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Materials Chemistry
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Synthesis and characterization of high efficiency and stable Ag3PO4/TiO2

visible light photocatalyst for the degradation of methylene blue and
rhodamine B solutions†
Weifeng Yao,*a Bo Zhang,a Cunping Huang,b Chao Ma,a Xiulan Songa and Qunjie Xua
Received 6th September 2011, Accepted 19th December 2011
DOI: 10.1039/c2jm14410g

A facile and reproducible method for the synthesis of Ag3PO4/TiO2 visible light photocatalyst has been
developed to improve the photocatalytic activity and stability of Ag3PO4. The innovation of this
method is to in situ deposit Ag3PO4 nanoparticles onto the TiO2 (P25) surface forming
a heterostructure. The improved activity of the Ag3PO4/TiO2 heterostructured photocatalyst for the
degradation of methylene blue (MB) and rhodamine B (RhB) under visible light irradiation is
attributed to the increased surface area and enhanced absorption of MB and RhB. Furthermore,
depositing Ag3PO4 onto the surface of TiO2 facilitates electron–hole separation that leads to the
elevated photocatalytic activity. The heterostructured Ag3PO4/TiO2 photocatalyst significantly
decreases the loading of noble metal Ag from 77 wt% to 47 wt%, thereby significantly reducing the cost
for the practical application of Ag3PO4 photocatalyst.

1. Introduction photocatalyst for water oxidation and photodecomposition of

Semiconductor based photocatalysts have received great atten-
tion due to their applications in environmental pollution medi-
ation and solar energy conversion.1–6 Of the well-known
photocatalysts, titanium dioxide (TiO2) has proven to be the
most promising and most cost effective material for its photo-
catalytic activity, stability and innocuousness.1–3,7,8 However,
TiO2 is a wide band gap energy semiconductor, active only under
UV light irradiation. Because only a small fraction (ca. 4%) of
solar radiation is in the ultraviolet region and visible light is far
more abundant (ca. 46%),7 it is one of the key objectives in the
field of material science research to develop visible light active
photocatalysts for solar energy conversion.
During past decades numerous semiconductor materials, such
as Ag-based photocatalysts,9–13 solid solution photocatalysts14–17
and N or S doped TiO2 photocatalysts,6,18–20 have been developed
for photocatalytic water-splitting, degradation of organics in
wastewater and photocatalytic oxidation of volatile organics in
air. Ye and co-workers have reported a breakthrough in using
Ag3PO4 semiconductor as an active visible light driven
a
College of Energy & Environmental Engineering, Shanghai University of
Electric Power, 2103 Pingliang Road, Shanghai, 200090, China. E-mail:
yaoweifeng@shiep.edu.cn
b
University of Central Florida, Florida Solar Energy Center, 1679
Clearlake Road, Cocoa, FL, 32922-5703, USA
† Electronic supplementary information (ESI) available: The Xe light
illumination spectrum,
ln (C/C0) as a function of irradiation time for
MB and RhB degradation and MB adsorption over Ag3PO4 and
Ag3PO4/TiO2 photocatalysts under dark conditions. See DOI:
10.1039/c2jm14410g
organic compounds.21–23 They have reported that the activity of
Ag3PO4 is significantly higher than that of currently known
visible light photocatalysts, e.g., BiVO4 or N-doped TiO2.
However, Ag3PO4 nanoparticles suffer from stability issues in
practical applications because they can photochemically
decompose if no sacrificial reagent is involved.21–23 Furthermore,
the consumption of a large amount of noble metal, silver,
strongly limits its practical environmental applications. It is thus
desirable to develop a simple and effective technology to reduce
Ag usage for the Ag3PO4 photocatalyst and to improve its
stability in large scale applications. In addition to the stability
and silver usage, the particle size of Ag3PO4 photocatalysts
remains relatively large (0.5–2 mm),21
23 hindering their perfor-
mance in photocatalytic processes. To enhance the photo-
catalytic activity, the synthesis of a nanosized Ag3PO4 particle
based photocatalyst with a higher surface area is critical.
In this paper we report on a facile process to synthesize in situ
Ag3PO4 nanoparticles onto the surface of TiO2 (P25) photo-
catalyst particles under room conditions. The novel hetero-
structured photocatalyst has shown higher visible light activity as
well as higher stability. Moreover, the silver weight percentage of
the photocatalyst decreases from 77% to 47%, significantly
reducing the cost of Ag3PO4 based photocatalysts.
2. Experimental section
2.1 Synthesis of heterostructured Ag3PO4/TiO2 photocatalyst
The deposition of Ag3PO4 nanoparticles onto the TiO2 (P25)
surface was carried out by an in situ precipitation method. In

