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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint
MARK
A R T I C L E I N F O
A BS T RAC T
Keywords:
Photocatalysis
Photodegradation
Ag3PO4
NiTiO3
Composite
A series of NiTiO3/Ag3PO4 composites were prepared by a simple ion-exchange deposition method. The
composition and morphology of the samples were determined by XRD, EDS and SEM. UVvis DRS was used to
characterize their optical absorption properties. The loading of NiTiO3 could promote the ecient separation of
photoinduced electron-hole pairs and enhance the charge carrier transport to improve the photocatalytic
activity. The APO-5 composite exhibited the best photocatalytic activity for the degradation of methyl violet
(MV). Kinetics studies indicated that the APO-5 composite showed an apparent rate constant of 0.115 min1,
which was 2.61 times that of pure Ag3PO4.
1. Introduction
In recent years, photocatalysis has become one of the most popular
research issues due to its great potential to solve energy shortages and
environmental pollution [14], ever since the photocatalytic properties
of TiO2 were discovered by Fujishima [5]. However, because of its large
band gap (3.2 eV for anatase), TiO2 can respond to only UV light,
resulting in the ineective use of solar energy. Accordingly, it is
imperative to develop ecient visible-light photocatalysts. Based on
this, as is currently required, many visible-light photocatalysts have
emerged, such as BiVO4[6], g-C3N4[7,8], BiOI [9], Ag3VO4[10],
Ag3PO4[11] and graphene-based materials [12,13].
Owing to its outstanding photocatalytic activity in water splitting
and waste-water clean-up under visible-light irradiation, Ag3PO4 has
captured substantial attention in the past few years [11,1416]. Thus
far, there are two main strategies to improve the stability or photocatalytic activity of Ag3PO4: one is to fabricate Ag3PO4 nanostructures
with dierent morphologies [11,15,1719], and the other is to
assemble composites by coupling Ag3PO4 with other semiconductors
such as Ag3PO4/CeO2[20], Fe3O4-Ag3PO4[21], Ag3PO4-bentonite [22],
Ag3PO4-graphene [23], Ag3PO4/TiO2[24,25], Ag3PO4/SnO2[26],
Ag3PO4/BiOI [27], Ag3PO4/BiOBr [28], NiFe2O4/Ag3PO4[29],
Ag3PO4/BiPO4[30], AgX/Ag3PO4 (X = Cl, Br, I) [31,32], and CQDs/
Ag3PO4[33]. Using these strategies, the photocatalytic activities of
these materials has been greatly improved. To theoretically provide a
plausible explanation for recent experimental results, rst-principles
density functional theory and the LDA+U formalism have been used to
Corresponding author.
E-mail address: gansonzhao@163.com (G.-y. Zhao).
http://dx.doi.org/10.1016/j.ceramint.2016.11.169
Received 22 September 2016; Received in revised form 22 November 2016; Accepted 23 November 2016
Available online 24 November 2016
0272-8842/ 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
2.2. Characterization
The crystal structures of the samples were determined by X-ray
powder polycrystalline diraction (Rigaku Ultima IV) using graphite
monochromatized Cu-K radiation (=1.54 ). The XRD patterns were
scanned in the range of 580 (2) at a scanning rate of 5 min1. The
morphology of the samples was investigated by eld-emission scanning
electron microscopy (FE-SEM), which was equipped with an energydispersive X-ray spectroscope (EDS) operated at an acceleration
voltage of 5 kV. The diuse reectance spectra (DRS) were obtained
using a UVvis spectrophotometer (Shimadzu UV-2700, Japan) in the
range of 200800 nm with BaSO4 as the reectance standard material.
Fig. 2. SEM images of Ag3PO4 (a), an NiTiO3/Ag3PO4 composite (b) and NiTiO3 (c). In addition, EDS patterns of APO-5 (d).
Table 1
The EDS quantitative results of APO-5.
Element
Line
Net Counts
Int.
