Mechanism of Low-Temperature Protonic Conductivity in Bulk, High-Density, Nanometric Titanium Oxide

Uncovering the mechanism of low‐temperature protonic conduction in highly dense nanostructured metal oxides opens the possibility to exploit the application of simple ceramic electrolytes in proton exchange fuel cells, overcoming the drawbacks related to the use of polymeric membranes. High proton conducting, highly dense (relative density 94 vol%) TiO2 samples are prepared by a fast pressure‐assisted sintering method, which allows leaving behind an interconnected network of open nanoporosity. Solid‐state 1H NMR is used to characterize the presence of strongly associated water confined in the nanopores and hydroxyl moieties bonded to the pores walls, providing a model to explain the unusually high protonic conductivity. At the lowest temperatures (T < 55 °C) protons hop between confined water molecules, according to a Grotthuss mechanism. The resulting conductivity values are however much higher than those of liquid water, indicating a significant increase in the charge carriers concentration. At higher temperatures (up to 450 °C) unexpected proton conduction is still present, thanks to the persistence of hydroxyl groups, derived from water chemisorption, which still produce protons by ionization. The phenomenon is strongly dependent on grain size, and not explicable by simple geometric brick‐layer models, suggesting that the enhanced ionization could rely on space charge region effects. Unexpected high proton conduction in highly dense sintered nano‐TiO2 electrolytes is explained by characterizing the open residual nanoporosity left behind by the fast pressure‐assisted sintering method used. Solid‐state 1H NMR identifies two sites involved in proton conduction: H2O confined in nanopores and –OH groups bonded to the nanopores walls. The effect of nanostructure on the enhanced proton conduction is discussed.