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Facile solvothermal synthesis of cube-like Ag@AgCl: a highly efficient visible
light photocatalyst†
Lei Han, Ping Wang, Chengzhou Zhu, Yueming Zhai and Shaojun Dong*
Published on 25 May 2011. Downloaded by Aston University on 09/01/2014 00:22:46.

Received 7th March 2011, Accepted 21st April 2011

DOI: 10.1039/c1nr10247h

In this paper, a stable and highly efficient plasmonic photocatalyst, Ag@AgCl, with cube-like
morphology, has been successfully prepared via a simple hydrothermal method. Using methylene
dichloride as chlorine source in the synthesis can efficiently control the morphology of Ag@AgCl, due
to the low release rate of chloride ions. Scanning electron microscopy (SEM), X-ray powder diffraction
(XRD), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectra were used to
characterize the obtained product. The photocatalytic activity of the obtained product was evaluated
by the photodegradation of methyl orange (MO) under visible light irradiation, and it was found,
interestingly, that Ag@AgCl exhibits high visible light photocatalytic activity and good stability.

1. Introduction electrons and holes in the semiconductor catalyst.14–16 In addi-

Since the discovery of the photocatalytic splitting of water on
TiO2 electrodes by Fujishima and Honda in 1972,1 the semi-
conductor-mediated photocatalytic decomposition of organic
contaminations has attracted much attention.2–9 Among the
various semiconductor photocatalysts, TiO2 is the most exten-
sively employed photocatalyst, owing to its high photocatalytic
activity, good chemical stability, non-toxicity, and low-cost.2–4,10
However, due to the large band gap of TiO2 (3.2 eV for anatase
and 3.0 eV for rutile), its excitation requires UV light, which will
result in the consumption of a large amount of energy. To reduce
the cost, the direct use of sunlight is assumed to be the best
choice; since about 48% of sunlight is visible light, it is necessary
to extend the absorption of the photocatalyst into the visible light
region. Furthermore, the recombination rate of its photo-
generated electron–hole pairs is fast.7,9 Therefore, it is of great
importance to develop a new visible-light-driven photocatalyst to
effectively utilize solar energy or indoor light.
Nanoparticles of noble metals can significantly absorb visible
light due to their localized surface plasmon resonance
(LSPR),11,12 that is, a plasmonic oscillation localized on the
surface of the nanoparticle which is induced when the conduction
band electrons of the noble metal nanoparticles couple with the
electric field of incident light at a resonant frequency.13 Mean-
while, LSPR can dramatically amplify the absorption of visible
light and accelerate the separation process of the photogenerated
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute
of Applied Chemistry, Chinese Academy of Sciences, Graduate School of
the Chinese Academy of Sciences, Changchun, 130022, Jilin, PR China.
E-mail: dongsj@ciac.jl.cn
† Electronic supplementary information (ESI) available: SEM images of
the AgCl samples synthesized by changing the addition amount of PVP
and AgNO3. See DOI: 10.1039/c1nr10247h
tion, noble metal nanoparticles exhibit unique optical and
physical properties compared to the corresponding bulk mate-
rials.17–19 Therefore, noble metal nanoparticles may be used as an
alternative class of sensitizers to enhance the absorption of large-
bandgap photocatalysts in the visible light region. For example,
Awazu et al.14 reported a plasmonic photocatalyst, in which they
noted that the photocatalytic activity of TiO2 would be greatly
boosted if it got assistance by the enhanced near-field amplitudes
of the LSPR of Ag nanoparticles.
It is well known that silver halides are photosensitive semi-
conductor materials and have been extensively used as the source
materials in photographic films. Among these silver halides,
silver chloride (AgCl) is a relatively stable photosensitive semi-
conductor material with a direct bandgap of 5.15 eV (241 nm)
and an indirect bandgap of 3.25 eV (382 nm).20 Although the
intrinsic light response of AgCl locates in the UV region, once it
absorbs a photon an electron–hole pair will be generated in the
silver chloride particle, and subsequently the photogenerated
electron combines with an Ag+ ion to form an Ag0 atom. Finally,
a cluster of silver atoms is formed on the surface of the AgCl
particle upon absorption of photons, which could extend the
light response of AgCl into the visible light region. Considering
the LSPR of noble metal nanoparticles and the good photosen-
sitivity of silver halides, Ag@AgCl has been proposed as a new
visible light plasmonic photocatalyst material. Recently, Huang
et al.21–23 synthesized an efficient and stable Ag@AgCl or
Ag@AgBr plasmonic photocatalyst by first treating Ag2MoO4
with HCl or HBr and then reducing some Ag+ ions to the Ag0
species under visible light irradiation. It was demonstrated that
the enhanced performance was attributed to the LSPR effect
from the photogenerated Ag nanoparticles. Uniform Ag@AgCl
core–shell nanowire heterostructures have been prepared for the
efficient degradation of methyl orange (MO) under visible-light

