Vanadyl phosphate dihydrate, a solid acid: the role of water in VOPO4�2H2O and its sodium derivatives Na x (VIV x VV 1?x O)PO4�(2?x)H2O

Sodium-containing intercalates having as general formula Na x VOPOP4·(2−x)H2O (0.25≤x<0.50) have been obtained and characterized. Orthorhombic phases, which essentially maintain the structure of the layered oxide hydrate VOPO4·2H2O result. Intercalated sodium ions act as ‘pillars’. The presence of H3O+ ions in the parent VOPO4·2H2O and also in some reduced phases, is detected. The understanding of the structural role of the water molecules is advanced and the topotactic dehydration/rehydration processes are studied. The formation of a new metastable VOPO4·H2O phase is established.