Modelling and synthesis of Magnéli Phases in ordered titanium oxide nanotubes with preserved morphology

Abstract

The presence of Magnéli phases in titanium oxide nanotubes (NTs) can open up frontiers in many applications owing to their electrical and optical properties. Synthesis of NTs with Magnéli phases have posed a challenge due to the degradation and loss of morphology in NTs upon high-temperature treatments (>600 °C) in a reducing environment. This study reports on the synthesis of anodically formed NTs containing Magnéli phases through a double annealing route: oxygen (O2) annealing followed by annealing in 2% hydrogen with a nitrogen balance (2%H2-N2). The nucleation, growth, and transformation of anodized amorphous NTs into crystalline phases was investigated. The NTs obtained through this route were highly ordered and composed of mixed phases of anatase, rutile, and the Magnéli phase (Ti4O7). Experimental results from scanning electron microscopy (SEM), X-ray diffraction (XRD), scanning transmission electron microscopy (S/TEM), and Raman spectroscopy were combined with first principle calculations to develop an understanding of the sequential phase transformations during annealing. A predictive model was developed using density functional theory (DFT) to potentially predict the titanium oxides formed and their stability with reference to the mole fraction of oxygen. The change in the density of states (DOS), band structure, optical properties, and stability of phases are also discussed using DFT simulations. The combination of experimental characterization and modelling helped to understand the nucleation of anatase and rutile and the reorganization of these phases to form Magnéli phases on the anodized amorphous NTs through annealing treatment.