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irradiation.24 Li et al.25 fabricated porous Ag@AgCl nano-
composites by means of a two-step route, and the sample
exhibited considerably high and stable visible light photo-
catalytic activity for the decomposition of MO dye. An and
coworkers introduced a one-pot approach for the synthesis of
hybrid nanoparticles consisting of AgCl cores coated with Ag
nanograins as highly efficient photocatalysts.26 The plasmonic
photocatalyst Ag@AgCl was prepared by an in situ hydro-
thermal method with the contribution of 1-octyl-3-methyl-
imidazolium chloride ([Omim]Cl), which was efficient and stable
for MO degradation under visible light irradiation.27 Very
recently, near-spherical AgCl micro-crystals were prepared by an
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ionic liquid-assisted hydrothermal method.28 However, most of
the reported synthesis procedures are multistep or time-
consuming, or the morphology of the Ag@AgCl is not well
controlled due to the high reaction rate between the silver and the
chloride ions.
In this report, we propose a new and facile approach to
prepare a stable and efficient cube-like Ag@AgCl plasmonic
photocatalyst. First, AgCl was synthesized by means of a simple
hydrothermal process in the presence of silver nitrate (AgNO3),
poly(vinyl pyrrolidone) (PVP-K30) and methylene dichloride
(CH2Cl2). Then, the obtained AgCl powder was irradiated under
a Xenon lamp. As far as we can see, there are the following
advantages in our work. Firstly, Ag@AgCl was synthesized by
a one-pot hydrothermal process and then a light-induced
chemical reduction for the formation of Ag nanoparticles.
Secondly, using CH2Cl2 as the chlorine source can efficiently
control the morphology of Ag@AgCl. Additionally, the
obtained photocatalyst is very stable and efficient because of the
LSPR of Ag nanoparticles.
2. Experimental
Materials
Silver nitrate (AgNO3), poly(vinyl pyrrolidone) (PVP-K30,
molecular weight: 40 000), methylene dichloride (CH2Cl2), and
all chemicals were of analytical grade and used as received
without further purification.
The synthesis of Ag@AgCl photocatalyst
In a typical synthesis, 0.182 g of AgNO3 and 0.713 g of PVP were
placed in 30 mL of distilled water at room temperature. After the
solution was stirred vigorously for 30 min, 0.2 mL of CH2Cl2 was
added. The solution was then transferred into a Teflon-lined
stainless steel autoclave (50 mL capacity), followed by hydro-
thermal treatment of the mixture at 150
C for 6 h, and then
allowed to cool to room temperature naturally. The resulting
solid product was collected by centrifugation, washed with
distilled water three times to remove possible ionic species in the
product, and then dried at 50
C overnight. Then, the obtained
AgCl powder was dispersed in MO dye solution, which was then
irradiated with a 500 W xenon lamp equipped with an ultraviolet
cutoff filter to provide visible light with l $ 400 nm. The
resulting product was washed and dried in air before
characterization.
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Characterization
SEM images were taken with a XL30 field-emission scanning
electron microscope at an accelerating voltage of 15 kV. XRD
patterns were collected by a D8 ADVANCE (Germany) with

in the range of 20–80
(2q).
Cu-Ka radiation (l ¼ 1.54056 A)
XPS analysis was carried on an ESCALAB-MKII X-ray
photoelectron spectrometer. UV-vis diffuse reflectance spectra
were obtained with a Shimadzu UV-3600 spectrophotometer.
Evaluation of photocatalytic activity
Photocatalytic degradation of MO dye was carried out with
0.04 g of the powdered photocatalyst suspended in 40 mL of MO
dye solution, prepared by dissolving 5 mg of MO powder in
500 mL of distilled water in a homemade quartz photochemical
reactor at room temperature under air. Before light irradiation,
the mixture was first sonicated for 5 min and then kept in the
dark for 30 min with stirring to reach the adsorption–desorption
equilibrium. The optical system for detecting the catalytic reac-
tion included a 500 W xenon lamp (CHFXQ500W) with a UV
cutoff filter (providing visible light with l $ 400 nm). At the
given time intervals, analytical samples were taken from the
suspension and immediately centrifuged at 13 000 rpm for 1 min.
The concentration analysis of MO was determined using a Cary
50 UV-Vis-NIR spectrophotometer (Varian, USA).
3. Results and discussion
Fig. 1 presents typical SEM images of the as-prepared Ag@AgCl
photocatalyst. As shown in Fig. 1a, the Ag@AgCl photocatalyst
has a cube-like morphology, with sizes of 2–5 mm. Fig. 1b is
a high-magnification SEM image of Ag@AgCl microcubes, and
the inset is a surface SEM image of the product, from which the
existence of silver nanoparticles on the surface of the cubes
cannot be clearly identified. The formation of a cube-like
morphology is assumed to be attributable to the lower reaction
rate from using CH2Cl2 as the chloride source. In the hydro-
thermal process, we envision that CH2Cl2 slowly releases Cl
ions to react with Ag+ ions to form AgCl particles. At the same
time, we also investigated the effect of the amount of PVP and
AgNO3 added in the synthesis of AgCl. Fig. S1† shows SEM
images of the as-prepared AgCl with different amounts of PVP
added into the reaction system. It is found, interestingly, that as
the amount of PVP increases the size of the obtained product
decreases and the morphology becomes more regular. Never-
theless, no significant effect of the amount of AgNO3 added on
the size of the as-prepared product is observed (shown in
Fig. S2†).
Fig. 1 SEM images of the as-prepared Ag@AgCl: (a) low resolution;
(b) high resolution (inset: a surface SEM image of the product).
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The crystal structure of the obtained Ag@AgCl product was

