Anodic Growth of Highly Ordered Titanium Oxide Nanotube Arrays: Effects of Critical Anodization Factors on their Photocatalytic Activity
Highly ordered arrays of TiO2 nanotubes (TiNTs) were grown vertically on Ti foil by electrochemical anodization. We controlled the lengths of these TiNTs from 2.4 to 26.8 ¶üÇóμm while varying the water contents (1, 3, and 6 wt%) of the electrolyte in ethylene glycol in the presence of 0.5 wt% NH4F with anodization for various applied voltages (20–80 V), periods (10–240 min) and temperatures (10–30 oC). For vertically aligned TiNT arrays, not only the increase in their tube lengths, but also their geometric (wall thickness and surface roughness) and crystalline structure lead to a significant influence on photocatalytic activity. The length optimization for methylene blue (MB) photodegradation was 18 μm. Further extending the TiNT length yielded lower photocatalytic activity presumably related to the limited MB diffusion and light-penetration depth into the TiNT arrays. The results indicated that a maximum MB photodegradation rate was obtained for the discrete anatase TiO2 nanotubes with thick and rough walls.
[1] Mills, A., Davies, R. H., and Worsley, D., "Water purification by
semiconductor photocatalysis," Chem. Soc. Rev., vol. 22, pp. 417-425,
1993.
[2] Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K. and Taga, Y.,
"Visible-light photocatalysis in nitrogen-doped titanium oxides,"
Science., vol. 293, pp. 269-271, 2001.
[3] Li, X. Z. and Li, F. B., "Study of Au/Au3+-TiO2 photocatalysts toward
visible photooxidation for water and wastewater treatment," Environ. Sci.
Technol., vol. 35, pp. 2381-2387, 2001.
[4] Lee, J. C., Kim, M. S., and Kim, B. W., "Removal of paraquat dissolved
in a photoreactor with TiO2 immobilized on the glass-tubes of UV
lamps," Water Res., vol. 36, pp. 1776-1782, 2002.
[5] Zhang, X., Pan, J. H., Du, A. J., Fu, W., Sun, D. D., Leckie, J. O.,
"Combination of one-dimensional TiO2 nanowire photocatalytic
oxidation with microfiltration for water treatment," Water Res., vol. 43,
pp. 1179-1186, 2009.
[6] Kar, A., Smith, Y. R., and Subramanian, V., "Improved photocatalytic
degradation of textile dye using titanium dioxide nanotubes formed over
titanium wires. Environ," Sci. Technol., vol. 43 (9), pp. 3260-3265, 2009.
[7] Kumar, P. S. S., Sivakumar, R., Anandan, S., Madhavan, J.,
Maruthamuthu, P., and Ashokkumar, M., "Photocatalytic degradation of
Acid Red 88 using Au-TiO2 nanoparticles in aqueous solutions," Water
Res., vol. 42, pp. 4878-4884, 2008.
[8] Wu, J. J. and Tseng, C. H., "Photocatalytic properties of nc-Au/ZnO
nanorod composites," Appl. Catal. B: Environ., vol. 66, pp. 51-57, 2006.
[9] Gong, D., Grimes, C. A., Varghese, O. K., Hu, W., Singh, R. S., Chen, Z.,
and Dickey, E. C., "Titanium oxide nanotube arrays prepared by anodic
oxidation," J. Mater. Res., vol. 16 (12), pp. 3331-3334, 2001.
[10] Tsuchiya, H., Macak, J. M., Ghicov, A., Taveira, L., Balaur, E., Ghicov,
A., Sirotna, L., and Schumuki, P., "Self-organized TiO2 nanotubes
prepared in ammonium floride containing acetic acid electrolytes,"
Electrochem. Commun., vol. 7, pp. 576-580, 2005.
[11] Mor, G. K., Shankar, K., Paulose, M., Varghese, O. K., and Grimes, C.
A., "Enhanced photocleavage of water using titania nanotube arrays,"
Nano Lett., vol. 5, pp. 191-195, 2005.
[12] Zheng, Q., Zhou, B., Bai, J., Li, L., Jin, Z., Zhang, J., Li, J., Liu, Y., Cai,
W., and Zhu, X., "Self-organized TiO2 nanotube array sensor for the
determination of chemical oxygen demand," Adv. Mater., vol. 20, pp.
1044-1049, 2008.