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a typical process, 1.598 g (0.02 mol) of commercial TiO2
(Degussa P25 with 80% anatase and 20% rutile and a surface area
of 50 m2 g
1) particles was dispersed in 50 ml of deionized water
and sonicated for five minutes. Immediately after sonication,
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onto the TiO2 surface due to the existence of O
anions. When
Ag+ ion is adsorbed, the reaction of Ag+(ad) and PO43
takes
place on the surface of TiO2 forming an Ag3PO4/TiO2 hetero-
structure. After separation of Ag3PO4/TiO2 from the solution,

3.05766 g (0.018 mol) of AgNO3 was added to the TiO2 dispersed the composite Ag3PO4/TiO2 photocatalyst is thus synthesized.
water (pH ¼ 7). After magnetically stirring for 10 minutes, The synthetic process of the Ag3PO4/TiO2 composite photo-
2.28072 g (0.006 mol) of Na3PO4, previously dissolved in 50 ml catalyst can be summarized as follows:
deionized water, was added drop wise to the solution. After the
resulting solution was magnetically stirred for 5 hours, the color TiO2(s) + Ag+(aq) / TiO2–Ag+(ad) pH ¼ 7
of the solution changed from white to yellow. The photocatalyst,
Ag3PO4/TiO2 (Ag3PO4 to TiO2 molar ratio ¼ 3 : 10), was then
filtered, washed and dried for photocatalytic reaction and char-
acterization. For comparison, Ag3PO4 particles were also TiO2–Ag+(ad) + PO43
(aq) / Ag3PO4/TiO2 pH ¼ 7
prepared under the same conditions without the presence of TiO2
particles.

