The Syntheses, Characterizations, and Photocatalytic Activities of Silver, Platinum, and Gold Doped TiO2 Nanoparticles

  • Received : 2010.06.13
  • Accepted : 2011.04.25
  • Published : 2011.06.30


Different weight percentages of Ag, Pt, and Au doped nano $TiO_2$ were synthesized using the acetic acid hydrolyzed sol-gel method. The crystallite phase, surface morphology combined with elemental composition and light absorption properties of the doped nano $TiO_2$ were comprehensively examined using X-ray diffraction (XRD), $N_2$ sorption analysis, transmission electron microscopic (TEM), energy dispersive X-ray, and DRS UV-vis analysis. The doping of noble metals stabilized the anatase phase, without conversion to rutile phase. The formation of gold nano particles in Au doped nano $TiO_2$ was confirmed from the XRD patterns for gold. The specific surface area was found to be in the range 50 to 85 $m^2$/g. TEM images confirmed the formation a hexagonal plate like morphology of nano $TiO_2$. The photocatalytic activity of doped nano $TiO_2$ was evaluated using 4-chlorophenol as the model pollutant. Au doped (0.5 wt %) nano $TiO_2$ was found to exhibit higher photocatalytic activity than the other noble metal doped nano $TiO_2$, pure nano $TiO_2$ and commercial $TiO_2$ (Degussa P-25). This enhanced photocatalytic activity was due to the cathodic influence of gold in suppressing the electron-hole recombination during the reaction.


