Photocatalytic Destruction of Methylene Blue on Ag@TiO2 with Core/Shell Structure


A series of Ag@TiO2 catalysts with core-shell structure were successfully synthesized by a sol-gel method. The samples were prepared by a sol-gel method using silver nitrate, hydrazine, cetyltrimethylammonium bromide and titanium tetra-isopropoxide as the starting materials. The catalysts were characterized by ICP-MS, XRD, TEM, HRTEM and XPS. The results indicated that the silver core was in metallic state and the TiO2 shell was in anatase state. The size of Ag nanoparticles in core was about 5 and 10 nm, and the shell size of titanium dioxide was 10 and 20 nm. The core was single crystalline Ag nanoparticle and the shell was made up of many TiO2 nanoparticles. The photocatalytic activity of Ag@TiO2 was much higher than that of bare TiO2. Large amounts of hydroxyl groups were present on the surface of TiO2. The catalysts which were treated by hydrothermal method had the higher lattice oxide percentage and higher photocatalytic activities. The core-shell structure can prevent Ag from aggregation.

Share and Cite:

Chen, Y. and Lee, D. (2014) Photocatalytic Destruction of Methylene Blue on Ag@TiO2 with Core/Shell Structure. Open Access Library Journal, 1, 1-14. doi: 10.4236/oalib.1100504.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Bischoff, B.L. and Anderson, M.A. (1995) Peptization Process in the Sol-Gel Preparation of Porous Anatase TiO2. Chemical Materials, 7, 1772-1778.
[2] Chrysicopoulou, P., Davazoglou, D., Trapalis, C. and Kordas, G. (1998) Optical Properties of Very Thin (<100 nm) Sol-Gel TiO2 Films. Thin Solid Films, 323, 188-193.
[3] Dibble, L.A. and Raupp, G.B. (1992) Fluidized-Bed Photocatalytic Oxidation of Trichloroethylene in Contaminated Airstreams. Environmental Science and Technology, 26, 492-495.
[4] Cojocaru, B., Neatu, S., Parvulescu, V.I., Somoghi, V., Petrea, N., Epure, G., Alvaro, M. and Garcia, H. (2009) Synergism of Activated Carbon and Undoped and Nitrogen-Doped TiO2 in the Photocatalytic Degradation of the Chemical Warfare Agents. ChemSusChem, 2, 427-436.
[5] Arabatzis, I.M., Stergiopoulos, T., Bernard, M.C., Labou, D., Neophytides, S.G. and Falaras, P. (2003) Silver-Modified Titanium Dioxide Thin Films for Efficient Photodegradation of Methyl Orange. Applied Catalysis B: Environmental, 42, 187-201.
[6] Aruna, S.T., Tirosh, S. and Zaban, A. (2000) Nanosize Rutile Titania Particle Synthesis via a Hydrothermal Method without Mineralizers. Journal of Materials Chemistry, 10, 2388-2391.
[7] Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K. and Taga, Y. (2001) Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides. Science, 293, 269-271.
[8] Babapour, A., Akhavan, O., Azimirad, R. and Moshfegh, A.Z. (2006) Physical Characteristics of Heat-Treated Nano-Silvers Dispersed in Sol-Gel Silica Matrix. Nanotechnology, 17, 763-771.
[9] Balek, V., Li, D., Subrt, J., Vecerníková, E., Hishita, S., Mitsuhashi, T. and Haneda, H. (2007) Characterization of Nitrogen and Fluorine Co-Doped Titaniaphotocatalyst: Effect of Temperature on Microstructure and Surface Activity Properties. Journal of Physical Chemistry and Solids, 68, 770-774.
[10] Carp, O., Huisman, C.L. and Reller, A. (2004) Photoinduced Reactivity of Titanium Dioxide. Progress in Solid State Chemistry, 32, 33-177.
[11] Li, C.H., Hsieh, Y.H., Chiu, W.T., Liu, C.C. and Kao, C.L. (2007) Study on Preparation and Photocatalytic Performance of Ag/TiO2 and Pt/TiO2 Photocatalysts. Separation and Purification Technology, 58, 148-151.
[12] Li, F.B. and Li, X.Z. (2002) Photocatalytic Properties of Gold/Gold Ion-Modified Titanium Dioxide for Wastewater Treatment. Applied Catalysis A: General, 228, 15-27.
