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Introduction
Since the first Ag@AgCl plasmonic photocatalyst was proposed,[12] plasmonic photocatalysts have attracted more and
more attention.[310] Unlike traditional photocatalysts,[1114] plasmonic photocatalysts are based on the localized surface plasmon resonance (LSPR) of the noble metal, metal-semiconductor contact, and semiconductor photocatalysts. The LSPR is essentially light waves trapped on the metal surface as a result
of the interaction with the free electrons of the metal.[1516] Excitation of the conduction electrons occurs when there is resonance between the electrons and the oscillating electric field
of the incident light, and this LSPR can be monitored as an extinction spectrum as light is passed through the sample. The
LSPR of metal nanoparticles can be modulated by their size,
shape, and surrounding medium.[1719] The plasmonic photocatalyst Ag@AgCl has proven to be a highly efficient and stable
photocatalyst under visible-light illumination. Based on the research of Ag@AgCl, we have changed the surrounding
medium of silver nanoparticles and succeed in fabricating the
new plasmonic photocatalysts Ag@Ag(Cl,Br) and Ag@AgCl-AgI.
By changing the surrounding medium, the photocatalytic performance and LSPR have been tuned.[20] The new plasmonic
photocatalysts Ag@Ag(Cl,Br) and Ag@AgCl-AgI are highly efficient for the photooxidization of methylic orange (MO) dye
and the photoreduction of CrVI.
The properties of Ag(Cl,Br) are similar to halide silver, but
Ag(Cl,Br) is seldom researched. Ag(Cl,Br) is also photosensitive
and can be decomposed by visible light. Just as AgCl, Ag(Cl,Br)
can also be used as a photocatalyst if photogenerated electrons are prevented from combining with Ag + ions.
Herein, we have synthesized the plasmonic photocatalysts
Ag@Ag(Cl,Br) and Ag@AgCl-AgI. The oxidative ability of the
plasmonic photocatalysts (photogenerated holes, degradation
of organic pollution) and reduction ability of the plasmonic
photocatalysts (photogenerated electrons, reducing CrVI) were
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examined. The oxidative abilities of the plasmonic photocatalysts Ag@Ag(Cl,Br) and Ag@AgCl-AgI are stronger than N-TiO2.
The reducing ability of the plasmonic photocatalyst Ag@AgClAgI is stronger than N-TiO2, whereas the reducing ability of the
plasmonic photocatalyst Ag@Ag(Cl,Br) is weaker than N-TiO2.
The surrounding medium plays important role in the plasmonic performance of the photocatalysts. By changing the surrounding medium, the performance of the photocatalyst could
be tuned.
irradiation, XPS results indicated that the Ag@Ag(Cl,Br) contained Ag, Cl, Br, and C elements. The C element was attributed to adventitious hydrocarbon from the XPS instrument itself.
The Ag, Cl and Br peaks were attributed to the as-obtained
Ag@Ag(Cl,Br) samples. Shown in Figures 2 and 3 are the XPS
spectra of Ag@Ag(Cl,Br). The binding energy values taken from
Figure 4. SEM images of a) Ag@Ag(Cl,Br) and b) Ag@AgCl-AgI samples.
the XPS spectra were calibrated by using C 1s (284.8 eV). In Figure 2 a, the Ag 3d spectra of Ag@Ag(Cl,Br) consists of two individual peaks at 373 and 367 eV, which were attributed to
Ag 3d3/2 and Ag 3d5/2 binding energies, respectively. The
Ag 3d3/2 and Ag 3d5/2 peaks can be further divided in two,
373.64, 374.11 eV, and 367.65 eV, 368.49 eV, respectively. The
peaks at 374.11 and 368.49 eV were attributed to metal Ag0,
whereas the peaks at 367.65 and 373.64 eV were attributed to
AgI of Ag(Cl,Br). The surface Ag0 content (4.13 mol %) and the
surface Ag + content (51.00 mol %) of the corresponding samChemCatChem 2011, 3, 360 364
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Figure 7. a) Changing UV/Vis spectrum of the aqueous solution in the presence of Ag@AgCl-AgI under visible-light irradiation. (using diphenycarbazide
as a developer at l = 540 nm) b) Photocatalytic reduction of CrVI in a slurry
system over plasmonic photocatalysts Ag@Ag(Cl,Br), Ag@AgCl-AgI,
Ag@AgCl, and N-TiO2 under visible-light irradiation (l 400 nm). C is the
concentration of CrVI at time t, and C0 that in the slurry system immediately
after it is kept in the dark to obtain equilibrium adsorption state.
