Abstract
Generally, anatase is the most desirable TiO(2) polymorphic phase for photovoltaic and photocatalytic applications due to its higher photoconductivity and lower recombination rates compared to the rutile phase. However, in applications where temperatures above 500 °C are required, growing pure anatase phase nanoparticles is still a challenge, as above this temperature TiO(2) crystallite sizes are larger than 35 nm which thermodynamically favors the growth of rutile crystallites. In this work, we show strong evidence, for the first time, that achieving a specific fraction (50%) of the {112} facets on the TiO(2) surface is the key limiting step for anatase-to-rutile phase transition, rather than the crystallite size. By using a fluorinated ionic liquid (IL) we have obtained pure anatase phase crystallites at temperatures up to 800 °C, even after the crystallites have grown beyond their thermodynamic size limit of ca. 35 nm. While fluorination by the IL did not affect {001} growth, it stabilized the pure anatase TiO(2) by suppressing the formation of {112} facets on anatase particles. By suppressing the {112} facets, using specific concentrations of fluorinated ionic liquid in the TiO(2) synthesis, we controlled the anatase-to-rutile phase transition over a wide range of temperatures. This information shall help synthetic researchers to determine the appropriate material conditions for specific applications.