[13] Li, F.B. and Li, X.Z. (2002) The Enhancement of Photodegradation Efficiency Using Pt/TiO2 Catalyst. Chemosphere, 48, 1103-1111.
[14] Li, J., Xu, J., Dai, W.L., Li, H. and Fan, K. (2009) Direct Hydro-Alcohol Thermal Synthesis of Special Core-Shell Structured Fe-Doped Titania Microspheres with Extended Visible Light Response and Enhanced Photoactivity. Applied Catalysis B: Environmental, 85, 162-170.
[15] Haruta, M. (2007) Size- and Support-Dependency in the Catalysis of Gold. Catalysis Today, 36, 153-166.
[16] Hashimoto, K., Irie, H. and Fujishima, A. (2005) TiO2 Photocatalysis: A Historical Overview and Future Prospects. Japanese Journal of Applied Physics, 44, 8269-8278.
[17] Hirakawa, T. and Kamat, P.V. (2005) Charge Separation and Catalytic Activity of Ag@TiO2 Core-Shell Composite Clusters under UV-Irradiation. Journal of American Chemical Society, 127, 3928-3934.
[18] Hirakawa, T. and Kanat, P.V. (2004) Photoinduced Electron Storage and Surface Plasmon Modulation in Ag@TiO2 Clusters. Langmuir, 20, 5645-5647.
[19] Hu, C., Hao, Z., Wong, P.K. and Yu, J.C. (2003) Photocatalytic Degradation of Triazine-Containing Azo Dyes in Aqueous TiO2 Suspensions. Applied Catalysis B: Environmental, 42, 47-55.
[20] Yu, J.C., Yu, J., Yip, H., Wong, P.K., Zhao, J. and Ho, W. (2005) Efficient Visible-Light-Induced Photocatalytic Disinfection on Sulfur-Doped Nanocrystalline Titania. Environmental Science and Technology, 39, 1175-1179.
[21] Zhang, R. and Gao, L. (2002) Preparation of Nanosized Titania by Hydrolysis of Alkoxide Titanium in Micelles. Materials Research Bulletin, 37, 1659-1666.
[22] Behar, D. and Rabani, J. (2006) Kinetics of Hydrogen Production upon Reduction of Aqueous TiO2 Nanoparticles Catalyzed by Pd0, Pt0, or Au0 Coatings and an Unusual Hydrogen Abstraction; Steady State and Pulse Radiolysis Study. Journal of Physical Chemistry B, 110, 8750-8755.
[23] Kim, C.S., Moon, B.K., Park, J.H. and Son, S.M. (2003) Synthesis of Nanocrystalline TiO2 in Toluene by a Solvothermal Route. Journal of Crystal Growth, 254, 405-410.
[24] Kim, S.B. and Hong, S.C. (2002) Kinetic Study for Photocatalytic Degradation of Volatile Organic Compounds in Air Using Thin Film TiO2 Photocatalyst. Applied Catalysis B: Environmental, 35, 305-315.
[25] Kim, S.K., Choi, W. and Hwang, S.J. (2005) Visible Light Active Platinum-Ion-Doped TiO2 Photocatalyst. Journal of Physical Chemistry B, 109, 24260-24267.
[26] Pastoriza-Santos, I., Mamedov, A.A., Giersig, M., Kotov, N.A., Liz-Marzán, L.M. and Koktysh, D.S. (2000) One-Pot Synthesis of Ag@TiO2 Core-Shell Nanoparticles and Their Layer-by-Layer Assembly. Langmuir, 16, 2731-2735.
[27] Chan, S.C. and Barteau, M.A. (2005) Preparation of Highly Uniform Ag/TiO2 and Au/TiO2 Supported Nanoparticle Catalysts by Photodeposition. Langmuir, 21, 5588-5595.
[28] Wang, W., Zhang, J., Chen, F., He, D. and Anpo, M. (2008) Preparation and Photocatalytic Properties of Fe3+-Doped Ag@TiO2 Core-Shell Nanoparticles. Journal of Colloid and Interfacial Science, 323, 182-186.
[29] Chuang, H.Y. and Chen, H. (2009) Fabrication and Photocatalytic Activities in Visible and UV Light Regions of Ag@TiO2 and NiAg@TiO2 Nanoparticles. Nanotechnology, 20, Article ID: 105704.
[30] Jia, H., Xu, H., Hu, Y., Tang, Y. and Zhang, L. (2007) TiO2@CdS Core-Shell Nanorods Films: Fabrication and Ramatically Enhanced Photoelectrochemical Properties. Electrochemical Communications, 9, 354-360.
