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Arrays of TiO 2 nanotubes (TiO 2 NTs) with grassy surfaces were observed on titanium foil anodised at 60 V in fluorinated ethylene glycol (EG) with added hydrogen peroxide (H 2 O 2 ). The grassy surface was generated by the chemical etching and dissolution of the surface of the TiO 2 NTs walls, which was accelerated by the temperature increase on the addition of H 2 O 2 . Upon annealing at 600 °C, the grassy part of the TiO 2 NTs was found to consist of mostly anatase TiO 2 whereas the bottom part of the anodic oxide comprised a mixture of anatase and rutile TiO 2 . The TiO 2 NTs were then used to reduce hexavalent chromium (Cr(VI)) under ultraviolet radiation. They exhibited a rather efficient photocatalytic effect, with 100% removal of Cr(VI) after 30 min of irradiation. The fast removal of Cr(VI) was due to the anatase dominance at the grassy part of the TiO 2 NTs as well as the higher surface area the structure may have. This work provides a novel insight into the photocatalytic reduction of Cr(VI) on grassy anatase TiO 2 NTs.

Visible-light-active freestanding zirconia (ZrO 2 ) nanotube (FSZNT) arrays were fabricated by a facile electrochemical anodization method in fluoride containing ethylene glycol electrolyte added to it was 1 vol% of potassium carbonate (K 2 CO 3 ) at 60 V for 1 h. Poor adhesion at the metal∣oxide interface was induced by K 2 CO 3 leading to the formation of FSZNT flakes. The effect of the crystal structures of the FSZNTs e.g., amorphous, amorphous/tetragonal, and tetragonal/monoclinic was investigated towards the photocatalytic reduction of 10 ppm hexavalent chromium, Cr(VI) at pH 2 under sunlight. The results demonstrate the amorphous FSZNTs exhibited the highest Cr(VI) removal efficiency than the crystalline FSZNTs (95% versus 33% after 5 h). The high photocatalytic activity of the amorphous FSZNTs can be attributed to enhanced Cr(VI) adsorption, high visible light absorption, and better charge carrier separation. The low photocatalytic activity of the crystalline FSZNTs annealed at 500 °C was mainly attributed to poor Cr(VI) adsorption, low visible light absorption, and less photoactive monoclinic-ZrO 2 .

ZrO 2 nanotubes (ZrNTs) were produced by anodisation of zirconium foil in H 2 O 2 /NH 4 F/ethylene glycol electrolyte. The as-anodised foils were then soaked in the anodising electrolyte for 12 h. Soaking weakens the adherence of the anodic layer from the substrate resulting in freestanding ZrNTs (FS-ZrNTs). Moreover, the presence of H 2 O 2 in the electrolyte also aids in weakening the adhesion of the film from the foil, as foil anodised in electrolyte without H 2 O 2 has good film adherence. The as-anodised FS-ZrNTs film was amorphous and crystallised to predominantly tetragonal phase upon annealing at >300 °C. Annealing must, however, be done at <500 °C to avoid monoclinic ZrO 2 formation and nanotubes disintegration. FS-ZrNTs annealed at 450 °C exhibited the highest photocatalytic ability to degrade methyl orange (MO), whereby 82% MO degradation was observed after 5 h, whereas FS-ZrNTs with a mixture of monoclinic and tetragonal degraded 70% of MO after 5 h.

Self-organized, 23 μm-thick anodic TiO2 nanotube (TNT) arrays were formed in sodium hydroxide/fluoride/ethylene glycol (EG) electrolyte at 60 V for 60 min. The presence of sodium hydroxide (NaOH) in the fluoride/EG electrolyte accelerates the formation of the TiO2 nanotube arrays. The anodic film was then decorated with silver nanoparticles (Ag NPs) by the photodeposition process and used as a photoanode in a rear-side-illuminated dye-sensitized solar cell. The Ag NPs decorated TNT arrays, with the former having diameters of 10-30 nm formed from 0.2 M of Ag-precursor solution and exhibiting the highest photoconversion efficiency (η) of 3.7% and a short-circuit current density of 12.2 mA cm(-2) compared to η = 3% and short-circuit current density of 9.1 mA cm(-2) for a sample without Ag NPs. The increase in η is thought to be due to the surface plasmon resonance and excess electrons from the nanoparticles.

In this work, 18.5 microm titanium oxide (TiO(2)) 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 TiO(2) 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 microm 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.

The length of titania nanotubes formed by anodization of 0.1 mm thick titanium foil was found to be a strong function of the pH of the electrolyte. The longest nanotubes were formed by using an electrolyte consisting of 1 M Na(2)SO(4) plus 5 wt% NH(4)F with pH 7. At this pH, after 30 min of anodization, 3 microm length nanotubular titania arrays with top diameters of approximately 50 nm and bottom diameters of 100 nm were produced. No acid was added to this electrolyte. The formation of titania nanotubes in neutral pH systems was therefore successful due to the excess NH(4)F in the electrolyte which increases the chemical dissolution process at the metal/oxide interface. Since the pH of the electrolyte at the top part of the nanotubes is kept very high, the dissolution of the nanotubes at the surface is minimal. However, the amount is adequate to remove the initial barrier layer, forming a rather well-defined nanoporous structure. All anodized foils were weakly crystalline and the transformation to anatase phase was achieved by heat treatment at temperatures from 200 to 500 degrees C for 1 h in air. Annealing at temperatures above 500 degrees C induce rutile phase formation and annealing at higher temperatures accelerates the diffusion of Ti(4+) leading to excessive growth and the nanotubular structure diminishes.