Alloys platinum-rhenium

Some of the materials that have been examined as catalysts include Pure Platinum, Platinum-Iridium Alloys, Various Compositions of Platinum-Rhodium Alloys, Platinum-Palladium Alloys, Platinum-Ruthenium Alloys, Platinum-Rhenium Alloys, Platinum-Tungsten Alloys, FejOj-M CVI Oj (Braun Oxide), CoO-Bi20j, CoO with AI2O3, Thorium, Cerium, Zinc and Cadmium. 

Rhenium is a rare metal with total world production in 2007 estimated at about 50 tonnes. The principal industrial applications of rhenium are in high-temperature alloys used in jet engines and in platinum-rhenium catalysts used in the petroleum industry. In recent years, the demand for rhenium has increased and prices have risen to more than US 10,000 per kg. In late 2008, rhenium was the sixth most expensive traded element (WWW. lipmann.co.u k/fa cts/expe ns i ve. htm I)... 

The influence of the support is undoubted and spillover was further confirmed by the excess of hydrogen chemisorbed by a mechanical mixture of unsupported alloy and TJ-A1203 above that calculated from the known values for the separate components. It was also observed that the chemisorption was slower on the supported than on the unsupported metal and that the greater part of the adsorbate was held reversibly no comment could be made on the possible mediation by traces of water. On the other hand, spillover from platinum-rhenium onto alumina appears to be inhibited for ratios Re/(Pt Re) > 0.6. In an infrared investigation of isocyanate complexes formed between nitric oxide and carbon monoxide, on the surface of rhodium-titania and rhodium-silica catalysts, it seems that the number of complexes exceeded the number of rhodium surface atoms.The supports have a pronounced effect on the location of the isocyanate bond and on the stability of the complexes, with some suggestion of spillover. 

The catalysts were prepared by contacting alumina with aqueous solutions of chloroplatinic acid and ammonium perrhenate. The consumption of hydrogen during reduction corresponded to complete reduction of platinum from the +4 oxidation state to the metal and of rhenium from the +7 to the +4 state. The X-ray diffraction data on the metal residue from the leached catalysts showed no evidence for the presence of rhenium metal or a platinum-rhenium alloy. Most of the rhenium was found in the leaching solution. Finally, the authors stated that data from an electron spin resonance experiment on one of the reduced platinum-rhenium catalysts were consistent with their conclusion that the rhenium was present in the +4 state. 

For catalysts that were simply dried in air at 110°C after impregnation of the alumina with H2PtClfe and Re207, it was concluded that a platinum-rhenium alloy formed on reduction. This conclusion was based on the observation that the presence of platinum accelerated the reduction of oxygen chemisorbed on the rhenium and on results showing that the frequencies of the infrared absorption bands of carbon monoxide adsorbed on platinum and rhenium sites in platinum-rhenium catalysts were different from those found with catalysts containing only platinum or rhenium. However, for catalysts calcined in air at 500°C prior to reduction in hydrogen, it was concluded that the platinum exhibited much less interaction with the rhenium (66,71). 

Metals and alloys, the principal industrial metalhc catalysts, are found in periodic group TII, which are transition elements with almost-completed 3d, 4d, and 5d electronic orbits. According to theory, electrons from adsorbed molecules can fill the vacancies in the incomplete shells and thus make a chemical bond. What happens subsequently depends on the operating conditions. Platinum, palladium, and nickel form both hydrides and oxides they are effective in hydrogenation (vegetable oils) and oxidation (ammonia or sulfur dioxide). Alloys do not always have catalytic properties intermediate between those of the component metals, since the surface condition may be different from the bulk and catalysis is a function of the surface condition. Addition of some rhenium to Pt/AlgO permits the use of lower temperatures and slows the deactivation rate. The mechanism of catalysis by alloys is still controversial in many instances. 

The reason for it is not obvious since gold is not a very rare element on earth, and other metals, for example, platinum, rhodium, osmium, and rhenium, are less abundant and more expensive. Its yellow color cannot be the reason either, since other metals, such as copper, and its alloys as bronze or brass, have different colors from the bright silver of most of the metals. Probably, the reason resides in its noble character. In fact, gold does not tarnish with time, and coins and jewelry remain indefinitely unalterable even after long exposure to extremely aggressive conditions. 

Phillips and Timms [599] described a less general method. They converted germanium and silicon in alloys into hydrides and further into chlorides by contact with gold trichloride. They performed GC on a column packed with 13% of silicone 702 on Celite with the use of a gas-density balance for detection. Juvet and Fischer [600] developed a special reactor coupled directly to the chromatographic column, in which they fluorinated metals in alloys, carbides, oxides, sulphides and salts. In these samples, they determined quantitatively uranium, sulphur, selenium, technetium, tungsten, molybdenum, rhenium, silicon, boron, osmium, vanadium, iridium and platinum as fluorides. They performed the analysis on a PTFE column packed with 15% of Kel-F oil No. 10 on Chromosorb T. Prior to analysis the column was conditioned with fluorine and chlorine trifluoride in order to remove moisture and reactive organic compounds. The thermal conductivity detector was equipped with nickel-coated filaments resistant to corrosion with metal fluorides. Fig. 5.34 illustrates the analysis of tungsten, rhenium and osmium fluorides by this method. 

Space technology often uses alloys that are too expensive for everyday use. An example is the propulsion systems used for keeping satellites in place. Some of these systems use alloys made of iridium and another platinum metal, rhenium. These alloys remain strong at high temperatures and are not attacked by fuels used in the systems. 

In conclusion by using rhenium as adsorbent instead of platinum, it is possible to achieve the ensemble control by sulfur passivation, at sulfur levels comparable to those applied for nickel and much lower than that which would have been required on a non-alloyed Pt-catalyst. A similar ensemble effect is achieved by alloying alone on Pt-Sn catalysts ... 

Third, the doublet and, especially, sextet models require very precise superimposing of the molecule on the catalyst lattice. We have found that the cyclohexane derivatives, in accordance with the sextet model, smoothly dehydrogenate only on the following metals nickel, cobalt, iridium, palladium, platinum, ruthenium, osmium, and rhenium, all of which crystallize in Al, A3 lattices with certain interatomic distances. These results extend to the alloys of these metals. The catalytic activity of rhenium for this reaction was predicted by the multiplet theory as this metal maintains the square of activity this prediction was realized experimentally in the laboratory of the author. Similar correlations take place in the exchange of cyclanes with deuterium. 

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