[31] Li, X.Y., Yue, P.L. and Kutal, C. (2003) Synthesis and Photocatalytic Oxidation Properties of Iron Doped Titanium Dioxide Nanosemiconductor Particles. New Journal of Chemistry, 27, 1264-1269.
[32] Sakai, H., Kanda, T., Shibata, H., Ohkubo, T. and Abe, M. (2006) Preparation of Highly Dispersed Core/Shell-Type Titania Nanocapsules Containing a Single Ag Nanoparticle. Journal of American Chemical Society, 128, 4944-4945.
[33] Tom, R.T., Nair, A.S., Singh, N., Aslam, N., Nagendra, C.L., Philip, R., Vijayamohanan, K. and Pradeep, T. (2003) Freely Dispersible Au@TiO2, Au@ZrO2, Ag@TiO2, and Ag@ZrO2 Core-Shell Nanoparticles: One-Step Synthesis, Characterization, Spectroscopy, and Optical Limiting Properties. Langmuir, 19, 3439-3445.
[34] Galindo, C., Jacques, P. and Kalt, A. (2001) Photooxidation of the Phenylazonaphthol AO20 on TiO2: Kinetic and Mechanistic Investigations. Chemosphere, 45, 997-1005.
[35] Rauf, M.A. and Ashraf, S.S. (2009) Fundamental Principles and Application of Heterogeneous Photocatalytic Degradation of Dyes in Solution. Chemical Engineering Journal, 151, 10-18.
[36] Lin, Y.C. and Lin, C.H. (2008) Catalytic and Photocatalytic Degradation of Ozone via Utilization of Controllable Nano-Ag Modified on TiO2. Environmental Progress, 27, 496-502.
[37] Moulder, J.F., Stickle, W.F., Sobol, P.E. and Bomben, K.E. (1995) Handbook of X-Ray Photoelectron Spectroscopy. Physical Electronics.
[38] Li, X.Z., Li, F.B., Yang, C.L. and Ge, W.K. (2001) Photocatalytic Activity of WOx-TiO2 under Visible Light Irradiation. Journal of Photochemistry and Photobiology A: Chemistry, 141, 209-217.
[39] Linsebigler, A.L., Lu, G. and Yates Jr., J.T. (1995) Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results. Chemical Review, 95, 735-758.
[40] Martin, S.T., Morrison, C.L. and Hoffmann, M.R. (1994) Photochemical Mechanism of Size-Quantized Vanadium-Doped TiO2 Particles. Journal of Physical Chemistry, 98, 13695-13704.
[41] Meichtry, J.M., Rivera, V., Iorio, Y.D., Rodríguez, H.B., Román, E.S., Grela, M. and Litter, M.I. (2009) Photoreduction of Cr(VI) Using Hydroxoaluminiumtricarboxymonoamide Phthalocyanine Adsorbed on TiO2. Photochemistry and Photobiological Science, 8, 604-612.
[42] Natarajan, C. and Nogami, G. (1996) Cathodicel Ectrodeposition of Nanocrystalline Titanium Dioxide Thin Films. Journal of Electrochemical Society, 143, 1547-1550.
[43] O’Regan, B. and Grätzel, M. (1991) A Low-Cost, High-Efficiency Solar Cell Based on Dye-Sensitized Colloidal TiO2 Films. Nature, 353, 737-740.
[44] Ohno, T., Akiyoshi, M., Umebayashi, T., Asai, K., Mitsui, T. and Matsumura, M. (2004) Preparation of S-Doped TiO2 Photocatalysts and Their Photocatalytic Activities under Visible Light. Applied Catalysis A: General, 265, 115-121.
[45] Park, H.K., Moon, Y.T., Kim, D.K. and Kim, C.H. (1996) Formation of Monodisperse Spherical TiO2 Powders by Thermal Hydrolysis of Ti(SO4)2. Journal of American Ceramic Society, 79, 2727-2732.
[46] Poznyak, S.K., Kokorin, A.I. and Kulak, A.I. (1998) Effect of Electron and Hole Acceptors on the Photoelectrochemical Behaviour of Nanocrystalline Microporous TiO2 Electrodes. Journal of Electroanalytic Chemistry, 442, 99-105.
