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Facile hydrothermal synthesis and photocatalytic activity of rod-like

nanosized silver tungstate

Article  in  Micro & Nano Letters · December 2012

DOI: 10.1049/mnl.2012.0765

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Facile hydrothermal synthesis and photocatalytic activity of rod-like nanosized
silver tungstate
Rongxian Zhang1, Haiying Cui2, Xiaofei Yang3, Hua Tang3, Heng Liu3, Yang Li3
1
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People’s Republic of China
2
School of Food and Biological Engineering, Jiangsu University, Zhenjiang 212013, People’s Republic of China
3
School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, People’s Republic of China
E-mail: xyang@ujs.edu.cn

Published in Micro & Nano Letters; Received on 6th October 2012; Revised on 28th November 2012

Rod-like nanosized silver tungstate (Ag2WO4) was synthesised via a facile hydrothermal method and characterised by field emission scanning
electron microscopy, X-ray diffraction, Raman spectroscopy and electron spin resonance spectroscopy. Under ultraviolet (UV) light, nearly
complete degradation of rhodamine B (RhB) was observed in Ag2WO4 suspension after irradiation for 60 min, around 15% RhB was absorbed
in the dark. However, more than 60% of methyl blue was .
absorbed in the dark and the rest was observed to be completely degraded upon UV
light irradiation for 10 min. The formed superoxide (O2 .
2 ) and hydroxyl ( OH) radicals, as well as photoinduced holes were considered to be the
dominant active species in the photocatalytic process.

