Efficient suppression of nanograss during porous anodic TiO2 nanotubes growth

When Ti foil was anodized in fluoride-containing electrolyte for a long time, undesired etching-induced “nanograss” would inevitably generate on the top of porous anodic TiO2 nanotubes (PATNTs). The nanograss will hinder the ions transport and in turn yield depressed (photo) electrochemical performance. In order to obtain nanograss-free nanotubes, a modified three-step anodization and two-layer nanostructure of PATNTs were designed to avoid the nanograss. The first layer (L1) nanotubes were obtained by the conventional two-step anodization. After washing and drying processes, the third-step anodization was carried out with the presence of L1 nanotubes. The L1 nanotubes, serving as a sacrificed layer, was etched and transformed into nanograss, while the ultralong nanotubes (L2) were maintained underneath the L1. The bi-layer nanostructure of the nanograss/nanotubes (L1/L2) was then ultrasonically rinsed in deionized water to remove the nanograss (L1 layer). Then much longer nanotubes (L2 layer) with intact nanotube mouths could be obtained. Using this novel approach, the ultralong nanotubes without nanograss can be rationally controlled by adjusting the anodizing times of two layers.