The photochemical behavior of xanthene dyes (fluorescein, erythrosine, and eosin) with colloidal SnO2 nanoparticles was probed by UV-visible, steady state, and time resolved fluorescence measurements. The prepared SnO2 nanoparticles were characterized by using UV-visible and powder XRD measurements. The xanthene dyes were adsorbed on the surface of colloidal SnO2 nanoparticles through electrostatic interaction. Apparent association constant ( ) was calculated from the relevant fluorescence data. The larger value of apparent association constant indicates a strong association between xanthene dyes and SnO2 nanoparticles. The fluorescence quenching is mainly attributed to electron transfer from the excited state xanthenes to the conduction band of colloidal SnO2. The electron transfer mechanism was explained based on the Rehm-Weller equation as well as the energy level diagram. 1. Introduction The photosensitization of electron transfer across the semiconductor solution interface plays a vital role in light energy conversion in photoelectrochemical cells, wastewater treatment, nanoelectric devices, silver halide photography, and electrophotography. Effort in this area has concentrated on improving the visible light response of wide-band semiconductors such as SnO2, ZnO, and TiO2. Sensitization is achieved by adsorption of dye molecules at the semiconductor surface which, upon excitation, inject an electron into its conduction band [1, 2]. The first successful experiment of this type was described by Putseiko and Terenin [3] who found that the Dember effect of ZnO powder in visible light was sensitized by xanthene and cyanine dyes. The investigation and development of the dye-semiconductor systems are essential for various fields of applications. Recently Ferrere et al. and Tian et al. used perylene-SnO2 systems for dye sensitized solar cells [4–6]. The SnO2 is a stable n-type semiconductor with a wide-band gap ( ？eV) being used for various applications, including solid-state gas sensor, photovoltaic devices, dye-based solar cells, transparent conductive films for display and solar cells, catalysis, and anode materials of secondary lithium ion battery [7–9]. Xanthenes belong to the most widely used organic dyes, serving as luminophores [10], molecular probes, bioconjugates, stains, and biologically active substances [11, 12]. These dyes are utilized for photosensitization of redox processes [13, 14] in energy transfer and light sensitization studies [15]. They are also used in light-harvesting dendrimers [16], in biochemistry and medicine as reactants for
References
[1]
J. Moser and M. Gratzel, “Photosensitized electron injection in colloidal semiconductors,” Journal of the American Chemical Society, vol. 106, pp. 6557–6564, 1984.
[2]
C. D. Jaeger, F.-R. F. Fan, and A. J. Bard, “Semiconductor electrodes. 26. Spectral sensitization of semiconductors with phthalocyanine,” Journal of the American Chemical Society, vol. 102, no. 8, pp. 2592–2598, 1980.
[3]
E. K. Putseiko and A. N. Terenin, “Photosensitization of the internal photoeffect in zinc oxide and other semiconductors by adsorbed dyes,” Zhurnal Fizicheskoi Khimii, vol. 23, p. 676, 1949.
[4]
S. Ferrere, A. Zaban, and B. A. Gregg, “Dye sensitization of nanocrystalline tin oxide by perylene derivatives,” Journal of Physical Chemistry B, vol. 101, no. 23, pp. 4490–4493, 1997.
[5]
S. Ferrere and B. A. Gregg, “Large increases in photocurrents and solar conversion efficiencies by UV illumination of dye sensitized solar cells,” Journal of Physical Chemistry B, vol. 105, no. 32, pp. 7602–7605, 2001.
[6]
H. Tian, P.-H. Liu, W. Zhu, E. Gao, D.-J. Wu, and S. Cai, “Synthesis of novel multi-chromophoric soluble perylene derivatives and their photosensitizing properties with wide spectral response for SnO2 nanoporous electrode,” Journal of Materials Chemistry, vol. 10, no. 12, pp. 2708–2715, 2000.
[7]
P. Thangadurai, A. C. Bose, S. Ramasamy, R. Kesavamoorthy, and T. R. Ravindran, “High Pressure effects on electrical resistivity and dielectric properties of nanocrystalline SnO2,” Journal of Physics and Chemistry of Solids, vol. 66, no. 10, pp. 1621–1627, 2005.
[8]
J. A. Toledo-Antonio, R. Gutiérrez-Baez, P. J. Sebastian, and A. Vázquez, “Thermal stability and structural deformation of rutile SnO2 nanoparticles,” Journal of Solid State Chemistry, vol. 174, no. 2, pp. 241–248, 2003.
