Growth and in situ transformation of TiO2 and HTiOF3 crystals on chitosan-polyvinyl alcohol co-polymer substrates under vapor phase hydrothermal conditions

Abstract

A chitosan-polyvinyl alcohol (CS/PVA) co-polymer substrate possessing a large number of amino and hydroxyl groups is used as a substrate to induce the direct growth and in situ sequential transformation of titanate crystals under HF vapor phase hydrothermal conditions. The process involves four distinct formation/transformation stages. HTiOF3 crystals with well-defined hexagonal shapes are formed during stage I, and are subsequently transformed into {001} faceted anatase TiO2 crystal nanosheets during stage II. Interestingly, the formed anatase TiO2 crystals are further transformed into cross-shaped and hollow squareshaped HTiOF3 crystals during stages III and IV, respectively. Although TiO2 crystal phases and facet transformations under hydrothermal conditions have been previously reported, in situ crystal transformations between different titanate compounds have not been widely reported. Such crystal formation/transformations are likely due to the presence of large numbers of amino groups in the CS/PVA substrate. When celluloses possessing only hydroxyl groups are used as a substrate, the direct formation of {001} faceted TiO2 nanocrystal sheets is observed (rather than any sequential crystal transformations). This substrate organic functional group-induced crystal formation/transformation approach could be applicable to other material systems.