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Nanoscience and Nanotechnology
All rights reserved Vol. 15, 70457048, 2015
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The effects of the preparation conditions of ZnO-modified TaON on the photocatalytic activity
for degradation of rhodamine B dye (Rh. B) under simulated solar light were investigated. The
ZnO/TaON nanocomposite were prepared by loading particulate Ta2 O5 with ZnO using different ZnO
contents, followed by thermal nitridation at 1123 K for 5 h under NH3 flow (20 ml min1 ). The as-
prepared samples were characterized by XRD, UV-Vis-DRS, and SEM-EDX. The results revealed
that the band gap energy absorption edge of as prepared nanocomposite samples was shifted to
a longer wavelength as compared to ZnO and Ta2 O5 , and the 60 wt% ZnO/TaON nanocomposite
exhibited the highest percentage (99.2%) of degradation of Rh. B and the highest reaction rate con-
stant (0.0137 min1 ) in 4 h which could be attributed to the enhanced absorption of the ZnO/TaON
nanocomposite photocatalyst. Hence, these results suggest that the ZnO/TaON nanocomposite
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exhibits enhanced photocatalytic activity for the degradation of rhodamine B under simulated solar
IP: 117.253.220.142 On: Tue, 08 Dec 2015 14:16:30
light irradiation in comparison to the commercial
Copyright: AmericanZnO, Ta2 O5 ,Publishers
Scientific and TaON.
Keywords: Ball-Mill Method, ZnO/TaON, Thermal Ammonolysis, Photocatalysts, Rhodamine B.
1. INTRODUCTION and Ti4+ , such as Ta3 N5 , TaON, and Ta2 O5x Ny were also
In recent year, semiconductor photocatalysts have been found to have the potential activity for water-splitting or
attracted much attention because of their high pho- decomposition of pollutants under visible-light irradiation.
tocatalytic activity, high stability, non-toxicity and However, the photocatalytic activities of these nanoparti-
environmentally-harmonious characteristics.13 TiO2 pho- cles were found to be low. Therefore, more efficient pho-
tocatalysts are presently the most actively and widely tocatalytic structures need to be developed.
investigated for applications that can effectively address In this study, the ball-mill method and thermal
environmental pollution.46 However, TiO2 photocatalysts ammonolysis was used to prepare ZnO/TaON nanocom-
operate only under UV light of wavelengths shorter than posite. The photocatalytic activity was performed by
400 nm which means only 35% of the solar light can degradation of Rh B dye in aqueous solution under simu-
activate these wide band-gap materials.7 ZnO nanoparticles lated solar light irradiation.
has many advantages, such as low price, large initial rates
of activities, many active sites with high surface area, high 2. EXPERIMENTAL DETAILS
absorption efficiency of light radiations, and environmental 2.1. Synthesis of the Photocatalyst
safety.8 It has also been discovered that high photocatalytic The ZnO/TaON nanocomposites were prepared by mix-
activities in some alkaline and alkaline earth tantalates, ing synthesized ZnO with Ta2 O5 powders using ball-
including NaTaO3 , KTaO3 , LiTaO3 , SrTa2 O6 , BaTa2 O6 , milling method in 50 ml of ethanol with zirconia balls
and Sr2 Ta2 O7 .9 10 However, most of these tantalum oxides at 200 rpm for 24 h in a polyethylene bottle. After ball
have the band gap energies that are too large to use solar milling method, the product was collected by evaporation,
radiation efficiently. Recently, oxynitrides containing Ta5+ and dried in an oven at 80 C for 24 h. According to
this method, 20 wt% ZnO/TaON and 60 wt% ZnO/TaON
Author to whom correspondence should be addressed. nanocomposites samples were obtained by varying the
2.2. Characterization
The crystalline structure of the synthesized pow-
ders were determined by X-ray diffraction (XRD,
RIGAKU D/MAX2200HR diffractometer, Tokyo, Japan)
analysis using a Cu-K radiation ( = 15406 ).
The BrunauerEmmettTeller (BET, Micrometrics Instru-
ments ASAP2020, Atlanta, GA) surface areas (SBET of
the samples were analyzed by nitrogen physisorption on a
nitrogen adsorption apparatus at 77 K. The catalyst mor-
phology was observed by using a scanning electron micro-
Figure 1. XRD patterns of (a) ZnO, (b) Ta2 O5 , (c) TaON, (d) 20 wt%
scope (SEM, SEC SNE-3000M). The diffuse reflectance ZnO/TaON, (e) 60 wt% ZnO/TaON nanocomposite.
spectroscopy (DRS, JASCO V-570) spectra were obtained
on a UV-vis spectrophotometer. 20 wt% ZnO/TaON, and 60 wt% ZnO/TaON nanocompos-
ites, respectively. This result indicates the different crys-
2.3. Photocatalytic Activity tallite size of ZnO/TaON nanocomposites, which can be
The photocatalytic activity of the samples was investigated ascribed to the inhibition of aggregation of TaON by the
by means of degradation of rhodamine B (Rh. B) dye ZnO nanoparticles during ball-mill method.
