High temperature–pressure synthesis of Ti-doped tohdite and corundum from hydrous Al2O3–TiO2 gel

Hydrous Al2O3–TiO2 (78:22 in molar ratio) gel was fired at various P–T conditions using a piston-cylinder apparatus and identified by XRD, FTIR, optical microscopy and electron microscopy. Below 675 °C, the sample remained amorphous at ambient pressure, yet transformed at 1.5 kbar to Ti-doped tohdite, which is elongated along the crystallographic c-axis, with well-developed (0 0 0 1) base and { 1   0   1 ¯   0 } ledges. Tohdite has a significant water/hydroxy content and is therefore susceptible to pore coalescence parallel to the basal layer upon electron dosage. Tohdite also contains Ti4+ up to 3 at.%, which replaces Al3+ in tetrahedral and/or octahedral sites to form superstructures and defect microstructures. In contrast, a higher T–P condition (above 675 °C and 8 kbar) caused the formation of more stable Ti-doped corundum, which is hexagonal-rhombohedral in shape and in epitaxial association with rutile nuclei. Ti-doped tohdite and corundum shed light on a sol–gel route for their occurrence in peraluminous metamorphic rock. The nanoporous and nanodelaminated tohdite may have potential catalytic applications.