2.2 Characterizations
UV-Vis diffusion reflectance spectra were recorded using a UV/
VIS spectrometer (UV-2550, Shimadzu) and were converted to
absorption spectra by the standard Kubelka–Munk method.
Transmission electron microscopy (TEM) was performed on
a Hitachi H-500 Transmission Electron Microscope at an
accelerating voltage of 100 kV, and scanning electron micros-
copy (SEM) images were obtained using a SU-1500 scanning
electron microscope. The specific surface areas of the prepared
photocatalysts were measured using the BET method (3H-
2000A). The X-ray diffraction spectra (XRD) patterns were
obtained using an instrument (BRUKER-D8) with Cu Ka
radiation. X-Ray photoelectron spectra (XPS) were recorded
using a PHI 5000 VersaProbe X-ray photoelectron spectrometer
with Al Ka radiation.
2.3 Photocatalytic degradation of aqueous MB and RhB
solutions
In all photocatalytic experiments, 0.050 g of as prepared Ag3PO4
and Ag3PO4/TiO2 samples were dispersed in 100 ml of 20 mg l
1
methylene blue (MB) solution or 100 ml of 20 mg l
1 rhodamine
B (RhB) solution. The light source was a 300 W Xe arc lamp
(Perfectlight Co., PLS-SXE300) equipped with a UV cutoff filter
(UVCUT400, l > 400 nm) and 140 mW cm
2 illumination
intensity (ESI, Fig. S1†). Prior to irradiation, solutions sus-
pended with photocatalysts were stirred in the dark for 50 min to
ensure that the surface of photocatalysts was saturated with MB
or RhB. The degradation of organic dyes was monitored by
measuring the changes of UV-Vis absorption spectra as a func-
tion of irradiation time. After photoreaction the catalyst
powders were removed from MB or RhB solution using
a dialyzer.
3.2 Catalyst characterizations with XRD, SEM and TEM
Fig. 1 shows X-ray diffraction patterns of as prepared Ag3PO4
photocatalyst and Ag3PO4/TiO2 heterostructure photocatalyst. For
comparison, the XRD of commercial TiO2 (Degussa P25) is also
included in the figure. Diffraction peaks corresponding to the body-
centered cubic phase of Ag3PO4 are presented for both Ag3PO4/
TiO2 composite and the Ag3PO4 sample. Three Ag3PO4 samples
(Ag3PO4, Ag3PO4/TiO2 composite with molar ratio ¼ 3 : 10 and
molar ratio ¼ 4 : 10) have the same XRD peak intensities. This
result indicates that Ag3PO4/TiO2 composites exhibit the same
crystalline integrity based on the present synthetic technology.
Moreover, the XRD peaks for the commercial TiO2 can be clearly
distinguished from the XRD patterns of Ag3PO4 and Ag3PO4/TiO2
photocatalysts.
SEM observation shown in Fig. 2a and b has revealed high
agglomeration of Ag3PO4 and Ag3PO4/TiO2 composite particles.
However, although XRD analyses have indicated the composite
structure of Ag3PO4 and TiO2, the SEM images do not have
sufficient resolution for the analysis of particle size distributions.
TEM images (Fig. 2c) show that the particle size of as prepared
Ag3PO4 crystals is in the range of 30 to 100 nm. Regarding the
Ag3PO4/TiO2 composite photocatalyst, two distinct particles

3. Results and discussion

3.1 Synthesis process of Ag3PO4 and Ag3PO4/TiO2
photocatalysts
TiO2 is an amphoteric oxide. When it is suspended in a solution
with pH greater than 6 the surface of TiO2 particles is negatively Fig. 1 XRD patterns of the prepared Ag3PO4/TiO2 (molar ratio ¼ 3 : 10
charged with O
anions which are the main surface species.24,25 In and 4 : 10) and Ag3PO4/TiO2 powders (a), Ag3PO4 (b), Ag3PO4 : TiO2 ¼
this case, positively charged silver ions (Ag+) can be adsorbed 4 : 10 (c), and Ag3PO4 : TiO2 ¼ 3 : 10 (d).

