Sites sputtering

Work has also been conducted that involved the investigation, via infrared spectroscopy, of matrix-isolated, plutonium oxides (40), with the appropriate precautions being taken because of the toxicity of plutonium and its compounds. A sputtering technique was used to vaporize the metal. The IR spectra of PuO and PUO2 in both Ar and Kr matrices were identified, with the observed frequencies for the latter (794.25 and 786.80 cm", respectively) assigned to the stretchingmode of Pu 02. Normal-coordinate analysis of the PUO2 isotopomers, Pu 02, Pu 02, and Pu 0 0 in Ar showed that the molecule is linear. The PuO molecule was observed in multiple sites in Ar matrices, but not in Kr, with Pu 0 at 822.28 cm" in the most stable, Ar site, and at 817.27 cm" in Kr. No evidence for PuOa was observed. 

Some physical techniques can be classified into flame treatments, corona treatments, cold plasma treatments, ultraviolet (UV) treatment, laser treatments, x-ray treatments, electron-beam treatments, ion-beam treatments, and metallization and sputtering, in which corona, plasma, and laser treatments are the most commonly used methods to modify silicone polymers. In the presence of oxygen, high-energy-photon treatment induces the formation of radical sites at surfaces these sites then react with atmospheric oxygen forming oxygenated functions. 

Susac et al. [33] showed that the cobalt-selenium (Co-Se) system prepared by sputtering and chemical methods was catalytically active toward the ORR in an acidic medium. Lee et al. [34] synthesized ternary non-noble selenides based on W and Co by the reaction of the metal carbonyls and elemental Se in xylenes. These W-Co-Se systems showed catalytic activity toward ORR in acidic media, albeit lower than with Pt/C and seemingly proceeding as a two-electron process. It was pointed out that non-noble metals too can serve as active sites for catalysis, in fact generating sufficient activity to be comparable to that of a noble metal, provided that electronic effects have been induced by the chalcogen modification. 

The Fe(l1l) surface is composed of four-fold coordinated atoms and exposed second layer atoms that are seven-fold coordinated while the Fe(l10) and Fe(lOO) planes have only six-fold and four-fold coordinated atoms respectively. Here we have defined the coordination number as the number of nearest neighbor atoms. Dumesic s proposal that the seven-fold coordinated atom is an important component of the catalytically active site is not contradicted by our results ( ). It is also worth noting that the relative roughness or openess of the each plane follows the same progression as their catalytic activities. Table II also shows that the activity of each of the two less active surfaces was markedly enhanced by sputtering with Ar. It is possible that sputtering has exposed seven-fold coordinate atoms at the surface or that it is the roughness of the surface that is responsible for the structure senstivity of the reaction rate. 

Steady-state molecular beam studies of the reaction of methylacetylene on reduced Ti02 (001) surfaces were undertaken to determine whether this reaction could be performed catalytically under UHV conditions. A representative experiment is presented in Figure 1. Prior to each experiment, the surface was sputtered and annealed to a temperature between 400 K and 550 K surfaces prepared in this manner have the highest fraction of Ti(+2) sites (ca. 30% of all surface cations) of any surface we have been able to create by initial sputtering [3]. Thus these are the surfaces most active for cyclotrimerization in TPD experiments [1]. Steady-state production of trimethylbenzene (as indicated by the m/e 105 signal detected by the mass spectrometer) was characterized by behavior typical of more traditional catalysts a jump in activity upon initial exposure of the crystal to the molecular beam, followed by a decay to a lower, constant level of activity over a longer time scale. Experiments of up to 6 hours in duration showed... 

Figure 3.2. Sequence of PM-RAIR spectra taken on a sputtered Co(0001) surface. The starting conditions were lOOmbar of CO at 298 K 200mbar of H2 was then added and the temperature increased stepwise to 490 K. It can be seen that the absorption signal due to CO attached to defect sites is removed in an irreversible process. The lowest curve was obtained at room temperature and under vacuum conditions and the hydrogen desorbs from the Co, while the CO and hydrocarbons remain. (After Beitel et al. 1997.)...

In order to understand the observed shift in oxidation potentials and the stabilization mechanism two possible explanations were forwarded by Kotz and Stucki [83], Either a direct electronic interaction of the two oxide components via formation of a common 4-band, involving possible charge transfer, gives rise to an electrode with new homogeneous properties or an indirect interaction between Ru and Ir sites and the electrolyte phase via surface dipoles creates improved surface properties. These two models will certainly be difficult to distinguish. As is demonstrated in Fig. 25, XPS valence band spectroscopy could give some evidence for the formation of a common 4-band in the mixed oxides prepared by reactive sputtering [83],... 

A similar study was performed by the same group on a model catalyst system i.e., a Mn/Ru (0001) surface, prepared by sputtering Mn on a Ru (0001) surface at room temperature using a sputtered ion gun. The techniques of choice were SSIMS, EELS and TPD. It was concluded that Mn reduces the coverage of CO adsorbed on the surface by physically blocking the adsorption sites. The adsorbed CO molecule is predominantly linearly bonded, whereas EELS indicated a possible existence of an electronic interaction between the deposited Mn and Ru. This was reflected by the change in the CO stretching frequency to lower wavenumbers once Mn was deposited on the Ru surface. 

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