathin tungsten oxide nanowires
catalytic activity by forming W–C bond to benet the electron with the diameter closing to one cell unit size (<2 nm) is of
transfer;6 advanced nanoarchitecture tuning to increase great interest for enhancing photocatalytic activity. Moreover,
surface area and pores, etc.7 it is also vital to clarify their growth mechanism for extending
One-dimension (1D) nanomaterials, such as nanowires, their applications.
nanobelts and nanorods are one of the hot research topics in In this work, we presented an oleylamine (OA)-assisted
synthesis of ultrathin tungsten oxide nanowires in benzyl
alcohol (BA) solution. Three critical factors, the amount of
a
Hubei Collaborative Innovation Center for Advanced Organochemical Materials, oleylamine, reaction temperature and time, were investigated to
Ministry-of-Education Key Laboratory for the Synthesis and Applications of Organic gure out the growth mechanism of ultrathin nanowires in
Functional Molecules, Hubei University, Wuhan 430062, China. E-mail: tian7978@ detail. The diameter of nanowires could be reduced to around
hubu.edu.cn
1 nm and the length could reach several micrometers. More-
b
Department of Chemistry, University of Missouri – Kansas City, Kansas City, Missouri
over, the photocatalytic performance of ultrathin nanowires was
64110, USA. E-mail: chenxiaobo@umkc.edu
† Electronic supplementary information (ESI) available. See DOI:
also studied in visible light region.
10.1039/c5ra12993a

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2. Results and discussion

2.1 XRD patterns and Raman spectra
The simple one-spot synthesis with tungsten chloride in benzyl
alcohol resulted in the formation of a yellow-green powder
(reference sample), which was characterized by XRD and shown
in Fig. 1a. The sharp and intensive peaks indicated a highly
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crystalline nanostructure. The obvious diffractive peaks with 2q

at 23.1
, 23.7
, 24.2
, 34.1
corresponded to the (002), (020),
(200), and (202) crystal planes of monoclinic phase of WO3 with
lattice parameters of a ¼ 7.297, b ¼ 7.539, and c ¼ 7.688  A
(JCPDS no. 43-1035),13 respectively, which is different from Nie-
derberger's report.14 Interestingly, with the addition of oleyl-
amine and when the molar ratio of WCl6 to OA was 0.5, only the
diffractive peaks of (002) plane was observed and the other
reections were much weak, thus manifesting tungsten oxide
nanowires selectively grew along the [002] direction.15 Here, it
was difficult to assign the nanowire to special crystal structure
from XRD pattern because amount of stoichiometric or Fig. 2 (a) The whole spectroscopy of WO3x (1–2) nanowires, (b) W 4f
nonstoichiometric tungsten oxide had rather similar structure.16 and (c) O 1s XPS spectra of WO3 (reference sample) and WO3x (1–2)
The Raman spectrum of the tungsten oxide nanowires is nanowires, (d) FT-IR spectrum of WO3x (1–2) nanowires.
shown in Fig. 1b. The strong and well-dened bands at 807, 713,
326, 270 cm1 could be assigned to monoclinic tungsten oxide,
which could support the XRD results. The bands at 270 cm1 binding energy (35.8 eV and 37.8 eV), indicating the presence
corresponded to O–W–O bending modes, and the bands at 713 of W–O–N bond.20 The linkage of W atoms and oleylamine
and 807 cm1 were ascribed to the stretching modes of the (W–O–N) likely induced the charge imbalance of W–O and
W–O–W.17 The relatively strong peak observed at low frequency resulted in the surface defect, even the color change (see
(136 cm1) and the weak band at 326 cm1 were attributed to following UV-vis DRS results). More importantly, two peaks
the O–O deformation and W–O deformation modes, respec- occurred at relatively low binding energy (34.8 eV and 33.3 eV),
tively,18 indicating the anisotropic atoms aligning on the surface revealing the existence of W5+ and W4+ in nanowires, accom-
of nanowires. panying with the appearance of oxygen vacancy.21 Also, an
obvious difference was shown in Fig. 2c: the O 1s spectrum of
WO3 nanosheets demonstrated the obvious peaks ascribed to
2.2 XPS and FT-IR spectra lattice oxygen (530.0 eV) and the hydroxyl groups (532.0 eV).
Unlike WO3 nanosheets, the band of lattice oxygen up-shied
XPS spectra were conducted to detect the surface composition
to 530.7 eV and a new peak at 528.7 eV was possibly attributed
and valence of elements in tungsten oxide nanowires. It can be
to the W–O–N bond. The shis of both W 4f and O 1s in
seen from Fig. 2a that W and O were the main constituent
nanowires indicated that the chemical environment of W and
elements and carbon probably came from the impurity of XPS
O atoms in nanowires changed compared with that in WO3
detect and residual organic molecule. The W 4f XPS spectra in
nanosheets and likely resulted in the deformation of W–O and
Fig. 2b presented two strong peaks at the binding energy of
O–O bond, coincident with the Raman investigation.
35.3 eV and 37.3 eV matched well with reported values of the
The FT-IR spectrum of tungsten oxide nanowires was
W6+ oxidation state for WO3 nanosheets,19 whereas a distinct
shown in Fig. 2d. The strong bands in the region of 1000–500
difference shown in the tted curves of WO3x nanowires that
cm1 were assigned to the characteristic stretching vibrations
two peaks corresponding to W6+ shied to much higher
of W–O (950 cm1) units and the bridging oxygen atoms
O–W–O (600–780 cm1).22 The peaks at 1626 and 3400 cm1
came from the physically adsorbed water and the hydroxyl
groups. Two vibrations at 2921 cm1 and 2844 cm1 were
attributed to the –CH3 and –CH2 stretching vibrations,
indicating the presence of residual oleylamine molecule on
the surface of tungsten oxide.

