ScVO4 under non-hydrostatic compression:a new metastable polymorph

Abstract

Se estudia el comportamiento bajo alta presión del vanadato de scandio, ScVO4, bajo compresión no hidrostática. El estudio se realiza mediante difracción de rayos X en polvo usando radiación sincrotrón. Se detecta una transición no reversible desde la fase zircon a la fase fergusonita alrededor de 6 GPa con una discontinuidad en el volumen de un 10%. La fase fergusonota se puede recuperar como metaestable confirmandose mediante XRD. Las simulaciones ab intio confirman los resultados experimentales. Las propiedades ópticas y la propiedades vibracionales de la fase fergusonita son discutidas. A presión ambiuente el gap de la fase zircon (fergusonita) es 2.75 eV (2.3 eV). Esto sugiere que este nuevo polimorfo metaestable del ScVO4 puede tener aplicaciones en tecnologias verdes, por ejemplo siendo usado como materal fotocatalitico para producción de hidrógeno mediante disociación de agua.

The high-pressure (HP) behaviour of scandium vanadate (ScVO4) is investigated under non-hydrostatic compression. The compound is studied by means of synchrotron-based powder x-ray diffraction (XRD) and optical-absorption techniques. The occurrence of a non-reversible phase transition is detected. The transition is from the zircon structure to the fergusonitetype structure and takes place around 6 GPa with nearly 10% volume discontinuity. XRD measurements on the pressure cycled sample confirm for the first time that the fergusonitetype ScVO4 can be recovered as the metastable phase at ambient conditions. Raman spectroscopic measurements verify the metastable phase to be of a fergusonite-type phase. Theoretical calculations also corroborate the experimental findings. The fergusonite phase is found to be stiffer than the ambient-pressure zircon phase, as indicated by the observed experimental and theoretical bulk moduli. The optical properties and lattice-dynamics calculation of the fergusonite ScVO4 are discussed. At ambient pressure the band gap of the zircon (fergusonite)-type ScVO4 is 2.75 eV (2.3 eV). This fact suggests that the novel metastable polymorph of ScVO4 can have applications in green technologies; for instance, it can be used as photocatalytic material for hydrogen production by water splitting.