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The synthesis of a novel Ag–NaTaO3 hybrid

with plasmonic photocatalytic activity under
Cite this: CrystEngComm, 2014, 16,
1384 visible-light
Dongbo Xu, Min Chen,* Shuyan Song, Deli Jiang, Weiqiang Fan and Weidong Shi*

In this work, a visible-light-driven plasmonic Ag–NaTaO3 nanocomposite photocatalyst is prepared by

a photochemical reduction process. The structure analyses of the Ag–NaTaO3 reveal that the
Ag nanoparticles (5–10 nm) are uniformly loaded on the surface of the cube NaTaO3 nanocrystals. The
plasmonic Ag–NaTaO3 nanocomposite showed an enhanced photocatalytic activity for the degradation
of rhodamine B (RhB) under visible-light irradiation. In particular, the Ag–NaTaO3 nanocomposite shows
Received 23rd September 2013, the highest photocatalytic activity at the nominal atomic ratio of silver to tantalum as 0.6, which is more
Accepted 23rd October 2013
than 3 times that of pure NaTaO3. The enhancement of the photocatalytic activity was attributed
DOI: 10.1039/c3ce41919c
to the effective charge transfer from the plasmon-excited Ag nanoparticles to NaTaO3, which suppresses
the charge recombination during the photocatalytic process. This work may provide a new insight into
www.rsc.org/crystengcomm the design and preparation of the advanced NaTaO3-based visible-light photocatalytic materials.

Introduction activities under UV irradiation. However, the absorption

toward visible-light and the photocatalytic activity are
In the past two decades, semiconductor photocatalysts have still “bottleneck” for tantalates to meet the requirement of
attracted extensive attention due to their wide potential appli- practical application.
cation in environmental procedures such as air purification, Recently, the surface plasmon resonance of noble metal
water disinfection, hazardous waste remediation, and water nanoparticles (such as Au and Ag) has found to be excited
purification.1 Nanostructured titania as a cheap, nontoxic, under visible-light and exhibits photocatalytic activity in the
efficient photocatalyst for the detoxification of air and water whole solar spectral region.17 As is well-known, surface
pollutants has received much research attention. Unfortu- plasmons exist on the surface of noble metals by a collective
nately, shortcomings such as a poor solar efficiency hinder oscillation of free electrons. By this collective oscillation,
its extensive application. Although much work has been transient local electromagnetic fields are generated by
devoted to the improvement of the photocatalytic perfor- forming electron–hole-rich areas near the surface. When an
mance of TiO2, the improvement is limited.2,3 Therefore, external electromagnetic field such as light is imposed, the
some researchers have diverted their attention to exploit surface plasmon could be excited if their frequencies are
novel photocatalysts. Tantalates exhibit a high photocatalytic matching, which is denoted as surface plasmonic resonance,
performance due to the fact that they possess conduction SPR.18 As for composite photocatalysts such as Ag-loaded
bands consisting of a Ta5d orbital located at a more negative TiO2 and SiO2,19 Au-loaded TiO2,20,21 Au-loaded CdS,22 Ag-loaded
position than that of the titanates (Ti3d), which have conduc- SrTiO3,23 Ag-loaded N–TiO2 and Au-loaded N–TiO2,24 Ag-loaded
tion bands at a high potential.4 A variety of tantalates ZnO,25 and Ag-loaded AgCl26 synergistic effects are expected to
containing closed-shell Ta5+ transition-metal ions such as play a positive role in enhancing the photocatalytic activity.
K3Ta3Si2O13,5 lanthanum-doped NaTaO3,6 SnMn2O6 and However, to the best of our knowledge, the visible-light-
SnM2O7 (M = Nb and Ta),7 lanthanide tantalates LnTaO4 induced effect of Ag on the photocatalytic activity of the
(Ln = La, Ce, Pr, Nd, and Sm),8 NiOx/In0.9Ni0.1TaO4,9 R3MO7 NaTaO3 crystal has not been investigated before.
(R = Y, Ga, La; M = Nb, Ta),10,11 BaTa4O15,12 BaTa2O6,13 In this study, for the first time, we report the synthesis of
Y1−xTaxO1.5+x,14 alkali tantalates ATaO3 (A = Li, Na, and K),15 a Ag–NaTaO3 nanocomposite photocatalyst by a facile photo-
and alkaline earth tantalates BTa2O6 (B = Ca, Sr, and Ba),16 chemical reduction process. The as-prepared hybrid photo-
have been studied recently. These tantalates show reasonable catalyst shows a visible-light photocatalytic activity for the
degradation of rhodamine B. The effects of the Ag nanoparticles
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang in terms of the Ag content and the SPR effect on the visible-
212013, PR China. E-mail: [email protected], [email protected] light photocatalytic activity of the nanocomposite were studied.