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Fig. 2 SEM images of Ag3PO4 (a) and Ag3PO4/TiO2 (b) and TEM
images of Ag3PO4 (c) and Ag3PO4/TiO2 heterostructure (molar ratio ¼
3 : 10) (d).
were found (Fig. 2d). The average size of the large particles which
ranges from 16 to 65 nm is assigned to the commercial TiO2
(Degussa P25) particles, which are reported with an average
particle size of 21 nm.26 Nanosized particles, which are assigned
to Ag3PO4 crystals with size ranging from 7 to 10 nm, are found
on the surface of TiO2 particles. The smaller particle size of
Ag3PO4 supported on TiO2, in comparison with that of unsup-
ported Ag3PO4, is attributed to the pre-adsorption of silver
cations onto the TiO2 surface. The adsorption of silver ions limits
the growth of Ag3PO4 particles. Adjusting the concentration of
silver ions in the AgNO3 precursor solution can optimize the size
of Ag3PO4 on TiO2. This facile and reproducible method can also
be used for the synthesis of several other Ag-based semi-
conductor composites, including AgCl/TiO2, AgBr/TiO2, (AgCl–
Ag3PO4)/TiO2, etc. These semiconductors can potentially be
used in photocatalytic and electrocatalytic processes.
3.3 UV-Vis absorption spectra of Ag3PO4 and Ag3PO4/TiO2
Fig. 3 shows the UV-Vis absorption spectra of Ag3PO4, TiO2 and
Ag3PO4/TiO2 composite. The UV-Vis spectrum of the Ag3PO4
Fig. 3 UV-Vis absorption spectra of (a) Ag3PO4, (b) Ag3PO4/TiO2
(molar ratio ¼ 3 : 10) and (c) the commercial TiO2.
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sample indicates that it absorbs sunlight with a wavelength less
than 503 nm, corresponding to 2.5 eV of band gap energy. This
result agrees the light-absorption property of Ag3PO4 powders
reported by another group.27 However, for the Ag3PO4/TiO2
composite, except for the absorption band edge (500 nm) in the
visible light range, a feature band edge (370 nm) of pure TiO2
appears in the UV light range based on its UV-Vis spectrum. This
feature of UV-Vis light absorption properties of the prepared
Ag3PO4/TiO2 photocatalyst suggests that the heterostructured
Ag3PO4/TiO2 photocatalyst could be used for visible light pho-
tocatalytic reactions.
3.4 Photocatalytic activities for the degradation of methylene
blue and rhodamine B solutions
3.4.1 Visible light photocatalytic activities of Ag3PO4 and
Ag3PO4/TiO2. In this study, methylene blue (MB), with a major
absorption band at 664 nm, was chosen as a model pollutant for
testing photocatalytic activities of Ag3PO4 and Ag3PO4/TiO2.
The photocatalytic degradation of MB was carried out under
visible light irradiation from a 300 W Xe lamp using a UV cutoff
filter (>400 nm). Fig. 4a depicts the degradation of a 20 mg l
1
aqueous MB solution based on its concentration changes. In this
experiment 0.050 g of the Ag3PO4/TiO2 composite catalyst
(molar ratio ¼ 3 : 10) was suspended in a 100 ml and 20 mg l
1
aqueous MB solution. Visible light photocatalytic degradation of
the aqueous MB solution led to a significant reduction in the MB
concentration when the Ag3PO4/TiO2 photocatalyst was present.
The result shows that 90% of the MB was photocatalytically
degraded after 6 minutes of irradiation (Fig. 4a). When no
photocatalyst was present, the degradation of the MB was
extremely slow—only 8% of the MB was decolorized after 30
minutes of irradiation. For comparison, the activity of the
Ag3PO4 photocatalyst was carried out under the same condi-
tions. As shown in Fig. 4a, the photocatalytic activity of the
Ag3PO4 sample for MB degradation is much lower than that of
the Ag3PO4/TiO2 heterostructured photocatalyst. The Ag3PO4
photocatalyst required 9 minutes to decolorize 90% of the MB
solution in comparison with 6 minutes needed by the Ag3PO3/
TiO2 photocatalyst. Similar results were also obtained when
these two photocatalysts were used for the degradation of an
aqueous rhodamine B (RhB, a typical Azo dye) solution. As
shown in Fig. 4b, the Ag3PO4/TiO2 composite also exhibits
a much higher photocatalytic degradation rate than that of the