[47] Pruden, A.L. and Ollis, D.F. (1983) Photoassisted Heterogeneous Catalysis: The Degradation of Trichloroethylene in Water. Journal of Catalysis, 82, 404-417.
[48] Sato, S. (1986) Photocatalytic Activity of NOx-Doped TiO2 in the Visible Light Region. Chemical Physics Letter, 123, 126-128.
[49] Sonawane, R.S., Kale, B.B. and Dongare, M.K. (2004) Preparation and Photo-Catalytic Activity of Fe-TiO2 Thin Films Prepared by Sol-Gel Clip Coating. Materials Chemistry and Physics, 85, 52-57.
[50] Sonawane, R.S., Hegde, H.G. and Dongare, M.K. (2003) Preparation of Titanium(IV) Oxide Thin-Film Photocatalyst by Sol-Gel Dip Coating. Materials Chemistry and Physics, 77, 744-750.
[51] Vamathevan, V., Tse, H., Amal, R., Low, G. and McEvoy, S. (2001) Effects of Fe3+ and Ag+ Ions on the Photocatalytic Degradation of Sucrose in Water. Catalysis Today, 68, 201-208.
[52] Wang, C.Y., Liu, C.Y., Zheng, X., Chen, J. and Shen, T. (1998) The Surface Chemistry of Hybrid Nanometer-Sized Particles I. Photochemical Deposition of Gold on Ultrafine TiO2 Particles. Colloids Surfaces A: Physicochemical and Engineering Aspects, 131, 271-280.
[53] Wang, J., Zhao, H., Liu, X., Li, X., Xu, P. and Han, X. (2009) Formation of Ag Nanoparticles on Water-Soluble Anatase TiO2 Clusters and the Activation of Photocatalysis. Catalysis Communications, 10, 1052-1056.
[54] Xu, N., Shi, Z., Fan, Y., Dong, J., Shi, J. and Hu, M.Z.C. (1999) Effects of Particle Size of TiO2 on Photocatalytic Degradation of Methylene Blue in Aqueous Suspensions. Industrial Engineering Chemistry Research, 38, 373-379.
[55] Yildiz, A., Lisesivdin, S.B., Kasap, M. and Mardare, D. (2009) Non-Adiabatic Small Polaron Hopping Conduction in Nb-Doped TiO2 Thin Film. Physica B: Condensed Matter, 404, 1423-1426.
[56] Yin, S., Fujishiro, Y., Wu, J., Aki, M. and Sato, T. (2003) Synthesis and Photocatalytic Properties of Fibrous Titania by Solvothermal Reactions. Journal of Materials Processing Technology, 137, 45-48.
[57] Zhang, F., Pi, Y., Cui, J., Zhang, X., Guan, N. and Yang, Y. (2007) Unexpected Selective Photocatalytic Reduction of Nitrite to Nitrogen on Silver-Doped Titanium Dioxide. Journal of Physical Chemistry C, 111, 3756-3761.
[58] Zhang, H. and Chen, G. (2009) Potent Antibacterial Activities of Ag/TiO2 Nanocomposite Powders Synthesized by a One-Pot Sol-Gel Method. Environmental Science and Technology, 43, 2905-2910.
[59] Zhang, T., Oyama, T., Aoshima, A., Hidaka, H., Zhao, J. and Serpone, N. (2001) Photooxidative N-Demethylation of Methylene Blue in Aqueous TiO2 Dispersions under UV Irradiation. Journal of Photochemistry and Photobiology A: Chemistry, 140, 163-172.
[60] Zhao, X.F., Meng, X.F., Zhang, Z.H., Liu, L. and Jia, D.Z. (2004) Preparation and Photocatalytic Activity of Pb-Doped TiO2 Thin Films. Journal of Inorganic Materials, 19, 140-146.
[61] Dobosz, A. and Sobczyński, A. (2003) The Influence of Silver Additives on Titaniaphotoactivity in the Photooxidation of Phenol. Water Resources, 37, 1489-1496.
[62] Dvoranová, D., Brezová, V., Mazúr, M. and Malati, M.A. (2002) Investigations of Metal-Doped Titanium Dioxide Photocatalysts. Applied Catalysis B: Environmental, 37, 91-105.
[63] Behpour, M., Ghoreishi, S.M. and Razavi, F.S. (2010) Photocatalytic Activity of TiO2/Ag Nanoparticle on Degradation of Water Pollutions. Digest Journal of Nanomaterial Biostructures, 5, 467-475.

Copyright © 2022 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.