diation time and nearly half the amount of CrVI was photoreduced after only 5 min irradiation; almost all of the CrVI was reduced to CrIII after irradiation for 10 min. Shown in Figure 7 b is
the photocatalytic reduction of CrVI over Ag@Ag(Cl,Br),
Ag@AgCl-AgI, Ag@AgCl, and N-TiO2. The results indicate that
the rate of CrVI reduction with the Ag@AgCl-AgI as a photocatalyst was faster than that with Ag@Ag(Cl,Br), N-TiO2, or
Ag@AgCl. Blank experiments in the absence of the photocatalyst, but under visible-light irradiation, and blank experiments
using Ag@Ag(Cl,Br) and Ag@AgCl-AgI without irradiation, demonstrated that the concentration of CrVI remained unchanged.
The plasmonic photocatalysts Ag@Ag(Cl,Br) and Ag@AgClAgI can be used to decompose organic pollution, such as our
example methylic orange (MO), and reduce CrVI. By varying the
surrounding medium, plasmonic photocatalysts can show different efficiency in decomposing MO and reducing CrVI. During
the process of the destruction of MO, the amount of photogenerated holes that transfer to the surface of the system corresponds to the oxidation of the MO dye. The photogenerated
electrons are likely trapped by O2 in solution to form superoxide ions and other reactive oxygen species.[26] During the process of CrVI decay, the photogenerated electrons correspond to
the reduction of CrVI. The photogenerated holes were expected
to be trapped by EDTA.[24] The activities of the photogenerated
Conclusions
Plasmonic photocatalysts Ag@Ag(Cl,Br) and Ag@AgCl-AgI have
been fabricated by a simple ion-exchange process and light-induced chemical reduction. The photocatalysts have strong absorption in the visible-light region for the plasmon resonance
of Ag nanoparticles. The plasmonic photocatalysts show highly
efficiency in reduction of CrVI and degradation of MO under
visible-light irradiation. The study on plasmonic photocatalysts
Ag@Ag(Cl,Br) and Ag@AgCl-AgI strongly suggests that the performance of the plasmonic photocatalysts and the LSPR of the
noble metals can be tuned by changing the medium surrounding the noble metal nanoparticles.
Experimental Section
Preparation of AgCl: Silver molybdate was synthesized as previously described.[1] AgCl was synthesized by the ion-exchange reaction
between the prepared silver molybdate and HCl. Ag2MoO4 was sonicated in concentrated HCl until completion of the ion-exchange
process. The precipitated AgCl was collected, washed with deionized water, and dried in air.
Preparation of Ag@Ag(Cl,Br) and Ag@AgCl-AgI: AgCl (1.432 g) was
added into the reaction vessel, which contained a solution of KBr
(100 mL, 0.05 mol L 1, and KI). The vessel was stirred for about 3
5 days. The Ag(Cl,Br) and AgCl-AgI precipitate was then collected,
washed with deionized water and dried in air.
The as-obtained Ag(Cl,Br) and AgCl-AgI powders were put into a
solution of MO dye, which was then irradiated with a 300 W Xe arc
lamp equipped with an ultraviolet cutoff filter to provide visible
light with l 400 nm. The resulting precipitates, which consist of
silver NPs and Ag(Cl,Br), AgCl-AgI particles, were then washed and
dried in air.
The crystal structures of the samples were examined by using Xray diffraction (XRD, Bruker AXS D8), their morphology by using
scanning electron microscopy (SEM, Hitachi S-4800 microscopy),
and their diffuse reflectance by using UV/Vis spectroscopy (UV2550, Shimadzu). The content of Ag element in Ag(Cl,Br) and AgClAgI photocatalysts was confirmed by using X-ray photoelectron
spectroscopy measurements (VG MicroTech ESCA 3000 X-ray photoelectron spectroscope using monochromatic A1Ka with a photon
energy of 1486.6 eV at a pressure of > 1 10 9 Torr, a pass energy
of 40 eV, an electron takeoff angle of 60 8C, and an overall resolution of 0.05 eV). The XPS spectra were fitted by using a combined
ChemCatChem 2011, 3, 360 364
Acknowledgements
This work was financially supported by the National Basic Research Program of China (973 Program, Grant 2007CB613302),
the National Natural Science Foundation of China under Grant
50721002, 20973102 and 10774091 and China Postdoctoral Science Foundation under Grant 20090461200.
