Differences in the local structure and composition of anodic TiO2 nanotubes annealed in vacuum and air

This work is dedicated to the influence of thermal treatment procedures in vacuum and air atmosphere on the structural features of multiwalled TiO2 anodic nanotubes (NTs) formed in fluorine-containing ethylene glycol (EG) based electrolyte investigated by high-resolution transmission electron microscopy (HRTEM) in conjunction with EDX and electronic nanodiffraction (STEM nanodiffraction), IR and Raman spectroscopy, XPS and ToF SIMS. Using electron nanodiffraction technique, there were estimated TiO2 nanocrystallite sizes for the inner layer of the NTs after annealing in air and vacuum for the first time. The differences in carbon distribution profiles in TiO2 nanotube crosscut after thermal treatments in air and vacuum were discussed. It was found that thermal treatment in vacuum leads to different phase composition of TiO2 NTs IL comparing to annealing in air. A sequential thermal treatment (firstly in vacuum and then in air) enables to remove carbon from TiO2 NTs surface and partly from TiO2 NTs IL and prevent detachment of IL from OL at the same time. The obtained data will be useful for understanding the mechanisms of structural modifications during thermal treatments as well as for functional properties optimization of such nanostructures. © 2020