examined by means of X-ray diffraction (XRD). Fig. 2a shows
the XRD pattern of the Ag@AgCl. Compared with the JPCDS
standard data of AgCl (JCPDS file: 31-1238), the XRD pattern
of Ag@AgCl shows two additional peaks, which are indexed to
the metal silver (JCPDS file: 65-2871), indicating that silver
nanoparticles are produced on the surface of AgCl under visible
light irradiation. No characteristic peaks belonging to other
impurities or other phases such as AgxO are detected, demon-
strating that the obtained product is only composed of metallic
Ag and AgCl.
In addition, the elemental composition and chemical status
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were further investigated by XPS. Fig. 2b–d show the XPS

spectra of the as-prepared Ag@AgCl photocatalyst. Fig. 2b
displays the survey XPS spectrum of the as-prepared Ag@AgCl,
which mainly contains the peaks of Ag, Cl, and C. The carbon
peak is due to the adventitious hydrocarbon from the XPS
instrument itself. The sources of the Ag and Cl peaks correspond
to the obtained product. The spectrum of Ag 3d is shown in
Fig. 2c. It is observed that there are two peaks, centered at
367.3 eV and 373.3 eV, which are ascribed to the peaks of
Ag 3d5/2 and Ag 3d3/2, respectively. Furthermore, the peaks of
Ag 3d5/2 and Ag 3d3/2 could be further divided into different
peaks at 373.74 and 374.33 eV, and 367.74 and 368.64 eV,
respectively.22 The peaks at 374.33 and 368.64 eV could be
attributed to the peaks of Ag 3d5/2 and Ag 3d3/2 of metallic silver,
whereas the peaks at 367.74 and 373.74 eV could be ascribed to
the peaks of Ag 3d inside AgCl.29 As shown in Fig. 2d, the peaks
centered at 197.6 and 199.25 eV are consistent with the peaks of
Cl 2p1 and 2p3, respectively. The results illustrate that the
obtained product consists of metallic silver and silver chloride.
UV-visible diffuse reflectance spectroscopy (DRS) was used to
characterize the electronic states of the obtained product. Fig. 3
displays a typical UV-visible diffuse reflectance spectrum of the
obtained Ag@AgCl photocatalyst. It is found that the obtained
product, Ag@AgCl, has strong absorption both in the UV and
visible light regions, which is in accordance with the previous
literature.21,22 The absorption at 200–350 nm could be attributed
to the characteristic absorption of the AgCl, and the strong
Fig. 3 A UV-visible diffuse reflectance spectrum of the Ag@AgCl
sample.
absorption at 350–800 nm could be ascribed to the characteristic
absorption of the localized surface plasmon absorption of Ag
nanoparticles covering the surface of AgCl.
The photocatalytic activity of the obtained Ag@AgCl photo-
catalyst was evaluated by measuring the photodegradation of
MO dye under visible light irradiation. Fig. 4 shows the photo-
degradation dynamic curves of MO dye. It can be seen that the
peak intensity decreases rapidly at the wavelengths of 270 nm
and 464 nm, which correspond to the functional groups of phenyl
and azo, respectively.30 Furthermore, the MO dye is almost
completely decomposed after only 18 min under visible light
irradiation in the presence of the obtained Ag@AgCl photo-
catalyst. At the same time, a control experiment revealed that in
the presence of visible light and without a photocatalyst there is
almost no decomposition of MO dye. For comparison, the
photocatalytic activity of N-doped TiO2 was also examined in
the same system under the same conditions. The results show
that the MO dye can only be decomposed by 12.5% within
18 min. Therefore, the as-prepared photocatalyst exhibits
excellent photocatalytic activity under visible light irradiation.