Ag3PO4 sample.
The kinetics of these photocatalytic reactions can be described
using a first order reaction for low concentrations of MB and
RhB solutions. The apparent rate constants (kapp, min
1),
determined from regression curves of
ln (C/C0) versus irradia-
tion time, are 0.34 min
1 for MB degradation and 0.13 min
1 for
RhB degradation over the Ag3PO4/TiO2 photocatalyst (ESI,
Fig. S2†). In comparison, the apparent rate constants for the
degradation of MB and RhB over the Ag3PO4 photocatalyst are
0.23 min
1 and 0.06 min
1, respectively. As shown in Table 1, the
heterostructured Ag3PO4/TiO2 photocatalyst has notably
improved the activity of the Ag3PO4 photocatalyst. In addition
to the enhanced activity, the mass percentage of silver is reduced
from 77% for Ag3PO4 to 47% for the Ag3PO4/TiO2 composite,
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Fig. 4 Photocatalytic degradation of (a) methylene blue (MB) solution and (b) rhodamine B (RhB) solution over Ag3PO4 and Ag3PO4/TiO2 (molar
ratio ¼ 3 : 10) under visible light irradiation (l > 400 nm).
Table 1 Comparison of photocatalytic activities of Ag3PO4 and
Ag3PO4/TiO2 photocatalysts
Apparent rate constant/min
1
Solution Ag3PO4 Ag3PO4/TiO2 Change (%)
MB/20 mg l
1 0.23 0.34 47.8
RhB/20 mg l
1 0.06 0.13 116.7
leading to a significant cost reduction for Ag3PO4 based
photocatalysts.
3.4.2 UV light photocatalytic activities of Ag3PO4 and
Ag3PO4/TiO2. The commercial TiO2 (P25) shows little activity
for MB or RhB degradation under visible light irradiation (>400
nm). This is attributed to its higher band gap energy (e.g., 3.2 eV
for anatase and 3.0 eV for rutile). For comparison, the photo-
catalytic degradation of MB over TiO2 and the Ag3PO4/TiO2
composite under UV and visible light irradiation from the full
light spectrum of a 300 W Xe arc lamp (350–800 nm) was per-
formed. As shown in Fig. 5, the Ag3PO4/TiO2 composite exhibits
a much higher activity for MB degradation than that of TiO2.
The apparent rate constant of MB degradation over the Ag3PO4/
TiO2 composite (0.50 min
1) is nearly three times greater than
Fig. 5 Photocatalytic degradation of methylene blue (MB) solution over
TiO2 (P25) and the Ag3PO4/TiO2 composite photocatalyst under Xe light
irradiation without a cutoff filter (350–800 nm).
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that over TiO2 particles (0.14 min
1). It is noted that although the
surface area of TiO2 (51.5 m2 g
1) particles is larger than that of
the Ag3PO4/TiO2 composite (23.5 m2 g
1), the rate is only about
¼ of that of Ag3PO4/TiO2. This result suggests that the high
activity of the Ag3PO4/TiO2 composite should be mainly
ascribed to the performance of Ag3PO4, but not to TiO2 particles
in the composite.
3.4.3 Effect of the Ag3PO4 content on its photocatalytic
activity. Fig. 6 shows the effect of Ag3PO4 to TiO2 molar ratio on
the rate of MB degradation under visible light irradiation (>400
nm). As shown in Fig. 4, pure TiO2 photocatalyst (Deguss-P25)
shows a very low visible light photocatalytic activity for MB
degradation (kapp ¼ 0.02 min
1). This is attributed to the weak
visible light absorption of TiO2. Although a self-photosensitized
effect of adsorbed dyes onto TiO2 may slightly increase the TiO2
photocatalytic activity under visible light irradiation,7 the
pronounced enhancement of photocatalytic activity of Ag3PO4/
TiO2 is definitely attributable to the deposition of Ag3PO4
nanoparticles. The enhancement effect of Ag3PO4 is a function of
the molar ratio of Ag3PO4 to TiO2. It is noteworthy that the rate
of MB degradation quickly increases to 0.13 min
1 when 20%
(molar percentage) of Ag3PO4 is loaded onto the TiO2 surface.
Fig. 5 clearly shows that Ag3PO4 plays a more important role
than TiO2 does on the photocatalytic activity of the Ag3PO4/
TiO2 composite. The optimum Ag3PO4 to TiO2 molar ratio for
Fig. 6 Effect of Ag3PO4/TiO2 molar ratio on the rate of MB degradation
under visible light irradiation (400–800 nm).
J. Mater. Chem., 2012, 22, 4050–4055 | 4053