2.3 Morphology and structure

For further investigate the structure of WO3x nanowires, TEM
Fig. 1(a) XRD patterns of WO3 (reference sample) and WO3x (1–2) and HRTEM micrographs were performed and shown in Fig. 3.
nanowires, and (b) Raman spectrum of the WO3x (1–2) nanowires. The reference sample WO3 synthesized by benzyl alcohol route

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Fig. 4 TG-DTA curves of the WO3 (reference sample) and WO3x

(1–2) nanowires.

2.5 Growth of WO3x nanowires

Fig. 3 (a) TEM image of WO3 (reference sample), (b) TEM image of It is known that the synthesis of nanostructure usually
WO3x (1–2) nanowires, (c) HRTEM micrograph, and SAED pattern (the encounters with many sensitive reaction parameters. In order to
inset) of WO3x (1–2) nanowires, and (d) schematic representation of clarify the growth mechanism of WO3x nanowires, three main
monoclinic WO3 along c axis.
factors, the concentration of oleylamine, reaction temperature
and time, are investigated in detail here.
Using benzyl alcohol (BA) as the solvent and WCl6 as the
was nanosheets with size of 100–200 nm (Fig. 3a). Neverthe-
precursor, the controllable synthesis of tungsten oxide nano-
less, WO3x nanowires were achieved with the control of
wires could be achieved by straightforward solvothermal
oleylamine (Fig. 3b). The diameter of nanowires was uniform
method with the aid of OA. Fig. 5 clearly demonstrated the
and around 1.9 nm, but the length, from 200 nm to several
morphology transfer of tungsten oxide from nanosheets to
micrometers, could not be estimated accurately on account of
nanowires with increasing the amount of oleylamine. WO3
the twisted bundles in Fig. 3b. Also, the clear lattice fringes in
nanosheets assembled by small grains were obtained via benzyl
Fig. 3c (HRTEM) veried the highly crystalline tungsten oxide
alcohol route under the condition of 180
C and 24 h (Fig. 5a).
nanowires. An interplanar d-spacing of 0.383 nm should be
However, with low concentrations of OA (i.e. molar ratio of
ascribed to (002) crystal plane of monoclinic WO3, revealing
W : OA ¼ 2 : 1), nanosticks with widths of 15–30 nm and
nanowires grew along the c axis (Fig. 3d), which was in good
lengths of around 63–200 nm were formed, and moreover, the
agreement with the XRD results. The selected area electron
surface of nanosticks were crude (Fig. 5b). At higher OA
diffraction pattern in the inset only showed one intense
concentrations, such as molar ratio of W : OA ¼ 1 : 1, it seemed
diffraction ring, corresponding to the 002 reection of the
that nanosticks were stripped into the nanowires gradually and
WO3x nanowires. All other diffuse and broad diffraction
some short wires were visible in Fig. 5c. When the molar ratio
rings were attributed to the much weak reections. The
reached 1 : 1.5, uniform nanowires were formed with the
electron-induced X-ray uorescence (EDX) analysis was
diameter of about 1.1 nm and length of 100 nm (Fig. 5d), which
employed to determine the composition of the tungsten
was roughly same to the length of nanosticks in Fig. 5b. Much
oxide nanowires (see ESI Fig. S1†). There were oxygen, tung-
longer nanowires (>300 nm) grew at the molar ratio of W : OA ¼
sten and carbon elements existed in the nanowires. The
1 : 2, but the diameter did not change (Fig. 5e). Nanowires
signal of carbon probably came from the residual organic
began to be cut into short segments with the excess OA content
compound.
(W : OA ¼ 1 : 2.5) (Fig. 5f). Accordingly, oleylamine contributed
to the formation of ultrathin tungsten oxide nanowires, and
2.4 TG-DTA analysis their diameter and length could be tailored by simply adjusting
The thermal behaviour of the samples was studied by TG-DTA the molar ratio of WCl6 to OA.
analyses in an air atmosphere with a heating rate of 10
C In addition, an interesting shi of XRD diffractive peaks of
min1 and displayed in Fig. 4. The weight loss up to 350
C tungsten oxides took place in the presence of oleylamine (see
might be assigned to desorption of surface-adsorbed water, the ESI Fig. S2†). At the low OA concentration (molar ratio of
structural water elimination and physically adsorbed organic W : OA ¼ 2 : 1), the main diffractive peaks of (002), (020) and
molecule for both samples.23 It is noteworthy that WO3 (1–2) (200) shied 4
to low diffraction angle, indicating the OA
nanowires showed a dramatic weight loss about 17% compared molecule entered into the crystal lattice and likely resulting in
to that of WO3 nanosheets between 350–500
C, attributed to the lattice expansion of tungsten oxide. With the increasing of
the loss of surface capped OA molecule. OA concentration, the peaks ascribed to (020) and (200) planes