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The enhancement in the photocatalytic activity is attributed The suspensions were kept at a constant temperature by
to the effective charge transfer from the plasmon-excited circulating thermostatted water through the jacket. Prior to
Ag nanoparticles to NaTaO3, which suppresses charge recom- irradiation, the suspensions were magnetically stirred for
bination during the photocatalytic process. 30 min in the dark to ensure the adsorption–desorption equi-
librium between rhodamine B and the photocatalyst powders.
Experimental section At given time intervals, 10 mL of the suspension was sampled
and centrifuged to remove the photocatalyst particles. Then,
The preparation of the Ag–NaTaO3 photocatalyst
the absorption spectrum of the centrifugated solution was
A hydrothermal treatment was applied to synthesize NaTaO3.27 recorded using a Shimadzu UV-3100 UV–vis spectrophotometer.
All of the reagents were analytically pure, commercially avail- The change of the rhodamine B concentration was determined
able, and used without further purification. In a typical syn- by monitoring the optical intensity of the absorption spectra
thesis procedure, 0.60 g of NaOH, 0.221 g of Ta2O5 and 20 mL at 554 nm.
water were added into a Teflon-lined stainless steel autoclave
(25 mL capacity). The autoclave was kept at a temperature of Results and discussion
140 °C for 12 h under autogenous pressure. Then the autoclave
Crystal structure
was cooled to room temperature naturally, and the resulting
precipitates were collected by centrifugation at 6000 rpm, Fig. 1 shows the XRD patterns of the pure cube NaTaO3 crys-
washed with deionized water and ethanol thoroughly, and dried talline powders, and the Ag–NaTaO3 nanocomposite. All peaks
at 60 °C in an oven for 5 h before further characterization. can be indexed to the orthorhombic phase of NaTaO3 according
Ag–NaTaO3 was prepared by a photoreduction process as to the JCPDS card (25-0863).28,29 Perovskite-like NaTaO3 has
follows: the obtained NaTaO3 (0.5 mmol) was added into three polymorphs such as cubic perovskite, orthorhombic
25 mL of an AgNO3 solution by magnetic stirring. Photo- phase, and monoclinic phase. Only NaTaO3 with the ortho-
reduction was carried out under a 500 W Xe lamp for 1 h, during rhombic phase can be obtained under the present hydro-
which silver ions were reduced to form silver nanoparticles on thermal conditions and no other crystalline phase can be
the surface of NaTaO3. The obtained Ag–NaTaO3 was then detected. Moreover, due to the fact that the Ag nanoparticles
washed with deionized water, and dried in an oven at 60 °C are dispersedly loaded on the surface of the cube NaTaO3
for 5 h. The molar ratios of Ag to Ta (designated as R) were nanocrystals, no signal about silver can be detected for the
0.2, 0.6, 1 and 1.4. Ag element.