[13] Zwilling, V., Aucouturier, M., and Darque-Ceretti, E., "Anodic oxidation
of titanium and TA6V alloy in chromic media. An electrochemical
approach," Electrochim. Acta., vol. 45, pp. 921-929, 1999.
[14] Shankar, K., Mor, G. K., Fitzgerald, A., and Grimes, C. A., "Cation effect
on the electrochemical formation of very high aspect ratio TiO2 nanotube
arrays in formamide-water mixtures," J. Phys. Chem. C., vol. 111, pp.
21-26, 2007.
[15] Grätzel, M., "Molecular photovoltaics that mimic photosynthesis," Pure
Appl. Chem., vol. 73 (3), pp. 459-467, 2001.
[16] Guettai, N. and Ait Amar, H., "Photocatalytic oxidation of methyl orange
in presence of titanium dioxide in aqueous suspension. Part II: kinetics
study," Desalination, vol. 185, pp. 439-448, 2005.
[17] Chanmanee, W., Watcharenwong, A., Chenthanmarakshan, C. R.,
Kajitvichyanukul, P., de Tacconi, N. R., and Rajeshwar, K., "Formation
and characterization of self-organized TiO2 nanotube arrays by pluse
anodization," J. Am. Chem. Soc., vol. 130, pp. 965-974, 2008.
[18] Habazaki, H., Fushimi, K., Shimizu, K., Skeldon, P., and Thompson, G.
E., "Fast migration of fluoride ions in growing anodic titanium oxide,"
Electrochem. Commun., vol. 9, pp. 1222-1227, 2007.
[19] Mor, G. K., Varghese, O. K., Paulose, M., Shankar, K., and Grimes, C. A.,
"A review on highly ordered, vertically oriented TiO2 nanotube arrays:
Fabrication, material properties, and solar energy applications," Solar
Energy Materials and Solar Cells, vol. 90, pp. 2011-2075, 2006.
[20] Christophersen, M., Carstensen, J., Voigt, K., and F¶ÇçÀll, H., "Organic and
aqueous electrolytes used for etching macro- and mesoporous silicon,"
Phys. Stat. sol. (a), vol. 197 (1), pp. 34-38, 2003.
[1] Mills, A., Davies, R. H., and Worsley, D., "Water purification by
semiconductor photocatalysis," Chem. Soc. Rev., vol. 22, pp. 417-425,
1993.
[2] Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K. and Taga, Y.,
"Visible-light photocatalysis in nitrogen-doped titanium oxides,"
Science., vol. 293, pp. 269-271, 2001.
[3] Li, X. Z. and Li, F. B., "Study of Au/Au3+-TiO2 photocatalysts toward
visible photooxidation for water and wastewater treatment," Environ. Sci.
Technol., vol. 35, pp. 2381-2387, 2001.
[4] Lee, J. C., Kim, M. S., and Kim, B. W., "Removal of paraquat dissolved
in a photoreactor with TiO2 immobilized on the glass-tubes of UV
lamps," Water Res., vol. 36, pp. 1776-1782, 2002.
[5] Zhang, X., Pan, J. H., Du, A. J., Fu, W., Sun, D. D., Leckie, J. O.,
"Combination of one-dimensional TiO2 nanowire photocatalytic
oxidation with microfiltration for water treatment," Water Res., vol. 43,
pp. 1179-1186, 2009.
[6] Kar, A., Smith, Y. R., and Subramanian, V., "Improved photocatalytic
degradation of textile dye using titanium dioxide nanotubes formed over
titanium wires. Environ," Sci. Technol., vol. 43 (9), pp. 3260-3265, 2009.
[7] Kumar, P. S. S., Sivakumar, R., Anandan, S., Madhavan, J.,
Maruthamuthu, P., and Ashokkumar, M., "Photocatalytic degradation of
Acid Red 88 using Au-TiO2 nanoparticles in aqueous solutions," Water
Res., vol. 42, pp. 4878-4884, 2008.
[8] Wu, J. J. and Tseng, C. H., "Photocatalytic properties of nc-Au/ZnO
nanorod composites," Appl. Catal. B: Environ., vol. 66, pp. 51-57, 2006.
[9] Gong, D., Grimes, C. A., Varghese, O. K., Hu, W., Singh, R. S., Chen, Z.,
and Dickey, E. C., "Titanium oxide nanotube arrays prepared by anodic
oxidation," J. Mater. Res., vol. 16 (12), pp. 3331-3334, 2001.
