Fast-rate formation of TiO2 nanotube arrays in an organic bath and their applications in photocatalysis.

In this work, 18.5 µm titanium oxide (TiO2) nanotube arrays were formed by the anodization of titanium (Ti) foil in ethylene glycol containing 1 wt% water and 5 wt% fluoride for 60 min at 60 V. The fast growth rate of the nanotube arrays at 308 nm min − 1 was achieved due to the excess fluoride content and the limited amount of water in ethylene glycol used for anodization. Limited water content and excess fluoride in ethylene glycol inhibited the formation of a thick barrier layer by increasing the dissolution rate at the bottom of the nanotubes. This eased the transport of titanium, fluorine and oxygen ions, and allowed the nanotubes to grow deep into the titanium foil. At the same time, the neutral condition offered a protective environment along the tube wall and pore mouth, which minimized lateral and top dissolution. Results from x-ray photoelectron spectra revealed that the TiO2 nanotubes prepared in ethylene glycol contained Ti, oxygen (O) and carbon (C) after annealing. The photocatalytic activity of the nanotube arrays produced was evaluated by monitoring the degradation of methyl orange. Results indicate that a nanotube with an average diameter of 140 nm and an optimal tube length of 18.5 µm with a thin tube wall (20 nm) is the optimum structure required to achieve high photocatalytic reaction. In addition, the existence of carbon, high degree of anatase crystallinity, smooth wall and absence of fluorine enhanced the photocatalytic activity of the sample.

[1]  Christopher R. Bowen,et al.  Effect of heat treatment on the properties and structure of TiO2 nanotubes: phase composition and chemical composition , 2010 .

[2]  L. Schmidt‐Mende,et al.  The rapid growth of 3 µm long titania nanotubes by anodization of titanium in a neutral electrochemical bath , 2010, Nanotechnology.

[3]  W. Shen,et al.  The large diameter and fast growth of self-organized TiO2 nanotube arrays achieved via electrochemical anodization , 2010, Nanotechnology.

[4]  M. Ferenets,et al.  Thin Solid Films , 2010 .

[5]  Z. Lockman,et al.  Photoactivity of anatase–rutile TiO2 nanotubes formed by anodization method , 2009 .

[6]  Yue Liu,et al.  The fabrication and characterization of novel carbon doped TiO2 nanotubes, nanowires and nanorods with high visible light photocatalytic activity , 2009, Nanotechnology.

[7]  Hai-chao Liang,et al.  Effects of structure of anodic TiO(2) nanotube arrays on photocatalytic activity for the degradation of 2,3-dichlorophenol in aqueous solution. , 2009, Journal of hazardous materials.

[8]  Zhaoxiong Xie,et al.  Synthesis of titania nanosheets with a high percentage of exposed (001) facets and related photocatalytic properties. , 2009, Journal of the American Chemical Society.

[9]  G. Cao,et al.  Carbon monoxide annealed TiO2nanotube array electrodes for efficient biosensor applications , 2009 .

[10]  Junxi Zhang,et al.  Fabrication of carbon-modified TiO2 nanotube arrays and their photocatalytic activity , 2008 .

[11]  L. Erickson,et al.  Synthesis of visible-light-active TiO2-based photocatalysts by carbon and nitrogen doping , 2008 .

[12]  Yun Lu,et al.  Facile preparation of micro-mesoporous carbon-doped TiO2 photocatalysts with anatase crystalline walls under template-free condition. , 2008, Chemical communications.

[13]  Haitao Wang,et al.  Multi-type carbon doping of TiO2 photocatalyst , 2007 .

[14]  V. K. Mahajan,et al.  Design of a Highly Efficient Photoelectrolytic Cell for Hydrogen Generation by Water Splitting: Application of TiO2-xCx Nanotubes as a Photoanode and Pt/TiO2 Nanotubes as a Cathode , 2007 .

[15]  M. Misra,et al.  Effect of water content of ethylene glycol as electrolyte for synthesis of ordered titania nanotubes , 2007 .

[16]  Craig A. Grimes,et al.  A new benchmark for TiO2 nanotube array growth by anodization , 2007 .

[17]  Tao Chen,et al.  Photoluminescence Characteristics of TiO2 and Their Relationship to the Photoassisted Reaction of Water/Methanol Mixture , 2007 .

[18]  Z. Zou,et al.  Low temperature preparation and visible light photocatalytic activity of mesoporous carbon-doped crystalline TiO2 , 2007 .

[19]  Craig A. Grimes,et al.  Highly-ordered TiO2 nanotube arrays up to 220 µm in length: use in water photoelectrolysis and dye-sensitized solar cells , 2007 .

[20]  Lixia Yang,et al.  Investigations on the self-organized growth of TiO2 nanotube arrays by anodic oxidization , 2006 .

[21]  Jan M. Macak,et al.  Anodic growth of self-organized anodic TiO2 nanotubes in viscous electrolytes , 2006 .

[22]  J. Macák,et al.  Smooth anodic TiO2 nanotubes: annealing and structure , 2006 .

[23]  Craig A. Grimes,et al.  Anodic Growth of Highly Ordered TiO2 Nanotube Arrays to 134 μm in Length , 2006 .

[24]  B. Liu,et al.  Template synthesis and characterization of WO3/TiO2 composite nanotubes , 2005 .

[25]  Keiji Kurashima,et al.  Self‐Organized Nanoporous Anodic Titania Films and Ordered Titania Nanodots/Nanorods on Glass , 2005 .

[26]  Sun-Jae Kim,et al.  Synthesis and characterization of carbon-doped titania as an artificial solar light sensitive photocatalyst , 2005 .

[27]  H. Kisch,et al.  Daylight photocatalysis by carbon-modified titanium dioxide. , 2003, Angewandte Chemie.

[28]  Fu Honggang,et al.  The preparation and characterization of nanoparticle TiO2/Ti films and their photocatalytic activity , 2003 .

[29]  T. Tamamura,et al.  Ordered Arrays of Nanopillars Formed by Photoelectrochemical Etching on Directly Imprinted TiO2 Single Crystals , 2003 .

[30]  Craig A. Grimes,et al.  Titanium oxide nanotube arrays prepared by anodic oxidation , 2001 .

[31]  J. Gilman,et al.  Nanotechnology , 2001 .

[32]  Vos,et al.  Preparation of photonic crystals made of air spheres in titania , 1998, Science.

[33]  P. Hoyer,et al.  Formation of a Titanium Dioxide Nanotube Array , 1996 .

[34]  W. Siripala,et al.  Interactions Between Photoinduced and Dark Charge Transfer across n-TiO[sub 2]Aqueous Electrolyte Interface , 1982 .

[35]  C. Gout,et al.  Electronic band structure of titanium dioxide , 1977 .