Fig. 4 The photodegradation dynamic curves of MO. C0: the original

Fig. 2 (a) The XRD pattern of the Ag@AgCl sample. (b) The survey concentration of MO (10 mg L1), and C: concentration of the remaining
XPS spectrum of the as-prepared Ag@AgCl. (c) Ag 3d and (d) Cl 2p XPS MO at time t. The inset on the right: the UV-visible spectrum of MO dye
spectra. after the corresponding degradation time.

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Due to the importance of the stability of a photocatalyst for its
practical application, the photocatalytic stability of the obtained
product was further investigated by cycle photodegradation
experiments. As shown in Fig. 5, no obvious loss of the photo-
catalytic activity of the obtained Ag@AgCl photocatalyst is
observed under visible light irradiation, even after four cycles of
the photodegradation of MO dye solution. In addition, the MO
dye is degraded more than 93% at each recycle within 18 min,
although the photocatalytic rate decreases slightly at the begin-
ning of the photodegradation process. The results demonstrate
that the obtained photocatalyst is highly stable under visible light
irradiation.
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The Ag@AgCl composite has a strong absorption in the
visible region due to the LSPR effect of Ag nanoparticles.11,12 In
addition, the electron distribution of Ag nanoparticles can be
polarized by the AgCl, resulting in regions of negative and
positive charges that are far from, and close to, the Ag/AgCl
interface, respectively.21,26 Therefore, visible light can be absor-
bed efficiently by Ag nanoparticles, and then a number of elec-
tron–hole pairs are generated. The photogenerated electrons
contribute to the reduction of the MO dye directly, or are
transferred to the present molecular oxygen to form active
species such as O2 and O2_. The active species also could oxidize
the MO dye molecule. At the same time, the photogenerated hole
can not only oxidize the MO dye directly, but can also be
transferred to the AgCl surface to oxidize a Cl ion to a Cl0 atom.
The Cl0 atom is also a reactive radical species, and could degrade
the MO dye. On the other hand, the well-defined interface
between Ag nanoparticles and AgCl particles facilitates the
interfacial electron transfer and promotes charge carrier sepa-
ration because of the in situ production of Ag nanoparticles on
the surface of AgCl particles, which may be another reason for
the high photocatalytic activity. Additionally, considering the
complexation of Ag+ ions with nitrogen in the MO dye mole-
cules, MO dye molecules could adsorb on the surface of the
photocatalyst, which may make another contribution to the high
photocatalytic activity.30 In a word, the LSPR of Ag nano-
particles, the well-defined interface, and the complexation of Ag+
ions are assumed to promote the photocatalytic rate.
As for the stability of the photocatalyst, there are following
reasons. An absorbed photon could be efficiently decomposed
Fig. 5 Four cycling experiment results of the as-prepared Ag@AgCl
photocatalyst.
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into an electron and a hole due to the dipolar character of the
LSPR of the Ag nanoparticles. Then, the photogenerated elec-
trons could be far from the surface of AgCl and transferred
quickly to the present molecular oxygen to form the reactive
oxygen species, owing to the negative charge of the surface of
AgCl and the excellent conductivity of Ag nanoparticles.21 Thus,
an Ag+ ion inside AgCl could avoid being reduced, leading to
high stability of the Ag@AgCl composite. In addition, the
photogenerated hole could be close to the surface of Ag@AgCl,
so that the Cl ion inside AgCl could be oxidized to a Cl0 atom
due to negative charge of the surface of AgCl. The chlorine atoms
could also oxidize the MO dye and hence be reduced to chlorine
ions again. This good cycle of chlorine may be another factor in
the stability of the photocatalyst. So, the LSPR effect of Ag
nanoparticles not only affects the photocatalytic activity of the
photocatalyst, but also plays an important role in the stability of
the photocatalyst.
4. Conclusions
In conclusion, we successfully synthesized the plasmonic pho-
tocatalyst Ag@AgCl, with cube-like morphology, through
a simple hydrothermal process and light-induced chemical
reduction. The morphology of Ag@AgCl can be efficiently
controlled by using methylene dichloride as the chlorine source,
due to the low release rate of chloride ions. The as-synthesized
Ag@AgCl photocatalyst exhibits high photocatalytic activity
under visible light irradiation and MO dye can be decomposed by
more than 96% within 18 min. In addition, the photocatalytic
activity of the photocatalyst has no obvious loss even after four
cycles of the photodegradation of MO dye solution. The supe-
riority of the as-prepared photocatalyst should be ascribed to the
LSPR effect from the photogenerated Ag nanoparticles, the well-
defined interface, and the complexation between Ag+ ions and
the nitrogen atoms in the MO dye. Therefore, it is believed that
the as-prepared Ag@AgCl photocatalyst has potential applica-
tions in the degradation of organic contaminations and disin-
fection of water, as well as the destruction of bacteria and
photovoltaic fuel cells.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Nos. 20935003, 20820102037) and the 973
Project 2010CB933603.
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