[10] Tsuchiya, H., Macak, J. M., Ghicov, A., Taveira, L., Balaur, E., Ghicov,
A., Sirotna, L., and Schumuki, P., "Self-organized TiO2 nanotubes
prepared in ammonium floride containing acetic acid electrolytes,"
Electrochem. Commun., vol. 7, pp. 576-580, 2005.
[11] Mor, G. K., Shankar, K., Paulose, M., Varghese, O. K., and Grimes, C.
A., "Enhanced photocleavage of water using titania nanotube arrays,"
Nano Lett., vol. 5, pp. 191-195, 2005.
[12] Zheng, Q., Zhou, B., Bai, J., Li, L., Jin, Z., Zhang, J., Li, J., Liu, Y., Cai,
W., and Zhu, X., "Self-organized TiO2 nanotube array sensor for the
determination of chemical oxygen demand," Adv. Mater., vol. 20, pp.
1044-1049, 2008.
[13] Zwilling, V., Aucouturier, M., and Darque-Ceretti, E., "Anodic oxidation
of titanium and TA6V alloy in chromic media. An electrochemical
approach," Electrochim. Acta., vol. 45, pp. 921-929, 1999.
[14] Shankar, K., Mor, G. K., Fitzgerald, A., and Grimes, C. A., "Cation effect
on the electrochemical formation of very high aspect ratio TiO2 nanotube
arrays in formamide-water mixtures," J. Phys. Chem. C., vol. 111, pp.
21-26, 2007.
[15] Grätzel, M., "Molecular photovoltaics that mimic photosynthesis," Pure
Appl. Chem., vol. 73 (3), pp. 459-467, 2001.
[16] Guettai, N. and Ait Amar, H., "Photocatalytic oxidation of methyl orange
in presence of titanium dioxide in aqueous suspension. Part II: kinetics
study," Desalination, vol. 185, pp. 439-448, 2005.
[17] Chanmanee, W., Watcharenwong, A., Chenthanmarakshan, C. R.,
Kajitvichyanukul, P., de Tacconi, N. R., and Rajeshwar, K., "Formation
and characterization of self-organized TiO2 nanotube arrays by pluse
anodization," J. Am. Chem. Soc., vol. 130, pp. 965-974, 2008.
[18] Habazaki, H., Fushimi, K., Shimizu, K., Skeldon, P., and Thompson, G.
E., "Fast migration of fluoride ions in growing anodic titanium oxide,"
Electrochem. Commun., vol. 9, pp. 1222-1227, 2007.
[19] Mor, G. K., Varghese, O. K., Paulose, M., Shankar, K., and Grimes, C. A.,
"A review on highly ordered, vertically oriented TiO2 nanotube arrays:
Fabrication, material properties, and solar energy applications," Solar
Energy Materials and Solar Cells, vol. 90, pp. 2011-2075, 2006.
[20] Christophersen, M., Carstensen, J., Voigt, K., and F¶ÇçÀll, H., "Organic and
aqueous electrolytes used for etching macro- and mesoporous silicon,"
Phys. Stat. sol. (a), vol. 197 (1), pp. 34-38, 2003.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:53698", author = "Chin-Jung Lin and Yi-Hsien Yu and Szu-Ying Chen and Ya-Hsuan Liou", title = "Anodic Growth of Highly Ordered Titanium Oxide Nanotube Arrays: Effects of Critical Anodization Factors on their Photocatalytic Activity", abstract = "Highly ordered arrays of TiO2 nanotubes (TiNTs) were grown vertically on Ti foil by electrochemical anodization. We controlled the lengths of these TiNTs from 2.4 to 26.8 ¶üÇóμm while varying the water contents (1, 3, and 6 wt%) of the electrolyte in ethylene glycol in the presence of 0.5 wt% NH4F with anodization for various applied voltages (20–80 V), periods (10–240 min) and temperatures (10–30 oC). For vertically aligned TiNT arrays, not only the increase in their tube lengths, but also their geometric (wall thickness and surface roughness) and crystalline structure lead to a significant influence on photocatalytic activity. The length optimization for methylene blue (MB) photodegradation was 18 μm. Further extending the TiNT length yielded lower photocatalytic activity presumably related to the limited MB diffusion and light-penetration depth into the TiNT arrays. The results indicated that a maximum MB photodegradation rate was obtained for the discrete anatase TiO2 nanotubes with thick and rough walls.
", keywords = "Anodic oxidation, nanotube, photocatalytic, TiO2.", volume = "4", number = "5", pages = "299-6", }