SEM, TEM, EDS and XPS analysis

Characterization
The SEM image shown in Fig. 2A indicates the cube morphology
The phase and composition of the as-prepared samples were
of the NaTaO3 sample with an average size of around 100 nm.
detected by X-ray diffraction (XRD) studies using an X-ray
The TEM image shown in Fig. 2B indicates that many smaller
diffractometer with Cu Kα radiation under 40 kV and 40 mA
Ag nanoparticles are separately loaded on the surface of
with the 4° min−1 ranging from 10° to 80° (Bruker AXS, Germany).
NaTaO3. A close observation of the sample shown in Fig. 2C
The morphologies and microstructures of the as-prepared
reveals that the nanoparticles are monodisperse with a size of
samples were investigated by resolution transmission electron
about 5–10 nm. Furthermore, the successful reduction of
microscopy (TEM, FEI JEM-2100 and FEI Tecnai G2 F20). The
Ag on NaTaO3 by light irradiation was verified by the X-ray
scanning electron microscopy (SEM) images were obtained on
a Hitachi S-4800 II, Japan. The Energy Dispersive Spectrometer
(EDS) analysis of the samples was also performed during the
SEM measurements. X-rays photoelectron spectroscopy (XPS)
was performed with a VG ESCALAB 250 spectrometer using a
nonmonochromatized Al Kα X-ray source. The UV–vis diffuse-
reflectance spectra (DRS) of the samples were recorded with
a UV–vis spectrophotometer (Shimadzu UV-3100) using BaSO4
as a reference.

Photocatalytic reactions
The photocatalytic activity of the Ag–NaTaO3 photocatalyst
was evaluated by the photodegradation of rhodamine B
under visible-light irradiation provided by a 300 W Xe lamp
(λ > 425 nm). A 100 mL beaker with a water jacket was used as
a photoreactor. The experiments were performed as follows: Fig. 1 The XRD patterns of pure NaTaO3 (a) and the Ag–NaTaO3
0.1 g of the photocatalyst were suspended in 100 mL of a composite samples prepared with varying R. R = 0.2 (b), 0.6 (c), 1.0 (d)
rhodamine B solution (10 mg L−1) by stirring magnetically. and 1.4 (e).

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Fig. 2 (A) SEM and (B, C) TEM images pattern of pure NaTaO3 and the Ag–NaTaO3 nanocomposite samples prepared at R = 0.6, respectively.

photoelectron spectroscopic (XPS) data, as shown in Fig. 3(a–c).

The two peaks in Fig. 3(b) centered at 367 and 372.9 eV can
be attributed to Ag 3d5/2 and Ag 3d3/2, and the Ta 4f peak for
the Ag–NaTaO3 sample is shown in Fig. 3(c), with the value
of about 25.99 eV, confirming that Ta exists mainly in the
Ta5+ chemical state on the sample surface. EDS was also used
to further confirm the existence of Ag. As shown in Fig. 3(d),
signals corresponding to the Ta, Na, O and Ag elements are
detected, which indicated the formation of a Ag–NaTaO3
nanocomposite.

UV–Vis diffuse reflectance spectra

The UV–vis diffuse reflectance spectrum (DRS) of the Ag–NaTaO3 Fig. 4 The UV–Vis absorption spectra of the pure NaTaO3 and
sample was compared to that of the pure NaTaO3, as shown Ag–NaTaO3 composite samples prepared at R = 0.2, 0.6, 1.0 and 1.4,
respectively.
in Fig. 4. According to the spectrum, the pure NaTaO3 sample
presents the photoresponse property in the UV light region,
which is due to the intrinsic band gap transition. The absorp-
tion spectrum of Ag–NaTaO3 is obviously different from that of exist in the samples. The prominent absorption in the visible-
NaTaO3. The Ag–NaTaO3 sample shows a shallow peak with light region could be attributed to the surface plasmon reso-
higher intensities observed at around 520 nm, which indicates nance (SPR) effect of the Ag nanoparticles.30–32 The SPR effect
that it is the silver metal rather than silver compounds that of the Ag nanoparticles may have a partial contribution to the
photocatalytic activity of Ag–NaTaO3.

