Self-organized, free-standing TiO2 nanotube membranes: Effect of surface electrokinetic properties on flow-through membranes

In the present work we investigate the effect of the surface electrokinetic properties and presence of background ions on the flow of a marker dye through TiO2 nanotube membranes. We believe the results to be of high significance not only for filtration but also for the design of microphotoreactor application based on photoactive TiO2 nanotubes membrane. First, both-side open, high aspect ratio TiO2 nanotube membranes were obtained by fast anodization of Ti to self-aligned TiO2 nanotube layers, followed by a lift-off process. Then we investigated the permeation through the TiO2 nanotube membranes by diffusion of acid orange 7 (AO7) and extracted the dye diffusion rates. The effects of pH, ionic concentration, and size of ions were investigated, and the results were compared with theoretical modeling of the surface charge of TiO2 and the neighbouring electric double layer as a function of different species of ions; the modeling confirms the experimental data. We observed a remarkable influence of the background ion species, as well as of ion concentrations and pH in the feed solution on the diffusion rate of AO7. The results of modeling are well in line with the observed influence of TiO2 nanotube inner surface charge and effective size (hydrodynamic radius) of the ions in the background solution. It is also observed that the absolute permeate flux and the membrane's permeability strongly depend on the electric and wetting conditions of the membrane surface.