Cps/
nA
Weight %
Weight
% Error
Atom %
Atom
%
Error
OK
PK
Ti K
Ni L
Ag L
Total
1893
3011
177
489
15980
3.786
6.022
0.354
0.978
31.960
13.11
5.22
1.36
2.72
77.59
100.00
45.98
9.46
1.59
2.60
40.37
100.00
0.40
0.12
0.25
0.35
1.52
1.41
0.21
0.30
0.33
0.79
h = A(h Eg)2
Fig. 3. UVvis DRS spectra of NiTiO3, Ag3PO4 and the NiTiO3/Ag3PO4 composites (a) and the band gap energy (Eg) of NiTiO3, Ag3PO4 and the APO-5 composite (b).
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Fig. 4. (a) Photodegradation curve of MV under visible-light irradiation in the presence of the composite samples. (b) Kinetics rate constants for the photodegradation of MV by the
NiTiO3/Ag3PO4 composites.
of Ag3PO4, where the holes can serve as active sites for MV photodegradation. The essence of the mechanism is that the formation of
heterojunctions promoted the separation of photoinduced electronhole pairs, as well as charge carrier transfer, and improved the
photocatalytic activity of the photocatalysts. Fig. 5.
4. Conclusion
This article provided a facile method for preparing NiTiO3/Ag3PO4
composites with improved photocatalytic activity. The experimental
results showed that the APO-5 composite possessed excellent photocatalytic activity for MV degradation under visible-light irradiation,
which could be ascribed to the ecient separation of photoinduced
electron-hole pairs and enhanced charge carrier transfer. In conclusion, the fabrication of semiconductor composites is indeed an eective
way to improve the photocatalytic activity of photocatalysts, which will
gain increasing attention in the eld of photocatalysis.
MV aqueous solution and the photocatalyst was stirred in the dark for
40 min to reach adsorption-desorption equilibration. Fig. 4a shows the
MV photodegradation over Ag3PO4 and NiTiO3/Ag3PO4 composites. As
shown in Fig. 4a, pure Ag3PO4 exhibited a removal rate of 89.3% after
40 min of visible-light irradiation (before irradiation, the decrease in
concentration is because of adsorption). The APO-5 composite showed
the best photocatalytic activity among the samples, as more than 99.5%
of the MV molecules were removed within 40 min.
In accordance with the previous studies [42], it was suggested that
the photodegradation of dye obeyed pseudo-rst-order kinetics. The
pseudo-rst-order kinetics for the degradation of MV were calculated
as follows:
Acknowledgements
This work was nancially supported by the Science and Technology
Fund of Guizhou Province ([2015]2055), the Science and Technology
Cooperative Planning of Guizhou Province (LH[2016]7055, LH[2016]
7056, LH[2016]7058), and the High-Level Talents Fund of Guizhou
University of Engineering Science (G2015002).
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ln(C/C 0) = kt
where k is the apparent rate constant (min1), C0 is the initial
concentration of MV (mg L1), and C is the concentration of MV at
reaction time t (min). For all samples, the linear relationship between
ln(C0/C) and t showed that the degradation rate of the MV molecules
could be estimated by the pseudo-rst-order rate model with high
correlation coecients (R > 0.95). The calculated k values for pure
Ag3PO4 and the NiTiO3/Ag3PO4 composites are shown in Fig. 4b. The
results showed that the APO-5 composite had the best photocatalytic
activity with an apparent rate constant of 0.115 min1, which was 2.61
times that of pure Ag3PO4.
For the photocatalytic mechanism of the NiTiO3/Ag3PO4 composites, it can be illustrated that under visible-light irradiation, NiTiO3
and Ag3PO4 are both excited and the photoinduced electrons and holes
are produced simultaneously. The photoinduced electrons in the CB of
Ag3PO4 can be easily transferred to the surface of NiTiO3, while the
photoinduced holes in the VB of NiTiO3 can also migrate to the surface
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