[9]
A. Y. El-Etre and S. M. Reda, “Characterization of nanocrystalline SnO2 thin film fabricated by electrodeposition method for dye-sensitized solar cell application,” Applied Surface Science, vol. 256, no. 22, pp. 6601–6606, 2010.
[10]
N. Boens, W. Qin, N. Basari？, A. Orte, E. M. Talavera, and J. M. Alvarez-Pez, “Photophysics of the fluorescent pH indicator BCECF,” Journal of Physical Chemistry A, vol. 110, no. 30, pp. 9334–9343, 2006.
[11]
R. P. Haugland, Handbook of Fluorescent Probes and Research Products, Molecular Probes, Eugene, Ore, USA, 9th edition, 2002.
[12]
A. Zumbuehl, D. Jeannerat, S. E. Martin et al., “An amphotericin B-Fluorescein conjugate as a powerful probe for biochemical studies of the membrane,” Angewandte Chemie International Edition, vol. 43, no. 39, pp. 5181–5185, 2004.
[13]
D. C. Neckers and O. M. V. Aguilera, “Photochemistry of the xanthene dyes,” in Advances in Photochemistry, D. H. Volman, G. S. Hammond, and D. C. Neckers, Eds., vol. 18, pp. 313–394, 1993.
[14]
O. Shimizu, J. Watanabe, S. Naito, and Y. Shibata, “Quenching mechanism of rose bengal triplet state involved in photosensitization of oxygen in ethylene glycol,” Journal of Physical Chemistry A, vol. 110, no. 5, pp. 1735–1739, 2006.
[15]
M. H. V. Werts, J. W. Verhoeven, and J. W. Hofstraat, “Efficient visible light sensitisation of water-soluble near-infrared luminescent lanthanide complexes,” Journal of the Chemical Society, no. 3, pp. 433–439, 2000.
[16]
V. Balzani, P. Ceroni, S. Gestermann, M. Gorka, C. Kauffmann, and F. V？gtle, “Fluorescent guests hosted in fluorescent dendrimers,” Tetrahedron, vol. 58, no. 4, pp. 629–637, 2002.
[17]
M. H. Lim, B. A. Wong, W. H. Pitcock Jr., D. Mokshagundam, M.-H. Baik, and S. J. Lippard, “Direct nitric oxide detection in aqueous solution by copper(II) fluorescein complexes,” Journal of the American Chemical Society, vol. 128, no. 44, pp. 14364–14373, 2006.
[18]
H. Maeda, K. Yamamoto, Y. Nomura et al., “A design of fluorescent probes for superoxide based on a nonredox mechanism,” Journal of the American Chemical Society, vol. 127, no. 1, pp. 68–69, 2005.
[19]
C. R. Schr？der, B. M. Weidgans, and I. Klimant, “pH fluorosensors for use in marine systems,” Analyst, vol. 130, no. 6, pp. 907–916, 2005.
[20]
N. Nakayama-Ratchford, S. Bangsaruntip, X. Sun, K. Welsher, and H. Dai, “Noncovalent functionalization of carbon nanotubes by fluorescein- polyethylene glycol: supramolecular conjugates with pH-dependent absorbance and fluorescence,” Journal of the American Chemical Society, vol. 129, no. 9, pp. 2448–2449, 2007.
[21]
H. F. Gao, C. C. Wang, W. L. Yang, and S. K. Fu, “Preparation of a water-soluble fluorescent polymer,” Journal of Macromolecular Science A, vol. 41, no. 4, pp. 357–371, 2004.
[22]
N. O. McHedlov-Petrossyan, N. A. Vodolazkaya, Y. A. Gurina, W.-C. Sun, and K. R. Gee, “Medium effects on the prototropic equilibria of fluorescein fluoro derivatives in true and organized solution,” Journal of Physical Chemistry B, vol. 114, no. 13, pp. 4551–4564, 2010.
[23]
J. Pernak, A. ？wierczyńska, F. Walkiewicz, E. Krystkowiak, and A. Maciejewski, “Long alkyl chain bis-quaternary ammonium-based ionic liquids as biologically active xanthenes dyes,” Journal of the Brazilian Chemical Society, vol. 20, no. 5, pp. 839–845, 2009.