under simulated solar light irradiation. In a typical proce- The diffuse reflectance UV-vis spectra of the ZnO/TaON
dure, 0.1 g of photocatalyst was placed in a batch reactor nanocomposites are shown in Figure 2. Compared to the
containing 100 mL of Rh. B whose initial concentration absorption of Ta2 O5 and ZnO ( 300 nm and 380 nm),
was 20 mg L1 . The suspension was irradiated with sim- the absorption edge of TaON has an intense absorp-
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ulated solar light by means of aIP:
solar simulator PEC-L01,
117.253.220.142 tion
On: Tue, 08 in the2015
Dec visible region at 576 nm. For the 20 wt%
14:16:30
Peccell equipped with a 150 W Xe lamp Copyright:
(150 W 2
American ZnO/TaON and
cm , Scientific Publishers 60 wt% ZnO/TaON nanocomposites, the
1.5 AM). Samples of 1 mL were taken at given time absorption Edge was found at around 547 nm and 537 nm,
intervals and the photocatalyst was separated using a cen- respectively.
trifugation. After that, samples were analyzed by UV-vis The absorption edge for the ZnO/TaON nanocompos-
spectrophotometer (Mecasys Optizen 2120UV) to follow ites indicates that the TaON could be responded to visible
region by combined with ZnO. The absorption edge of
the kinetics of photocatalytic reaction, and the decrease
ZnO/TaON nanocomposites shifted towards longer wave-
in concentration of Rh. B in the solution was determined
lengths as compared to ZnO and Ta2 O5 . The absorp-
from the main absorbance band at a wavelength of 555 nm.
tion coefficient could be calculated according to the
The photodegradation of Rh. B by the different samples
was measured until 240 minutes at every 30 minutes time
interval.
Table I. Physicochemical properties of ZnO/TaON and corresponding the degradation was obtained in the 60 wt% ZnO/TaON
kinetics of Rhodamine B dye degradation.
nanocomposite (Table I). The photocatalytic activity of the
Eg Degradation K Half-life nanocomposite photocatalyst is due to the effective charge
Sample (eV) percentage (%) (min1 ) time (min) separation by means of heterojunction, which enhanced the
ZnO 3.22 543 0003 23105 evolution of reactive oxygen species (ROS) such as O2
Ta2 O5 3.92 239 00011 63013 and OH free radicals responsible for the photocatalytic
TaON 2.16 791 00055 12603 reaction.
20 wt% ZnO/TaON 2.27 901 00077 7702
60 wt% ZnO/TaON 2.31 992 00137 5059
Blank 07 000003 2310491 4. CONCLUSION
Solar-light-responsive ZnO/TaON nanocomposites were
successfully prepared by the ball-mill method and ther-
ZnO, TaON, and 20 wt% ZnO/TaON photocatalyst (t1/2
mal ammonolysis. Diffuse reflectance UV-Vis result of
of 630, 231, 126, and 77 min, respectively). However, the
60 wt% ZnO/TaON nanocomposite revealed a band gap
60 wt% ZnO/TaON nanocomposite showed the highest
of about 2.31 eV. 60 wt% ZnO/TaON nanocompos-
photoactivity, t1/2 = 50 min (Table I). The photocatalytic
ite has higher absorption than ZnO, Ta2 O5 , TaON, and
degradation of rhodamine B using ZnO, Ta2 O5 , TaON,
20 wt% ZnO/TaON in the visible region. ZnO/TaON
20 wt% ZnO/TaON, and 60 wt% ZnO/TaON nanocom-
nanocomposite exhibited good photocatalytic activity on
posite after 240 min in simulated solar light irradiation
the degradation of Rh. B dye under simulated solar light
reaches the percentages of 54, 24, 79, 90, and 99%, respec-
irradiation.
tively, with different behaviors (see Table I). Figure 4
indicates that 60 wt% ZnO/TaON nanocomposite prepared
Acknowledgment: This research was supported by
by thermal ammonolysis is more active for the degrada-
Global Research Laboratory Program of the National
tion of rhodamine B after 240 min of reaction, and its
Research Foundation of Korea (NRF) funded by the
performance is even better than the ZnO, Ta2 O5 , TaON, Ministry of Education, Science and Technology (MEST)
and 20 wt% ZnO/TaON. The photocatalytic degradation of Korea (Grant No.: 2010-00339) and also sup-
reaction with as-prepared samples approximately obeys
ported by Basic Science Research Program through the
pseudo-first-order kinetics, Delivered
and the apparent rate constant
by Publishing Technology to: McMaster
National Research University
Foundation of Korea (NRF) funded
/C117.253.220.142
was calculated by plotting lnC0IP: versus time, as shown
On: Tue, 08 Dec 2015 14:16:30
by the Ministry of Education, Science and Technology
Copyright:
in Figure 5. The slope of the plot represents the American
apparent Scientific Publishers
(2012R1A1A4A01011107).
rate constant. The highest rate constant (0.0137 min1 for