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DOI 10.1007/s10876-013-0562-7
ORIGINAL PAPER
Mirjana I. Čomor
Introduction
T. B. Novaković Z. M. Vuković
IChTM-Department of Catalysis and Chemical Engineering, University of Belgrade,
Njegoševa 12, 11000 Belgrade, Serbia
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All chemicals: Na2WO42H2O (99 % Riedel-de Haën), ZnCl2 (99 % Merck), non-
ionic copolymer surfactant Pluronic F68 (Polyoxyethylene-polyoxypropylene block
copolymer, Mn * 8,400 (Aldrich)), NaOH (98 % Fluka) and ZnO (C99 % Sigma-
Aldrich), were of the highest purity available and they were used without further
purification.
Synthesis
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respectively. During the reflux, precipitation of ZnO and ZnWO4 took place. The
obtained ZnO/ZnWO4 nanoparticles were separated from solvent containing
copolymer immediately after synthesis by using ultra-centrifugation. Synthesized
ZnO/ZnWO4 nanoparticles were washed several times with ethanol and distilled
water using centrifugation in every washing step and annealed at 95 °C for 18 h.
The chemical composition was checked using JEOL JSM 6460 LV (SEM)
equipped with the Energy Dispersive Spectrometer (EDS INCA x-sight Oxford
Instruments). The used acceleration potential was 25 kV. ZnO/ZnWO4 pellets with
thickness around 2 mm were coated with carbon. Only Zn, W and O were detected
in our samples. From atomic and weight present ratio of Zn and W we estimated that
ZnO:ZnWO4 ratio was about 1:2, in moles, for all samples.
Structural Characterization
Optical Properties
Diffuse reflectance spectra (DRS) of the ZnO/ZnWO4 pellets were recorded using
Perkin Elmer Lambda 9 UV–Vis-NIR Spectrophotometer. Photoluminescence (PL)
spectra were obtained using Perkin Elmer LS 45 Luminescence spectrometer.
Textural Properties
Photocatalytical Testing
Methylene blue (Fluka) and Rhodamin B (Sigma) were used as model dyes to
evaluate the photocatalytic activity of the commercial ZnO and synthesized ZnO/
ZnWO4 samples. In a typical experiment 0.5 mg/mL of catalyst was dispersed in a
water solution containing 1 9 10-5 M of disolved dye. The obtained dispersions
were thoroughly mixed and left in a dark over night, in order to obtaine equilibrium
between free dye and dye adsorbed on particle’s surface. The photocatalytic
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Powders obtained after heating and annealing were morphologically and structurally
characterized using TEM. Results are presented in Fig. 1, were typical TEM images
and ED patterns are presented. As can be seen sample A (Fig. 1a) is consisted of
irregularly shaped nanoparticles with fade and undistinguishable diffraction rings
referring that particles are amorphous or of very low crystallinity. Samples from B to D
(Fig. 1b, c and d, respectively) have nanoparticles with increasing definition of rod-
like shape and ED patterns are more and more easily distinguishable. For sample D,
ED rings are assigned to corresponding ZnWO4 planes (JCPDS 00-015-0774). No
diffraction that can be assigned to ZnO was obtained with this technique, although
ZnO is present in all samples as will be shown in optical characterization part of this
manuscript. Zhang et al. [17] also showed that ZnO nanoparticles can have small
crystalline domains, almost undetectable by XRD technique, but with pronounced
photoluminescence. It can be concluded that crystallinity of the samples increase with
increasing the reaction time at 95 °C from 1 to 120 h. From the TEM images with
higher magnification, sizes of ZnO/ZnWO4 rod-like nanoparticles were estimated to
be in the range from 10 to 30 nm (diameter *10 nm and length *30 nm).