[24]
M. Ali, V. Kumar, and S. Pandey, “Unusual fluorescein prototropism within aqueous acidic 1-butyl-3-methylimidazolium tetrafluoroborate solution,” Chemical Communications, vol. 46, no. 28, pp. 5112–5114, 2010.
[25]
M. Ali, P. Dutta, and S. Pandey, “Effect of ionic liquid on prototropic and solvatochromic behavior of fluorescein,” Journal of Physical Chemistry B, vol. 114, no. 46, pp. 15042–15051, 2010.
[26]
A. Kathiravan and R. Renganathan, “Effect of anchoring group on the photosensitization of colloidal TiO2 nanoparticles with porphyrins,” Journal of Colloid and Interface Science, vol. 331, no. 2, pp. 401–407, 2009.
[27]
M. A. Jhonsi and R. Renganathan, “Investigations on the photoinduced interaction of water soluble thioglycolic acid (TGA) capped CdTe quantum dots with certain porphyrins,” Journal of Colloid and Interface Science, vol. 344, no. 2, pp. 596–602, 2010.
[28]
L. Jiang, G. Sun, Z. Zhou et al., “Size-controllable synthesis of monodispersed SnO2 nanoparticles and application in electrocatalysts,” Journal of Physical Chemistry B, vol. 109, no. 18, pp. 8774–8778, 2005.
[29]
E. J. H. Lee, C. Ribeiro, T. R. Giraldi, E. Longo, E. R. Leite, and J. A. Varela, “Photoluminescence in quantum-confined SnO2 nanocrystals: evidence of free exciton decay,” Applied Physics Letters, vol. 84, no. 10, pp. 1745–1747, 2004.
[30]
P. V. Kamat, J.-P. Chauvet, and R. W. Fessenden, “Photoelectrochemistry in particulate systems. 4. Photosensitization of a TiO2 semiconductor with a chlorophyll analogue,” Journal of Physical Chemistry, vol. 90, no. 7, pp. 1389–1394, 1986.
[31]
P. V. Kamat, “Photoelectrochemistry in particulate systems. 9. Photosensitized reduction in a colloidal titania system using anthracene-9-carboxylate as the sensitizer,” Journal of Physical Chemistry, vol. 93, no. 2, pp. 859–864, 1989.
[32]
J. Choi, K. Yeo, M. Yoon, S. J. Lee, and K. Kim, “Photoinduced intramolecular charge-transfer state of p-dimethylaminobenzoic acid in CdS and TiO2 colloid solutions,” Journal of Photochemistry and Photobiology A, vol. 132, no. 1-2, pp. 105–114, 2000.
[33]
P. V. Kamat, S. Das, K. G. Thomas, and M. V. George, “Ultrafast photochemical events associated with the photosensitization properties of a squaraine dye,” Chemical Physics Letters, vol. 178, no. 1, pp. 75–79, 1991.
[34]
J. Keizer, “Nonlinear fluorescence quenching and the origin of positive curvature in Stern-Volmer plots,” Journal of the American Chemical Society, vol. 105, no. 6, pp. 1494–1498, 1983.
[35]
J. R. Lakowicz, Principles of Fluorescence Spectroscopy, Plenum Press, NewYork, NY, USA, 1986.
[36]
J.-M. Wu and C.-H. Kuo, “Ultraviolet photodetectors made from SnO2 nanowires,” Thin Solid Films, vol. 517, no. 14, pp. 3870–3873, 2009.
[37]
G. J. Kavarnos and N. J. Turro, “Photosensitization by reversible electron transfer: theories, experimental evidence, and examples,” Chemical Reviews, vol. 86, no. 3, pp. 401–449, 1986.
[38]
S. Parret, F. M. Savary, J. P. Fouassier, and P. Ramamurthy, “Spin-orbit-coupling-induced triplet formation of triphenylpyrylium ion: a flash photolysis study,” Journal of Photochemistry and Photobiology A, vol. 83, no. 3, pp. 205–209, 1994.
[39]
S. Nath, H. Pal, D. K. Palit, A. V. Sapre, and J. P. Mittal, “Steady-state and time-resolved studies on photoinduced interaction of phenothiazine and 10-methylphenothiazine with chloroalkanes,” Journal of Physical Chemistry A, vol. 102, no. 29, pp. 5822–5830, 1998.