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Fig. 6 TEM images of WO3 (1–2) synthesized with different reaction

time and temperature at 180
C. (a) 6 h, (b) 18 h, (c) 30 h, (d) at 150
C,
24 h.

capping regents.25 In our experiments, byproducts, benzalde-

hyde (m/z ¼ 106), benzyl chloride (m/z ¼ 126) and benzyl ether
(m/z ¼ 198), were detected (GC-MS results). Accordingly, the
growth of tungsten oxide underwent the process that WCl6
reacted with benzyl alcohol rstly to produce the tungsten
alkoxide, then the condensation of tungsten alkoxide to form
Fig. 5 TEM images of all tungsten oxide synthesized with different
W–O–W unit, thus WO3 nanosheets emerged. This process is
molar ratio of WCl6 to OA at 180
C, 24 h. (a) Without OA, (b) W : OA ¼
2 : 1, (c) W : OA ¼ 1 : 1, (d) W : OA ¼ 1 : 1.5, (e) W : OA ¼ 1 : 2, and (f) proposed as follows:
W : OA ¼ 1 : 2.5.

wore off and the (002) peak intensied, ultimately monoclinic

WO3x nanowires grew.
Also, the effects of reaction time and temperature on the
formation of nanowires were studied at the condition of W : OA
¼ 1 : 2 (molar ratio) to gure out the optimal growing condition
of tungsten oxide nanowires. We found that reaction time
impacted the length of nanowires. As shown in Fig. 6, aer the It was similar to the other reported synthesis of metal oxide
solvothermal reaction for 6 h at 180
C, only short WO3 nano- by nonhydrolytic method.26 However, in the presence of oleyl-
rods with an average length of 20–50 nm accompanying nano- amine, the preferential growth direction of tungsten oxide
particles formed (Fig. 6a); the 18 h reaction led to slightly longer surprisingly changed. So it is interesting to see through the
WO3x nanowires and small amount of them attained 160 nm growth pathway of nanowires clearly. Based on the above results
(Fig. 6b); growth for 24 h produced nanowires with length > and the crystal structure of monoclinic WO3, we inferred that
300 nm (Fig. 5e). However, the longer reaction time (i.e. 30 h) oriented attachment of OA molecule on the (020) plane of
resulted in the nanowires tangled with each other (Fig. 6c). In monoclinic WO3 was responsible to the tungsten oxide nano-
addition, relatively low temperature brought about tungsten wires, as a large number of tungsten atom centrally located in
oxide bundles (Fig. 6d), which was likely related to high boil (020) plane and oxygen atom mainly distributed in the cross
point of OA and not fully extended C–C chain in low section of (002) and (200) planes (see the ESI Fig. S3†). As shown
temperature.24 in Scheme 1, at low OA concentration, OA molecule inserted
Benzyl alcohol solvent has been proven to provide a decent into lamellar spacing and coordinated with the W atom in (020)
environment to synthesize and tailor the shape and structure plane, limiting the crystal growth along b axis at a certain extent,
of metal oxide nano-architectures with the help of organic thus leading to the nanosticks (Fig. 5b). While increasing the

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and used without further purication. Briey, 0.8 g WCl6 was

quickly placed into mixed solution of 40 mL benzyl alcohol and
a desired content of OA by vigorously stirring. The color of
solution changed from yellow to dark blue. Subsequently, the
solution was transferred into a Teon-lined, stainless autoclave
at 180
C for 24 h. The powders were washed with acetone,
absolute ethanol and deionized water several times, then dried
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at 70
C for a day. The nal product was collected and denoted

as WO3x (a–b), wherein a–b is the molar ratio of WCl6 to OA.
The reference WO3 sample was prepared under the same
condition without oleylamine.