  1. Fujishima A, Rao TN, Tryk DA. Titanium dioxide photocatalysis. J. Photochem. Photobiol. C: Photochem. Rev. 2000;1:1-21.
  2. Rehman S, Ullah R, Butt AM, Gohar ND. Strategies of making $TiO_2$ and ZnO visible light active. J. Hazard. Mater. 2009;170:560-569.
  3. Moon J, Yun CY, Chung KW, Kang MS, Yi J. Photocatalytic activation of $TiO_2$ under visible light using Acid Red 44. Catal. Today 2003;87:77-86.
  4. Kim S, Choi W. Visible-light-induced photocatalytic degradation of 4-chlorophenol and phenolic compounds in aqueous suspension of pure titania: demonstrating the existence of a surface-complex-mediated path. J. Phys. Chem. B 2005;109:5143-5149.
  5. Li XZ, Li FB. Study of $Au/Au^{3+}-TiO_2$ photocatalysts toward visible photooxidation for water and wastewater treatment. Environ. Sci. Technol. 2001;35:2381-2387.
  6. Wu CG, Chao CC, Kuo FT. Enhancement of the photo catalytic performance of TiO2 catalysts via transition metal modification. Catal. Today 2004;97:103-112.
  7. Mitsuhara K, Kitsudo Y, Matsumoto H, et al. Electronic charge transfer between Au nano-particles and $TiO_2$-terminated $SrTiO_3$(0 0 1) substrate. Surf. Sci. 2010;604:548-554.
  8. Subramanian V, Wolf E, Kamat PV. Semiconductor-metal composite nanostructures. To what extent do metal nanoparticles improve the photocatalytic activity of $TiO_2$ films? J. Phys. Chem. B 2001;105:11439-11446.
  9. Haick H, Paz Y. Long-range effects of noble metals on the photocatalytic properties of titanium dioxide. J. Phys. Chem. B 2003;107:2319-2326.
  10. Ni M, Leung MK, Leung DY, Sumathy K. A review and recent developments in photocatalytic water-splitting using $TiO_2$ for hydrogen production. Renew. Sustain. Energ. Rev. 2007;11:401-425.
  11. Anpo M, Takeuchi M. The design and development of highly reactive titanium oxide photocatalysts operating under visible light irradiation. J. Catal. 2003;216:505-516.
  12. Subramanian V, Wolf EE, Kamat PV. Catalysis with $TiO_2$/gold nanocomposites. effect of metal particle size on the fermi level equilibration. J. Am. Chem. Soc. 2004;126:4943-4950.
  13. Liu SX, Qu ZP, Han XW, Sun CL. A mechanism for enhanced photocatalytic activity of silver-loaded titanium dioxide. Catal. Today 2004;93-95:877-884.
  14. Chao HE, Yun YU, Xingfang HU, Larbot A. Effect of silver doping on the phase transformation and grain growth of solgel titania powder. J. Eur. Ceram. Soc. 2003;23:1457-1464.
  15. Herrmann JM, Tahiri H, Ait-Ichou Y, Lassaletta G, Gonzalez-Elipe AR, Fernandez A. Characterization and photocatalytic activity in aqueous medium of $TiO_2$ and Ag-$TiO_2$ coatings on quartz. Appl. Catal. B Environ. 1997;13:219-228.
  16. Zhao G, Kozuka H, Yoko T. Sol-gel preparation and photo-electrochemical properties of $TiO_2$ films containing Au and Ag metal particles. Thin Solid Films 1996;277:147-154.
  17. Dobosz A, Sobczyński A. The influence of silver additives on titania photoactivity in the photooxidation of phenol. Water Res. 2003;37:1489-1496.
  18. Sclafani A, Herrmann JM. Influence of metallic silver and of platinum-silver bimetallic deposits on the photocatalytic activity of titania (anatase and rutile) in organic and aqueous media. J. Photochem. Photobiol. A Chem. 1998;113:181-188.
  19. Moonsiri M, Rangsunvigit P, Chavadej S, Gulari E. Effects of Pt and Ag on the photocatalytic degradation of 4-chlorophenol and its by-products. Chem. Eng. J. 2004;97:241-248.
  20. Wang X, Yu JC, Yip HY, Wu L, Wong PK, Lai SY. A mesoporous $Pt/TiO_2$ nanoarchitecture with catalytic and photocatalytic functions. Chem. Eur. J. 2005;11:2997-3004.
  21. Zanella R, Giorgio S, Henry CR, Louis C. Alternative methods for the preparation of gold nanoparticles supported on $TiO_2$. J. Phys. Chem. B 2002;106:7634-7642.
  22. Li H, Bian Z, Zhu J, Huo Y, Lu Y. Mesoporous $Au/TiO_2$ nano-composites with enhanced photocatalytic activity. J. Am. Chem. Soc. 2007;129:4538-4539.
  23. Johnson SK, Houk LL, Feng J, Houk RS, Johnson DC. Electrochemical incineration of 4-chlorophenol and the identification of products and intermediates by mass spectrometry. Environ. Sci. Technol. 1999;33:2638-2644.
  24. Cao Y, Tan H, Shi T, Tang T, Li J. Preparation of Ag-doped $TiO_2$ nanoparticles for photocatalytic degradation of acetamiprid in water. J. Chem. Technol. Biotechnol. 2008;83:546-552.
  25. Liu Y, Chen L, Hu J, Li J, Richards R. $TiO_2$ nanoflakes modified with gold nanoparticles as photocatalysts with high activity and durability under near UV irradiation. J. Phys. Chem. C 2010;114:1641-1645.
  26. Ma R, Sasaki T, Bando Y. Layer-by-layer assembled multilayer films of titanate nanotubes, Ag- or Au-loaded nanotubes, and nanotubes/nanosheets with polycations. J. Am. Chem. Soc. 2004;126:10382-10388.
  27. Liu ZL, Cui ZL, Zhang ZK. The structural defects and UV-VIS spectral characterization of $TiO_2$ particles doped in the lattice with $Cr^{3+}$ cations. Mater. Charact. 2005;54:123-129.
  28. Stathatos E, Lianos P, Falaras P, Siokou A. Photocatalytically deposited silver nanoparticles on mesoporous $TiO_2$ films. Langmuir 2000;16:2398-2400.
  29. He J, Ichinose I, Kunitake T, Nakao A. In situ synthesis of noble metal nanoparticles in ultrathin $TiO_2$-gel films by a combination of ion-exchange and reduction processes. Langmuir 2002;18:10005-10010.
  30. Driessen MD, Grassian VH. Photooxidation of trichloroethylene on $Pt/TiO_2$. J. Phys. Chem. B 1998;102:1418-1423.
  31. Bohren CF, Huffman DR. Absorption and scattering of light by small particles. New York: Wiley; 1983. p. 329.
  32. Li X, Fan T, Zhou H, Zhu B, Ding J, Zhang D. A facile way to synthesize biomorphic $N-TiO_2$ incorporated with Au nanoparticles with narrow size distribution and high stability. Microporous Mesoporous Mater. 2008;116:478-484.
  33. Chen S, Liu Y, Wu G. Stabilized and size-tunable gold nanoparticles formed in a quaternary ammonium-based room-temperature ionic liquid under gamma-irradiation. Nanotechnology 2005;16:2360-2364.
  34. Yang L, Li GH, Zhang LD. Effects of surface resonance state on the plasmon resonance absorption of Ag nanoparticles embedded in partially oxidized amorphous Si matrix. Appl. Phys. Lett. 2000;76:1537-1539.
  35. Jakob M, Levanon H, Kamat PV. Charge Distribution between UV-irradiated $TiO_2$ and gold nanoparticles: Determination of shift in the Fermi level. Nano Lett. 2003;3:353-358.
  36. Egerton TA, Mattinson JA. The influence of platinum on UV and 'visible' photocatalysis by rutile and Degussa P25. J. Photochem. Photobiol. A Chem. 2008;194:283-289.
  37. Smirnova N, Vorobets V, Linnik O, Manuilov E, Kolbasov G, Eremenko A. Photoelectrochemical and photocatalytic properties of mesoporous $TiO_2$ films modified with silver and gold nanoparticles. Surf. Interface Anal. 2010;42:1205-1208.
  38. Park JB, Graciani J, Evans J, et al. High catalytic activity of $Au/CeO_x/TiO_2(110)$ controlled by the nature of the mixed-metal oxide at the nanometer level. Proc. Natl. Acad. Sci. U S A 2009;106:4975-4980.

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