Photocatalytic activity
To demonstrate the potential application of the as-prepared
Ag–NaTaO3 nanocomposite in photocatalysis and the effect
of R on the photocatalytic activities, we evaluated the visible-
light photocatalytic activity of the prepared Ag–NaTaO3 rela-
tive to that of RhB without any photocatalysts and pure
NaTaO3 by employing the photocatalytic degradation of RhB
as a test reaction. Under dark conditions without visible-light
illumination, the concentration of RhB did not change for
every measurement using various Ag–NaTaO3 samples. Illu-
mination in the pure NaTaO3 sample did not show any result
in the photocatalytic decolorization of RhB. These results
suggested that the degradation decolorization of the RhB
aqueous solution was caused by the photocatalytic reactions
on the Ag–NaTaO3 samples under visible-light illumination.33
Fig. 5 shows that a sudden drop of the RhB concentration
Fig. 3 (a) The complete XPS spectra of the Ag–NaTaO3 composites
prepared with R = 0.6. The resolution spectra of the etched samples
occurs over the Ag–NaTaO3 nanocomposite under visible-light
for the elements of (b) Ag and (c) Ta. (d) The EDS microanalysis spectra irradiation, which is caused by the photocatalytic oxidation
of Ag–NaTaO3. process. It demonstrates that the Ag–NaTaO3 nanocomposite

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Mechanism of enhanced photoactivities

Based on the physical and structure characterization, the
enhanced plasmonic photocatalytic activity of the Ag–NaTaO3
nanocomposite should be ascribed to the efficient charge sepa-
ration and transfer. When subjected to visible-light irradiation,
the Ag–NaTaO3 nanocomposite is excited due to the localized
SPR of the Ag nanoparticles and generated electron–hole pairs
in the NaTaO3 nanocrystal. Because the surface of the Ag parti-
cles is usually terminated by Ta ions and therefore negatively
charged, the free electrons in the metallic Ag nanoparticles
deposited on NaTaO3 surface are polarized.34,35 Under the
polarization field provided by the NaTaO3 crystal, the plasmon-
excited electrons move and accumulate on the surface of the
Fig. 5 The variation of the RhB concentration as a function of irradiation Ag nanoparticles, while holes form on the surface of NaTaO3
time under visible-light (λ > 425 nm) with different photocatalysts. nanocrystal and oxidize the RhB molecules. Nevertheless, due
C is the RhB concentration at time t, and C0 is the RhB concentration to a Schottky barrier formed at the Ag–NaTaO3 interface for a
in the initial solution.
larger work function of silver (Fig. 7), the photoexcited elec-
trons from the silver inject into the NaTaO3 conduction band,
so the limitation imposed on the electron transport by the
has a much higher photocatalytic activity than pure NaTaO3 Ag–NaTaO3 nanostructure hinders the progress in achieving
under visible-light. Approximately 25% of the dye is removed a higher carrier separation efficiency, and then a higher photo-
on the Ag–NaTaO3 nanocomposite within 4 h, however, only catalytic efficiency. The electric field in the space-charge pro-
6% of the dye is degraded for the pure NaTaO3 catalyst during motes the transport of excited electrons from the Ag–NaTaO3
the same time duration. An exponential decay of the RhB con- interface to the NaTaO3 bulk, and enhances the charge sepa-
centration with the irradiation time is evident, indicating that ration between the photoexcited electrons and Ag+ ions.36,37
the photodegradation process follows a pseudo-first-order Subsequently, the injected electrons can be transferred to the
reaction. For the Ag–NaTaO3 nanocomposite photocatalyst ubiquitously present molecular oxygen to form superoxide radi-
with R values of 0.2, 0.6, 1.0 and 1.4 nominal atomic % (at.%), cal anions, O2−˙, and then protonation yields HOO˙ radicals.
the corresponding degradation rate constants (kRhB) are The HOO˙ radicals and the trapped electrons combine to pro-
estimated to be 0.34 h−1, 0.56 h−1, 0.35 h−1 and 0.32 h−1, duce H2O2, finally forming HO˙ radicals.38,39 Meanwhile the
respectively. The kRhB when R = 0.6 is up to 3-fold faster Ag+ ions, which are reactive radical species, are able to directly
than that of pure NaTaO3 (about 0.20 h−1 shown in Fig. 6). oxidize RhB. Some reports revealed that Ag+ can cause the
In the Ag–NaTaO3 system, although the nanocomposite with degradation decolorization of the RhB aqueous solution
R = 1.0 and 1.4 have more concentration of Ag than the under visible-light irradiation.40–42 However, the excessive sur-
sample with R = 0.6, the photodegradation rates of the face Ag concentration in the Ag–NaTaO3 system can also act
formers are much lower than that of the later. This indicates as a recombination site, resulting in a decrease in the photo-
that the major factor contributing to an enhanced photo- catalytic activity of the photocatalyst.
degradation efficiency is the photogenerated charge carriers. On the contrary, in this study, the catalyst cube structures
of NaTaO3 can enhance the photocatalytic activity of the