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A Synergy of ZnO and ZnWO4
Fig. 1 Typical TEM images of the as-synthesized ZnO/ZnWO4 nanoparticles obtained for sample A (a),
B (b), C (c) and D (d) reaction time and corresponding ED patterns. Pattern d contains corresponding
ZnWO4 planes (JCPDS 00-015-0774)
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A Synergy of ZnO and ZnWO4
Fig. 3 PL spectra of ZnO/ZnWO4 powders for two excitation wavelengths: 270 nm (a) and 330 nm (b)
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Table 1 Texture properties of ZnO/ZnWO4 nanopowders and corresponding pseudo-first order rate
constants of dye photodecomposition
Sample SBET (m2g-1) Vp (cm3g-1) Vmicro (cm3g-1) D (nm) MB, k(min-1) RhB, k(min-1)
Vp-total pore volume (Gurvich) at p/p0 0.99, d mean pore diameter. SBET of commercial ZnO (Sigma-
Aldrich) was calculated from data obtained from the producer
Fig. 4 Specific surface area and photodegradation rate constants (for degradation of MB and RhB) of
ZnO/ZnWO4 powders and commercial ZnO powder
core/shell structure of rod-like nanoparticles, where ZnO is core and ZnWO4 exist
as a shell which partially cover the surface of ZnO (as proposed by chemical
reactions (1) and (2) in Section ‘‘Optical Properties of ZnO/ZnWO4 Nanoparticles’’).
In sample C, most probably, a significant quantity of ZnWO4 is present at the
surface of ZnO but also part of ZnO surface is still free and available for
photocatalytic degradation of dyes. Figure 5 depicts energetic positions of the
conduction and valence bands (cb, vb) of ZnO and ZnWO4 and the values of their
band gap energies [20]. As presented in a part ‘‘Photocatalytical Testing’’ we used
for photocatalysis UV light with k = 254 nm (4.88 eV). Used photons have energy
greater than band gap energies of both constituents of composite and electron–hole
pairs were generated in both materials in our composite. The cb edge of ZnWO4 is
more negative than cb edge of ZnO and vb of ZnWO4 is more positive than vb edge
of ZnO (Fig. 5); as a result of these facts charge carriers from ZnWO4 tend to
‘‘escape’’ to ZnO through close junction of composite in order to lower their
energies (thermodynamically more stable positions). So, after light absorption, all
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photogenerated holes and electrons are transferred to ZnO part of the composite due
to band edge positions. This process is thermodynamically allowed (see Fig. 5) and
favored. This is the cause of synergistic effect of ZnO/ZnWO4 close junction. These
charge carriers can now react with adsorbed dye molecules, water and oxygen
which explain the above mentioned necessity to maintain free surface of ZnO core
for efficient photocatalysis. Obviously, sample C has optimal ratio between ZnO
and ZnWO4 for efficient absorption of light and enough free ZnO surface where
photodegradation can take place. Further growth and crystalization of the ZnWO4
shell is not beneficial for photocatalytic activity. Energetic diagram presented in
Fig. 5 also explain why all room-temperature photoluminescence characteristics of
ZnO/ZnWO4 nanoparticles belong entirely to ZnO part of composite. After
photogeneration of charge carriers in ZnWO4 shell, they undergo fast extraction in
ZnO core where they can be recombined with emission of photon or lead useful
chemical reactions if reactive species are adsorbed on its surface.
Conclusions
A low temperature method (95 °C), which involves non-ionic copolymer surfactant,
was used for preparation of ZnO/ZnWO4 rod-like composite nanoparticles. TEM
measurements showed that particles were of nanodimensions and with rod-like
shapes. The development of ZnO and ZnWO4 phase was followed by optical
absorption measurements. Room-temperature PL was observed for all samples,
using two excitation wavelengths (270 and 330 nm). They were characterized by
band edge emission of ZnO (380 nm) for both excitations, and green emission from
oxygen vacancies present in ZnO when kexc = 270 nm (4.88 eV) was used.
Photocatalytical and optical properties were correlated and explained by conduction
and valence band positions in our composite nanoparticles. The most effective
synergy between ZnO and ZnWO4 was clearly observed for nanoparticles obtained
after 48 h reaction time.
Acknowledgments Financial support for this study was granted by the Ministry of Education, Science
and Technological Development of the Republic of Serbia, Project No. III45020, III45001, ON172015
and ON172056.
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