Phase diagrams vanadium oxide

We refrain here from giving an extensive overview of studies on the surface structure of vanadium oxide nanolayers, as this has already been done for up to year 2003 in our recent review [97]. Instead, we would like to focus on prototypical examples, selected from the V-oxide-Rh(l 1 1) phase diagram, which demonstrate the power of STM measurements, when combined with state-of-the-art DFT calculations, to resolve complex oxide nanostructures. Other examples will highlight the usefulness of combining STM and STS data on a local scale, as well as data from STM measurements, and sample area-averaging spectroscopic techniques, such as XPS and NEXAFS, to derive as complete a picture as possible of the investigated system. 

The surface phase diagram of vanadium oxides on Rh(l 11) has been investigated in a series of papers of our group [4, 18, 19, 90, 101-103]. It is characterized by pronounced polymorphism and many different oxide structures have been detected as a function of coverage and growth temperature. The vanadium oxide structures for coverages up to the completion of the first monolayer formed on Rh(l 11) under the different preparation conditions may be subdivided into highly oxidized phases... 

Aircraft turbines in jet engines are usually fabricated from nickel-based alloys, and these are subject to combustion products containing compounds of sulphur, such as S02, and oxides of vanadium. Early studies of the corrosion of pure nickel by a 1 1 mixture of S02 and 02 showed that the rate of attack increased substantially between 922 K and 961 K. The nickel-sulphur phase diagram shows that a eutectic is formed at 910 K, and hence a liquid phase could play a significant role in the process. Microscopic observation of corroded samples showed islands of a separate phase in the nickel oxide formed by oxidation, which were concentrated near the nickel/oxide interface. The islands were shown by electron microprobe analysis to contain between 30 and 40 atom per cent of sulphur, hence suggesting the composition Ni3S2 when the composition of the corroding gas was varied between S02 02 equal to 12 1 to 1 9. The rate of corrosion decreased at temperatures above 922 K. 

The binary phase diagrams of the titanium oxides and sulphides are very complex with the formation of a very high number of intermediate phases (a similar behaviour is observed also for other intermediate transition metals such as vanadium). In the... 

Wenda, E. 1985. Phase diagram of vanadium pentoxide-molybdenum trioxide-silver oxide. I. Phase diagram of vanadium pentoxide-silver oxide system. J. Therm. Anal. 30 879-887. 

Catalyst fusion is essential to bring and keep the py-rosulfatc-vanadium oxide system into a homogeneous state which is the basis for operating the system at the eutectic in the ternary phase diagram. The reaction mechanism and the fact that the operation point of the... 

The link between structure and reactivity is again demonstrated by the complicated succession of vanadium oxide surface phases predicted by FP [77]. At certain O2 partial pressures, the metal substrate is computed to stabilise thin film phases that are not known in equivalent bulk form. The impliaation is that STM studies of thin insulator fihm on conducting substrates may have to contend with the complex, and sometimes novel, chemistry of thin films [2]. A phase diagram of non-stoichiometric surfaces is also generated by FP in Ref. [53], this time for silver oxidation. The aim is to bri(%e the pressure gap between ultra-high-vacuum research and the industrial reality of high-pressure reactors. 

Complex vanadium-phosphorus-oxide catalysts are the most successful industrial catalysts for the selective oxidation of /i-butane to maleic anhydride (MA) with uses in tetrahydrofurans (THE) and polyurethane intermediates. A schematic diagram of the reaction is shown in figure 3.21(a). These catalysts have been studied extensively (e.g. Centi et al 1993, Bordes 1987). In the selective catalysation of a-butane to MA, the best active phase in the V-P-0 system is identified as the vanadyl pyrophosphate, (VO)2P207 (hereafter... 

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