Density-functional studies of tungsten trioxide, tungsten bronzes, and related systems

Tungsten trioxide adopts a variety of structures which can be intercalated with charged species to alter the electronic properties, thus forming `tungsten bronzes'. Similar optical effects are observed upon removing oxygen from WO_3, although the electronic properties are slightly different. Here we present a computational study of cubic and hexagonal alkali bronzes and examine the effects on cell size and band structure as the size of the intercalated ion is increased. With the exception of hydrogen (which is predicted to be unstable as an intercalate), the behaviour of the bronzes are relatively consistent. NaWO_3 is the most stable of the cubic systems, although in the hexagonal system the larger ions are more stable. The band structures are identical, with the intercalated atom donating its single electron to the tungsten 5d valence band. Next, this was extended to a study of fractional doping in the Na_xWO_3 system (0 < x < 1). A linear variation in cell parameter, and a systematic change in the position of the Fermi level up into the valence band was observed with increasing x. In the underdoped WO_3-x system however, the Fermi level undergoes a sudden jump into the conduction band at around x = 0.2. Lastly, three compounds of a layered WO_4&#215;a,wdiaminoalkane hybrid series were studied and found to be insulating, with features in the band structure similar to those of the parent WO_3 compound which relate well to experimental UV-visible spectroscopy results.Comment: 12 pages, 16 figure

Aqueous hydroxylation mediated synthesis of crystalline calcium uranate particles

Metal uranates(VI) are solubility limiting U(VI) phases under high pH conditions and may act as suitable long-term wasteforms. The precipitation and thermal phase development mechanisms of calcium uranate particles formed via aqueous hydroxylation reactions are studied in order to address the lack of aqueous synthesis methods currently available. Hydrous Ca-deficient uranate particles formed from aqueous solutions saturated in U(VI) oligomers were found to thermally decompose via several weight-loss steps between 100 and 800 °C. Crystalline calcium uranate (Ca2U3O11) is initially formed at 700 °C via dehydration and dehydroxylation-olation reactions under redox-neutral conditions. This initial phase decomposes to biphasic CaUO4-UO2 particles at 800 °C via a reductive pathway