1. Introduction: With the emergence of the energy crisis and
environmental pollution concerns, the search for various materials
as highly active photocatalysts for hydrogen generation [1–6] from
water splitting and the photodegradation of pollutants [7–13] has
attracted considerable attention over the past few decades. Besides
conventional metal oxide semiconductor photocatalysts such as
TiO2 , ZnO etc., in past years a variety of complex oxides including
vanadate [14–20], molybdate [21–27] and phosphate [28–31] have
been explored as new types of photocatalysts for the degradation of
organic pollutants and H2 evolution. Among those complex oxides,
silver-containing complex oxide photocatalysts have aroused
growing interest. Metal tungstates are one of the important families
of inorganic material that have a high application potential in various
fields. Previous efforts have been made for the controlled synthesis of
tungstates with well-defined nanostructures and FeWO4 crystals [32],
spherical Bi2WO6 [33–35] and ZnWO4 [36– 38]. Facile synthesis
of nanosized Ag2WO4 for photocatalytic degradation of organic
pollutants is rarely found in the literature [39 –42].
In this Letter, we present a facile and effective process for the
preparation of nanosized Ag2WO4 . Rod-like Ag2WO4 nanopar-
ticles were obtained by a simple ion-exchange method in com-
bination with hydrothermal treatment. Organic dyes rhodamine B
(RhB) and methylene blue (MB) were used as model pollutants
to evaluate the photocatalytic activity of the sample under ultra-
violet (UV) light; the results revealed that the as-prepared rod-like
Ag2WO4 nanoparticles exhibited excellent photocatalytic activity,
where almost 20% absorption and 80% degradation were observed
for RhB, whereas more than 60% absorption and around 40% were
obtained for MB, suggesting that the as-synthesised sample has
absorption–degradation characteristics and demonstrates selectivity
towards different organic dyes.
2. Experimental: In a typical synthesis, Na2WO4.2H2O (5 mmol,
1.65 g) and AgNO3 (10 mmol, 1.70 g) were dissolved in deionised
water (40 ml). After the solution was gently stirred for a few
minutes, diluted NaOH (3 M) was dropwise added to adjust the
pH value of the solution to 8.5 with stirring. The reaction solution
was then transferred into a 100 ml Teflon-lined stainless steel auto-
clave and kept in an oven at 1808C for 20 h. The autoclave was left
to cool naturally to room temperature. The obtained precipitate was
collected by centrifugation, washed several times with deionised
water and ethanol and dried at 608C overnight.
The morphologies of the as-synthesised samples were examined
by field-emission scanning electron microscopy (JEOL, JSM-
7001F). The phases of the obtained products were collected on a
Bruker D8 Advance X-ray diffractometer (Cu Ka radiation,
l ¼ 0.15406 Å in a 2u range from 108 to 808 at room temperature.
Raman experiments were performed using a DXR spectrometer
using the 532 nm laser line and measurements were made in
backscattering geometry. UV– Visible diffuse reflectance spectra
were recorded within a 200– 800 nm wavelength range using a
Shimadzu UV2450 spectrometer. Electron spin resonance (ESR)
spectra were recorded at 77 K with an ESR spectrometer (Bruker,
ESP-300E) for the sample (20 mg) in liquid nitrogen under
irradiation with a 500 W mercury lamp.
The optical system for the photocatalytic reaction was a UV lamp.
Organic dye solutions (100 ml, 5 mg/l) containing 100 mg of samples
were put in a sealed glass beaker and first ultrasonicated for 10 min,
and then stirred in the dark for 30 min to ensure absorption–
desorption equilibrium. The suspension was then transferred into a
quartz reactor connected with cooling water. After illumination,
4 ml of samples were taken out at regular time intervals (20 min for
RhB, 10 min for MB) and separated through centrifugation
(10 000 rpm, 10 min). The supernatants were analysed by recording
variations of the absorption band maximum in the UV–Vis spectra
by using a Lambda 25 UV–Vis spectrophotometer.
3. Results and discussion: Figs. 1a and b show the typical scan-
ning electron microscopy (SEM) images of products synthesised
by reacting AgNO3 with Na2WO4 in the hydrothermal process. It
is shown in Fig. 1a that the obtained samples possess irregular
rod-like and plate-like morphology, the enlarged SEM image
shown in Fig. 1b reveals that main lengths of the as-prepared rod-
like Ag2WO4 particles range from 200 to 600 nm, with a diameter
range of 60– 100 nm. Rod-like particles were obtained in large
quantities and a few plate-like particles are believed to have come
from the parallel aggregation and growth of rod-like Ag2WO4 nano-
particles. It is believed that the pH value has a crucial effect on the
formation of a rod-like product, the formation of tiny crystalline
nuclei occurred at first, followed by the growth of larger particles
at the cost of smaller ones according to the well-known Gibbs-
Thomson law [42, 43]. As the reaction continued, irregular nano-
particles vanished and rod-like nanosized particles formed along
the lateral direction of Ag2WO4 .
Fig. 2a shows the X-ray diffraction (XRD) pattern of as-synthesised
Ag2WO4 . It can be clearly seen that the main diffraction peaks of the
sample could be primarily indexed to orthorhombic Ag2WO4 (Pn2n,
JCPDS No. 34–0061). Raman spectroscopy measurements were also
carried out on the sample for confirmation of the structural character-
istics and the spectrum is shown in Fig. 2b. The weak bands in the

Micro & Nano Letters, 2012, Vol. 7, Iss. 12, pp. 1285–1288 1285
doi: 10.1049/mnl.2012.0765 & The Institution of Engineering and Technology 2012

