Bipolar Anodization for the Synthesis of TiO2 Nanotube Layers: New Concepts and Cell Designs

Abstract

Self-organized TiO2 nanotube (TNT) layers have attracted considerable scientific and technological interest over the past almost 20 years, due to their wide range of applications, including (photo-) catalysis, hydrogen generation and biomedical uses [1,2]. The synthesis of these TNT layers is usually carried out by electrochemical anodization of valve Ti metal substrates in various F--containing electrolytes using a conventional 2-electrode set-up with the Ti substrate as anode and a Pt-foil as cathode.By now, the TiO2 nanotube layer modification of Ti substrates is mainly focused on planar substrates, such as Ti foils and 2D Ti meshes, as these substrates can easily be connected to the potentiostat during anodization. However, for the real application in photocatalytic cleaners, 3D Ti substrates, such as 3D meshes or Ti spheres, are of high interest due to their significantly increased surface area compressed in a small volume.To anodize such 3D Ti substrates towards TiO2 nanotube layers, bipolar electrochemistry can be employed instead of using a conventional set-up [3-5]. In such a bipolar set-up, the Ti substrate is not directly connected to the potentiostat but placed in an electrolyte between two so-called feeder electrodes. Due to the electric field between the feeder electrodes, the Ti substrate is polarized and can be anodized if the applied potential between the feeder electrodes is high enough. This method opens the door for the preparation of TNT layers with gradients in dimensions (i.e. diameter and length of the nanotubes) [3-5] as well as for the preparation of TNT layers on Ti substrates, which cannot be directly connected to the potentiostat, e.g. small Ti spheres [6] and complicated 3D printed structures [7].In this presentation, the preparation of TNT layers on small Ti spheres [6] as well as on 3D printed Ti substrates [7] using bipolar electrochemistry will be shown. Their application in liquid and gas phase photocatalysis will be discussed. Furthermore, we will also show the possibility of using closed bipolar electrochemical cells, consisting of two closed half-cells with the Ti substrate as obstacle between the cells for the preparation of TiO2 nanotube layers with different dimensions on the two sides of a classical Ti foil [8].