Fig. 6 A comparison of the photocatalytic activity of the NaTaO3

samples prepared with varying R = 0.2, 0.6, 1.0, 1.4, and pure NaTaO3 Fig. 7 A schematic drawing of the photocatalytic induction process in
for the photocatalytic rate of RhB aqueous solutions. the Ag–NaTaO3 catalyst.

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Ag nanoparticles and reduce the dissolvation of Ag+ ions into 12 T. G. Xu, C. Zhang, X. Shao, K. Wu and Y. F. Zhu, Adv. Funct.
solution. Furthermore, the as-prepared Ag–NaTaO3 is more Mater., 2006, 16, 1599.
favorable for environmental purification because it can be 13 T. Xu, X. Zhao and Y. Zhu, J. Phys. Chem. B, 2006, 110, 25825.
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In summary, a Ag–NaTaO3 nanocomposite has been success- Chem. C, 2012, 116, 25898.
fully synthesized through a photochemical reduction. Further- 19 K. Awazu, M. Fujimaki, C. Rockstuhl, J. Tominaga, H. Murakami,
more, the photocatalytic degradation of RhB under visible-light Y. Ohki, N. Yoshida and T. Watanabe, J. Am. Chem. Soc.,
is conducted to investigate the effect of Ag. The electronic 2008, 130, 1676.
effect of the Ag nanoparticles contributes to the enhanced 20 J. Fang, S.-W. Cao, Z. Wang, M. M. Shahjamali, S. C. J. Loo,
photocatalytic activity of pure the NaTaO3 crystalline powders J. Barber and C. Xue, Int. J. Hydrogen Energy, 2012, 37, 17853.
and a certain concentration of Ag is beneficial to the photo- 21 Z. Liu, W. Hou, P. Pavaskar, M. Aykol and S. B. Cronin,
catalytic performance, which are ascribed to the synergistic Nano Lett., 2011, 11, 1111.
effect of the strong surface plasmonic resonance (SPR) of the 22 M. Zayats, A. B. Kharitonov, S. P. Pogorelova, O. Lioubashevski,
electrons for fast carrier transfer between the semiconductor E. Katz and I. Willner, J. Am. Chem. Soc., 2003, 125, 16006.
materials and the Ag nanoparticles in the nanocomposite. 23 X. Yan, S. Sun, B. Hu, X. Wang, W. Lu and W. Shi,
Importantly, our work suggests that the idea of noble metal Micro Nano Lett., 2013, 1, 1–4.
Ag on the surface of NaTaO3 can be a plausible strategy to 24 D. B. Ingram and S. Linic, J. Am. Chem. Soc., 2011, 133, 5202.
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28 H. Zhang, X. Fan, X. Quan, S. Chen and H. Yu, Environ. Sci.
The authors are grateful for the National Natural Science Technol., 2011, 45, 5731.
Foundation of China (21276116 and 21201085), the Start-Up 29 C. C. Hu, C. C. Tsai and H. Teng, J. Am. Ceram. Soc., 2009,
Foundation of Jiangsu University (10JDG070), the Special 92(2), 460.
Financial Grant from the China Postdoctoral Science Foundation 30 W. S. Hummers and R. E. Offeman, J. Am. Chem. Soc., 1958,
(2013 T60501), and the Natural Science Foundation of Jiangsu 80, 1339.
Province (SBK2011460, BK2010340, BK2011517, and BK2012294). 31 Z. Liu, J. T. Robinson, X. Sun and H. J. Dai, J. Am. Chem. Soc.,
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