photocatalytic degradation of MB is about 35%. Further
increase in Ag3PO4 to TiO2 molar ratio resulted in the decrease of
photocatalytic activity of the photocatalyst composite due to the
aggregation of Ag3PO4 particles as shown in Fig. 2.
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3.4.4 MB degradation by reclaimed Ag3PO4/TiO2 composite.
The stability of a photocatalyst is one of the important param-
eters for its usefulness. The Ag3PO4 photocatalyst suffered from
stability issues in a practical application because it would
photochemically decompose apart from the presence of a sacri-
ficial reagent.21 Partial reduction of Ag3PO4 catalyst into metallic
silver was observed when it was used for photocatalytic degra-
dation of methyl orange solutions.23 The loss of silver ions from
an Ag3PO4 photocatalyst reduces its structural and photo-
catalytic stabilities during a photocatalytic process. To study the
stability of the Ag3PO4/TiO2 composite photocatalyst, used
Ag3PO4/TiO2 powder was collected and reused in three succes-
sive MB degradation experiments. These experiments were
carried out by adding used Ag3PO4 and Ag3PO4/TiO2 photo-
catalysts to fresh MB solutions with the same concentration
(20 mg l
1 MB in water). As shown in Fig. 7, the photocatalytic
activity of Ag3PO4/TiO2 is more stable than that of Ag3PO4 for
photocatalytic degradation of MB solutions. Although some
photocatalytic activity losses are observed for the Ag3PO4/TiO2
photocatalyst in three successive experimental runs, the rate of
MB degradation over pure Ag3PO4 particles decreased more
significantly after three degradation cycles under the same
conditions. The XRD pattern of the Ag3PO4/TiO2 catalysts after
three experiments is almost identical to that of the fresh sample.
This result indicates that the Ag3PO4/TiO2 composite photo-
catalyst is more stable than the Ag3PO4 photocatalyst.
The improved stability of the Ag3PO4/TiO2 photocatalyst
under visible light irradiation may result from silver nano-
particles that are produced from the decomposition of Ag3PO4
and deposited on Ag3PO4/TiO2 (ESI, Fig. S3†). This sandwiched
Ag/Ag3PO4/TiO2 structure can promote charge separation and
catalyze the photooxidation of the MB solution. The further
Fig. 7 Repeated photocatalytic degradation of an aqueous MB solution
under visible light irradiation (photocatalyst: Ag3PO4/TiO2 (molar ratio
¼ 3 : 10) (Circles), Ag3PO4 (triangles); MB solution: 100 ml with
a concentration of 20 mg MB in 1.0 litre of water).
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reduction of Ag3PO4 catalyst could be inhibited by injecting
photo-generated electrons into the conduction band of TiO2
through the Ag/TiO2 interface similar to that found on the Ag/
AgCl/TiO2 system.28,29 The large work function of silver metal
resulting from the electric field in the space-charge layer could
promote transportation of excited electrons at the Ag/TiO2
intersurface.7 XPS analysis was performed for Ag3PO4 and
Ag3PO4/TiO2 composite samples before and after the photo-
catalytic MB degradation (ESI, Fig. S3†). It was found that the
ratio of Ag to P increases after the photocatalytic reactions from
3.1 to 3.8 for Ag3PO4 samples and from 3.0 to 3.3 for Ag3PO4/
TiO2 composite samples. Low metallic Ag formation indicates
that depositing Ag3PO4 on the surface of TiO2 promotes the
stability of Ag3PO4 due to the chemical adsorption between O

