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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.
This journal is ª The Royal Society of Chemistry 2011 Nanoscale, 2011, 3, 2931–2935 | 2931
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2932 | Nanoscale, 2011, 3, 2931–2935 This journal is ª The Royal Society of Chemistry 2011
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This journal is ª The Royal Society of Chemistry 2011 Nanoscale, 2011, 3, 2931–2935 | 2933
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Due to the importance of the stability of a photocatalyst for its into an electron and a hole due to the dipolar character of the
practical application, the photocatalytic stability of the obtained LSPR of the Ag nanoparticles. Then, the photogenerated elec-
product was further investigated by cycle photodegradation trons could be far from the surface of AgCl and transferred
experiments. As shown in Fig. 5, no obvious loss of the photo- quickly to the present molecular oxygen to form the reactive
catalytic activity of the obtained Ag@AgCl photocatalyst is oxygen species, owing to the negative charge of the surface of
observed under visible light irradiation, even after four cycles of AgCl and the excellent conductivity of Ag nanoparticles.21 Thus,
the photodegradation of MO dye solution. In addition, the MO an Ag+ ion inside AgCl could avoid being reduced, leading to
dye is degraded more than 93% at each recycle within 18 min, high stability of the Ag@AgCl composite. In addition, the
although the photocatalytic rate decreases slightly at the begin- photogenerated hole could be close to the surface of Ag@AgCl,
ning of the photodegradation process. The results demonstrate so that the Cl ion inside AgCl could be oxidized to a Cl0 atom
that the obtained photocatalyst is highly stable under visible light due to negative charge of the surface of AgCl. The chlorine atoms
irradiation. could also oxidize the MO dye and hence be reduced to chlorine
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The Ag@AgCl composite has a strong absorption in the ions again. This good cycle of chlorine may be another factor in
visible region due to the LSPR effect of Ag nanoparticles.11,12 In the stability of the photocatalyst. So, the LSPR effect of Ag
addition, the electron distribution of Ag nanoparticles can be nanoparticles not only affects the photocatalytic activity of the
polarized by the AgCl, resulting in regions of negative and photocatalyst, but also plays an important role in the stability of
positive charges that are far from, and close to, the Ag/AgCl the photocatalyst.
interface, respectively.21,26 Therefore, visible light can be absor-
bed efficiently by Ag nanoparticles, and then a number of elec- 4. Conclusions
tron–hole pairs are generated. The photogenerated electrons
contribute to the reduction of the MO dye directly, or are In conclusion, we successfully synthesized the plasmonic pho-
transferred to the present molecular oxygen to form active tocatalyst Ag@AgCl, with cube-like morphology, through
species such as O2 and O2_. The active species also could oxidize a simple hydrothermal process and light-induced chemical
the MO dye molecule. At the same time, the photogenerated hole reduction. The morphology of Ag@AgCl can be efficiently
can not only oxidize the MO dye directly, but can also be controlled by using methylene dichloride as the chlorine source,
transferred to the AgCl surface to oxidize a Cl ion to a Cl0 atom. due to the low release rate of chloride ions. The as-synthesized
The Cl0 atom is also a reactive radical species, and could degrade Ag@AgCl photocatalyst exhibits high photocatalytic activity
the MO dye. On the other hand, the well-defined interface under visible light irradiation and MO dye can be decomposed by
between Ag nanoparticles and AgCl particles facilitates the more than 96% within 18 min. In addition, the photocatalytic
interfacial electron transfer and promotes charge carrier sepa- activity of the photocatalyst has no obvious loss even after four
ration because of the in situ production of Ag nanoparticles on cycles of the photodegradation of MO dye solution. The supe-
the surface of AgCl particles, which may be another reason for riority of the as-prepared photocatalyst should be ascribed to the
the high photocatalytic activity. Additionally, considering the LSPR effect from the photogenerated Ag nanoparticles, the well-
complexation of Ag+ ions with nitrogen in the MO dye mole- defined interface, and the complexation between Ag+ ions and
cules, MO dye molecules could adsorb on the surface of the the nitrogen atoms in the MO dye. Therefore, it is believed that
photocatalyst, which may make another contribution to the high the as-prepared Ag@AgCl photocatalyst has potential applica-
photocatalytic activity.30 In a word, the LSPR of Ag nano- tions in the degradation of organic contaminations and disin-
particles, the well-defined interface, and the complexation of Ag+ fection of water, as well as the destruction of bacteria and
ions are assumed to promote the photocatalytic rate. photovoltaic fuel cells.
As for the stability of the photocatalyst, there are following
reasons. An absorbed photon could be efficiently decomposed Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Nos. 20935003, 20820102037) and the 973
Project 2010CB933603.
2934 | Nanoscale, 2011, 3, 2931–2935 This journal is ª The Royal Society of Chemistry 2011
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