Different Reactivity of Rutile and Anatase TiO2 Nanoparticles: Synthesis and Surface States of Nanoparticles of Mixed-Valence Magnéli Oxides

Magnéli phases Ti_nO_2n−1 (3<n≤10) are mixed Ti⁴⁺/Ti³⁺ oxides with high electrical conductivity. When used for water remediation or electrochemical energy storage and conversion, they are nanostructured and exposed to various environments. Therefore, understanding their surface reactivity is of prime importance. Such studies have been hindered by carbon contamination from syntheses. Herein, this synthetic and characterization challenge is addressed through a new approach to 50 nm carbon-free Ti₄O₇ and Ti₆O₁₁ nanoparticles. It takes advantage of the different reactivities of rutile and anatase TiO₂ nanoparticles towards H₂, to use the former as precursor of Ti_nO_2n−1 and the latter as a diluting agent. This approach is combined with silica templating to restrain particle growth. The surface reactivity of the Magnéli nanoparticles under different atmospheres was then evaluated quantitatively by synchrotron-radiation-based X-ray photoelectron spectroscopy, which revealed oxidized surfaces with lower conductivity than the core. This finding sheds a new light on the charge transfer occurring in these materials.