Figure 1 Low- and high-magnification SEM images of nanosized Ag2WO4
a Low magnification
b High magnification
Figure 2 XRD pattern and Raman spectrum of as-prepared nanosized
Ag2WO4
a XRD pattern
b Raman spectrum
range of 200–800 cm21 correspond to the stretching mode of the
21
WO22 4 unit, whereas the intense peak around 880 cm is attributed
to the bending modes of the Ag–O–W unit [39–40].
The photocatalytic performance of the Ag2WO4 sample was
evaluated by the degradation of organic dyes RhB and MB under
UV light and the results are shown in Fig. 3. The photocatalytic
degradation of RhB and MB against irradiation time is displayed in
Figs. 3a and c, respectively. The photocatalytic experiments revealed
that the removal percentage of RhB in the dark is around 15% and the
elimination of MB in the dark is more than 60%, suggesting that the
absorption efficiency of RhB over the sample is obviously higher than
that of MB. When the Ag2WO4 sample was irradiated under the UV
light for 60 min, more than 80% of RhB was photocatalytically
degraded; a further 60 min has no obvious impact on the photo-
catalytic degradation of RhB. However, complete degradation of
MB was observed after only 10 min exposure to UV light, indicating
that the photocatalytic degradation activity of MB is higher than that
Figure 3 Photocatalytic degradation and UV–Vis spectrum of supernatant
of degraded RhB and MB solutions under UV light irradiation
a and c Photocatalytic degradation
b and d UV –Vis spectra
1286
& The Institution of Engineering and Technology 2012
of RhB over the same sample. Figs. 3b and d further demonstrate the
evolution of RhB and MB absorption spectra under different
irradiation times, from which we can see that the concentration of
MB decreased rapidly in a short time, while a gradual decrease in
the absorbance was observed for RhB.
To understand further the process of photoinduced electrons and
holes in photocatalysis, it is important to detect the nature of the reac-
tive oxygen species generated on the surface of catalysts under UV
light irradiation. According to the photocatalytic mechanism, H2O2
could be generated from the reactions of the photogenerated electrons
.
and holes with adsorbed oxygen/H2O, where O2 2 and OH were pos-
sibly involved. Figs. 4a and b show ESR spin-trap signals, with
dimethyl pyrroline oxide (DMPO) of the obtained sample; it is
clearly shown in Fig. 4a that four intensive characteristic peaks of
DMPO – .OH were observed in aqueous dispersion of the sample
after 14 min irradiation; no such signals were detected in the dark
and weak signals could be observed under shorter time (8 min)
irradiation, implying that certain visible light irradiation is essential.
for .OH generation on the surface of the catalyst. The DMPO–O2 2
species were also detected successfully in the methanol dispersion
.
of the sample and six characteristic peaks of the DMPO–O2 2
adducts were observed under 14 min visible light irradiation
(Fig. 4b), also no such signals were detected in the dark for the
sample and a shorter irradiation .
time offers weaker signals. The
ESR results confirmed that O2 .
2 and OH are produced on the surface
of the irradiated Ag2WO4 sample. It is suggested that in a photocata-
lytic process, the photogenerated electrons and holes were produced
under UV irradiation; the electrons and holes generated by the
Ag2WO4 sample could be separated efficiently. The separated elec-
.
trons can reduce O2 to form O2 2 radicals, whereas photoinduced
holes tend to remain on the surface of the Ag2WO4 sample and as a
result WO22 4 ions prefer to attract holes and repel electrons. As a
result, the absorbed H2O on the surface could be oxidised by active
.
holes to .OH radicals. Both the O2 .
2 and OH radicals lead to the.
decomposition of organic dyes; moreover, besides the formed O2 2
and .OH species, active photoinduced holes are able to decompose
organic dyes directly. Moreover, possible photocatalytic reaction
pathways on the basis of experimental results are shown in Fig. 5.
Figure 4 ESR spectra of radical adducts trapped by DMPO in Ag2WO4
aqueous and methanol dispersions
a Ag2WO4 aqueous dispersions
b Methanol dispersions
Figure 5 Possible photocatalytic reaction pathways of Ag2WO4 under
UV irradiation
Micro & Nano Letters, 2012, Vol. 7, Iss. 12, pp. 1285–1288
doi: 10.1049/mnl.2012.0765
4. Conclusions: Rod-like nanosized Ag2WO4 particles were
synthesised via a simple ion-exchanged hydrothermal method.
Under UV irradiation, the as-synthesised catalyst exhibited excel-
lent photocatalytic ability for the absorption and degradation
.
of
organic dyes. It is suggested that the generation of O2 2 and
.OH radicals, as well as the formation of holes, make main
contributions to the photocatalytic performance of nanosized
Ag2WO4 . The findings in this study provide an efficient photo-
catalyst for potential applications in the removal and degradation
of organic pollutants.
5. Acknowledgments: This work was partially supported by the
National Natural Science Foundation of China (grant no.
51102116), the Natural Science Foundation of Jiangsu Province
of China (grant numbers BK2011480 and BK2011534), the
China Postdoctoral Science Foundation (grant no.
2012M511223), the Priority Academic Programme Development
of Jiangsu Higher Education Institutions, the Natural Science
Foundation of Jiangsu Higher Education Institutions of China
(grant numbers 12KJB55000 and 10KJB430001) and the
Scientific Research Foundation for Advanced Talents, Jiangsu
University (grant numbers 11JDG050 and 10JDG057).
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