3.2 Characterizations
Scheme 1 The proposed growth process of WO3x nanowires.
The crystalline structure of as-prepared samples was deter-
mined by X-ray powder diffraction (XRD, Bruker D8 advance),
with Cu Ka radiation (l ¼ 1.54  A) at the scan rate of 5
min1
amount of OA molecule could destroy the nanosticks because of
with a step of 0.02
. Morphologies of samples were studied by
the strong mutual repulsion between the long C–C chains of OA,
transmission electron microscopy (TEM, FEI, Tecnai G20)
and prevent the formation of W–O–W unit along a axis due to
and a JEM-2100UHR high-resolution transmission electron
the coordination of W atoms and OA. Consequently, small
microscope (HRTEM). X-ray photoelectron spectroscopy
nanocrystals produced and self-assembled into ultrathin
(XPS) measurements were carried out using a VG Multilab
nanowires along c axis. This could be conrmed by TEM image
2000 spectrometer with an Al Ka X-ray source (Thermo
of nanowires in formamide, where only small uniform nano-
Electron Corporation), and all the spectra were calibrated to
particles can be observed (see ESI Fig. S4†).
the C 1s peak at 284.6 eV. The UV-vis diffuse reection spectra
were obtained for the dry-pressed disk samples on a UV-vis
2.6 Photocatalytic activity of WO3x nanowires spectrophotometer (UV-2550) by BaSO4 as the reectance
The photocatalytic activity of WO3x nanowires was evaluated by sample. Raman spectra were recorded on a laser micro-
the photodegradation of RhB dye under visible light irradiation. Raman spectrometer (Invia, Renishaw). Fourier transform
As seen from Fig. S5a (see ESI†), WO3 nanosheets showed very infrared spectroscopy (FT-IR) spectra were obtained on a
poor visible-light photocatalytic activity. The obtained products Nicolet IS10 spectroscope to investigate the surface organic
in the presence of OA manifested only slightly enhanced activity species on all tungsten oxide. Simultaneous thermogravi-
until the molar ratio of W : OA attained the 1 : 1.5, that is, metric and differential thermal analyses (TGA/DTA) of the
ultrathin nanowires presented the signicantly increased pho- samples were performed on a thermal analyzer (SDT Q600) in
toactivity under visible light. Apparently, the ultrathin WO3 (1–2) air with a heating rate of 10
C min1 in air atmosphere. Gas
nanowires with diameter about 1.1 nm showed the highest chromatography-mass spectrometry (GC/MS, QP2010, Ultra)
photocatalytic activity of WO3x nanowires. In our experiment, was used to analyzed the by-products in the nonhydrolytic
BET surface area is not the main contribution to the high pho- synthesis. BET surface area of samples was performed on a
tocatalytic activity because nanowires showed a relatively low BET surface area and porosity analyzer (GWGB SCI & TECH,
surface area compared with reference WO3 nanosheets (see the BK112T). Prior to the BET analysis, the powder samples were
ESI Table S1†), which likely related to the capped OA molecule on degassed at 200
C for 2 h to remove the adsorbed H2O from
the surface WO3x nanowires. Thus, the high photocatalytic the surface.
activity possibly ascribed to the enhanced absorption and oxygen
vacancy. As shown in Fig. S5b (see ESI†), all samples obtained
with the existence of OA had enhanced absorption in visible light 3.3 Photocatalytic test
region, matching with the color change from yellow-green to The photocatalytic performance of all samples was evaluated by
blue. Moreover, it is noted that all tungsten oxide nanowires degrading Rhodamine B (RhB) using a 300 W high-pressure
(W : OA < 1 : 1.5) exhibited a tailed absorption, likely indicating xenon lamp (CEL-HXF300). In a typical experiment, 10 mg of
the existence of oxygen vacancy on nanowires. They can likely photocatalysts were suspended in 50 mL of 10 mg L1 RhB
promote the enhanced absorption and separation of electrons aqueous solution. Before light irradiation, the suspension was
and holes and led to the enhanced photocatalytic activity.27 sonicated for 30 min and stirred for an hour in the dark to
ensure the establishment of the adsorption/desorption equi-
3. Experimental section librium of RhB on the catalyst surface. Then, the solution was
placed in a quartz reaction vessel and bubbled with air. At given
3.1 Synthesis of ultrathin tungsten oxide nanowires time intervals, 5 mL solution was taken out and centrifuged.
The tungsten oxide nanowires were synthesized by OA assisted The concentration of RhB was monitored by colorimetry using a
solvothermal method. All chemicals were of analytical grade UV-vis spectrophotometer (UV-2550).

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(b) B. Moshofsky and T. Mokari, Chem. Mater., 2013, 25,

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