Keywords: catalysis photocatalysis photochemistry
plasmon silver
[1] P. Wang, ; B. B. Huang, X. Y. Zhang, X. Y. Qin, H. Jin, Y. Dai, Z. Y. Wang,
J. Y. Wei, J. Zhan, S. Y. Wang, J. P. Wang, M.-H. Whangbo, Chem. Eur. J.
2009, 15, 1821 1824 B. B. Huang, X. Y. Qin, X. Y. Zhang, Y. Dai, J. Y. Wei,
M.-H. Whangbo, Angew. Chem. 2008, 120, 8049 8051; Angew. Chem.
Int. Ed. 2008, 47, 7931 7933.
[2] P. Wang, B. B. Huang, Z. Z. Lou, X. Y. Zhang, X. Y. Qin, Y. Dai, Z. K. Zheng,
X. N. Wang, Chem. Eur. J. 2010, 16, 538 544.
[3] K. Awazu, M. Fujimaki, C. Rockstuhl, J. Tominaga, H. Murakami, Y. Ohki,
N. Yoshida, T. Watanabe, J. Am. Chem. Soc. 2008, 130, 1676 1680.
[4] X. Chen, H. Y. Zhu, J. C. Zhao, Z. F. Zheng, X. P. Gao, Angew. Chem. 2008,
120, 5433 5436; Angew. Chem. Int. Ed. 2008, 47, 5353 5356.
[5] P. Wang, ; B. B. Huang, X. Y. Zhang, X. Y. Qin, H. Jin, Y. Dai, Z. Y. Wang,
J. Y. Wei, J. Zhan, S. Y. Wang, J. P. Wang, M.-H. Whangbo, Chem. Eur. J.
2009, 15, 1821 1824.
[6] C. Hu, T. W. Peng, X. X. Hu, Y. L. Nie, X. F. Zhou, J. H. Qu, H. He, J. Am.
Chem. Soc. 2010, 132, 857 862.
[7] Y. P. Bi, J. H. Ye, Chem. Commun. 2010, 46, 1532 1534.
[8] R. H. Li, W. X. Chen, H. Kobayashi, C. X. Ma, Green Chem. 2010, 12, 212
215.
[9] H. Y. Zhu, X. Chen, Z. F. Zheng, X. B. Ke, E. Jaatinen, J. C. Zhao, C. Guo,
T. F. Xie, D. J. Wang, Chem. Commun. 2009, 7524 7526.
[10] P. Wang, B. B. Huang, X. Y. Qin, X. Y. Zhang, Y. Dai, M.-H. Whangbo,
Inorg. Chem. 2009, 48, 10697 10702.
[11] Y. Z. Li, N. H. Lee, D. S. Hwang, J. S. Song, E. G. Lee, S. J. Kim, Langmuir
2004, 20, 10838 10844.
[12] L. B. Sun, J. H. Kou, Y. Chun, J. Yang, F. N. Gu, Y. Wang, J. H. Zhu, Z. G.
Zou, Inorg. Chem. 2008, 47, 4199 4208.
www.chemcatchem.org
363
364
www.chemcatchem.org
[23] J. A. Navio, G. Colon, M. Trillas, J. Peral, Appl. Catal. B 1998, 16, 187
196.
[24] P. Mohapatra, S. K. Samantaray, K. Parida, J. Photochem. Photobiol. A
2005, 170, 189 194.
[25] J. M. Meichtry, M. Brusa, G. Mailhot, M. A. Grela, M. I. Litter, Appl. Catal. B
2007, 71, 101 107.
[26] M. R. Hoffmann, ; S. T. Martin, W. Choi, W. Bahnemann, Chem. Rev. 1995,
95, 69 96; S. T. Martin, W. Choi, W. Bahnemann, Chem. Rev. 1995, 95,
69 96.
[27] K. Maeda, Y. Shimodaira, B. Lee, K. Teramura, D. Lu, H. Kobayashi, K.
Domen, J. Phys. Chem. C 2007, 111, 18264 18270.
[28] U.S. EPA, Chromium hexavalent (colorimetric), in: W. DC (Ed.), Vol
Method 7196A. SW-846, Governmental Printing Office, 1992.
[29] Y. C. Dai, G. R. Qian, Y. L. Cao, Y. Chi, Y. F. Xu, J. Z. Zhou, Q. Liu, Z. P. Xu,
S. Z. Qiao, J. Hazard. Mater. 2009, 170, 1086 1092.