anions in TiO2 and Ag+ cations in Ag3PO4.
3.5 Mechanism of the improved photocatalytic activity of the
Ag3PO4/TiO2 composite
The larger surface area of the Ag3PO4/TiO2 composite (23.5 g
m
2) than that of the Ag3PO4 photocatalyst (6.3 g m
2) is
responsible for the improvement of photocatalytic activity of the
heterostructured photocatalyst. Generally, the activity of a pho-
tocatalyst increases with the increase of catalyst surface area. A
large surface area can promote photocatalytic reaction because
(I) more active sites on the surface are involved in the photo-
catalytic reaction and (II) the efficiency of electron–hole sepa-
ration is enhanced.
Kinetically, the photocatalytic degradation of the MB solution
follows the Langmuir–Hinshelwood mechanism. In cases of very
low concentration, the degradation rate, r (mol l
1 min
1), is
approximately proportional to the concentration (C) of MB:
r ¼ kKC/(1 + KC) z kKC ¼ kappC
where k is the reaction rate constant, K is the equilibrium
adsorption constant of MB and kapp is the apparent reaction rate
constant (min
1). In order to increase the efficiency of a photo-
catalyst, both the reaction rate constant k and the equilibrium
adsorption constant K should be significantly large.30 A larger
surface area promotes adsorption capability of MB for Ag3PO4/
TiO2 as compared to the Ag3PO4 photocatalyst.
In order to determine the equilibrium adsorption constant K of
MB on Ag3PO4 and the Ag3PO4/TiO2 photocatalyst, a dark
experiment was conducted by suspending 0.1 g photocatalysts in
a 20 ppm 100 ml MB solution with continuous stirring. The
results (ESI, Fig. S4†) indicate that Ag3PO4/TiO2 shows a larger
adsorption affinity for MB than does the Ag3PO4 photocatalyst.
The higher adsorption capacity is in accordance with the higher
photocatalytic activity of photocatalyst samples. However,
although the commercial TiO2 (P25) has the largest surface area
(51.5 g m
2), its adsorption capability for MB is much lower than
that of the Ag3PO4 sample. These phenomena indicate that the
improved adsorption capability for MB of the Ag3PO4/TiO2
composite as compared to that of the Ag3PO4 photocatalyst was
caused by Ag3PO4, but not by TiO2 in the composite.
Furthermore, integrating Ag3PO4 with TiO2 facilitates the
electron–hole separation and thereby improves the photo-
catalytic activity. Fig. 8 shows the schematic charge separation in
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Fig. 8 A schematic of the charge separation in Ag3PO4/TiO2 composite
catalysts under visible-light irradiation.
the Ag3PO4/TiO2 system. Potentials of both conduction band
(
0.3 eV vs. NHE)31 and valence band (+2.7 eV vs. NHE)32 of
TiO2 are more negative than those of Ag3PO4 (conduction band
potential: +0.45 eV vs. NHE, valence band potential: +2.9 eV vs.
NHE).21 Under visible light irradiation, photon generated holes
in an Ag3PO4 particle quickly transfer to a TiO2 particle, whereas
photon generated electrons migrate to the surface of an Ag3PO4
particle. The separation of electrons (in Ag3PO4) and holes
(trapped in TiO2) prevents the charge recombination, leading to
higher photocatalytic activity of Ag3PO4.
4. Conclusions
We have demonstrated a facile method to improve the photo-
catalytic activity and stability of the Ag3PO4 photocatalyst by
deposition of Ag3PO4 nanoparticles onto TiO2 (P25), forming
a heterostructure. In addition to the significant improvement in
activities, the content of silver noble metal in the photocatalyst
composite reduces from 77 wt% for non-supported Ag3PO4 to
47 wt% for the Ag3PO4/TiO2 composite. The low Ag content
reduces the cost of the Ag3PO4 based photocatalysts. The facile
and reproducible approach for preparation of the Ag3PO4/TiO2
photocatalyst can also be adapted for the synthesis of other Ag-
based photocatalysts, such as AgCl/TiO2, AgBr/TiO2, AgCl–
Ag3PO4/TiO2, etc. In addition to higher activity, the Ag3PO4/
TiO2 heterostructured photocatalyst is more stable than unsup-
ported Ag3PO4 because the chemical adsorption of Ag+ and O

increases the stability of Ag3PO4.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (no. 21103106), Innovation
Program of Shanghai Municipal Education Commission
(12YZ144), Shanghai Rising-Star Program (10QA1402800),
Shanghai Nano Special Foundation (1052nm02600) and
Construction Capacity Projects (no. 10160502300 and
09230501400). Dr Yao, the leading author, is grateful for the
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Funding from Specially Appointed Professors (Oriental
Scholars) of Shanghai Universities and financial support from
the Key Laboratory in the Department of Resources Chemistry
at Shanghai Normal University.
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