Platinum cleaning surface

Ultraviolet photoelectron spectroscopy (UPS) results have provided detailed infomiation about CO adsorption on many surfaces. Figure A3.10.24 shows UPS results for CO adsorption on Pd(l 10) [58] that are representative of molecular CO adsorption on platinum surfaces. The difference result in (c) between the clean surface and the CO-covered surface shows a strong negative feature just below the Femii level ( p), and two positive features at 8 and 11 eV below E. The negative feature is due to suppression of emission from the metal d states as a result of an anti-resonance phenomenon. The positive features can be attributed to the 4a molecular orbital of CO and the overlap of tire 5a and 1 k molecular orbitals. The observation of features due to CO molecular orbitals clearly indicates that CO molecularly adsorbs. The overlap of the 5a and 1 ti levels is caused by a stabilization of the 5 a molecular orbital as a consequence of fomiing the surface-CO chemisorption bond. 

Figure A3.10.24 UPS data for CO adsorption on Pd(l 10). (a) Clean surface, (b) CO-dosed surface, (c) Difference spectrum (b-a). This spectrum is representative of molecular CO adsorption on platinum metals [M].

Platinum, palladium and the normal alloys of platinum used in industry are easily workable by the normal techniques of spinning, drawing, rolling, etc. To present a chemically clean surface of platinum and its alloys after fabrication, they may be pickled in hot concentrated hydrochloric acid to remove traces of iron and other contaminants —this is important for certain catalytic and high-temperature applications. In rolling or drawing thin sections of platinum, care must be taken to ensure that no dirt or other particles are worked into the metal, as these may later be chemically or elec-trolytically removed, leaving defects in the platinum. 

Numerous studies with low-energy electron diffraction (LEED) revealed that most of the clean surfaces of the platinum group metals exhibit an atomic arrangement that is identical to that expected from an undistorted termination of the bulk. Variations of the vertical lattice spacings between the topmost atomic layers are very small, if present at all (66). Exceptions are, however, found with the (100) and (110) planes of Ir and Pt. The clean and thermodynamically stable structures of the Pt(100) (67-69) and Ir(100) (70, 71) surfaces were found to reconstruct and to exhibit 5 x 1-LEED patterns. A plausible explanation (72) is that in these cases the topmost atomic layer forms a hexagonal arrangement, similar to that within the (111)... 

A variety of model catalysts have been employed we start with the simplest. Single-crystal surfaces of noble metals (platinum, rhodium, palladium, etc.) or oxides are structurally the best defined and the most homogeneous substrates, and the structural definition is beneficial both to experimentalists and theorists. Low-energy electron diffraction (LEED) facilitated the discovery of the relaxation and reconstruction of clean surfaces and the formation of ordered overlayers of adsorbed molecules (3,28-32). The combined application of LEED, Auger electron spectroscopy (AES), temperature-programmed desorption (TPD), field emission microscopy (FEM), X-ray and UV-photoelectron spectroscopy (XPS, UPS), IR reflection... 

The Pt NMR of small platinum particles on classic oxide supports show s that the clean-surface LDOS is largely independent of the support (sihca, alumina, and titania) and of the method of preparation (impregnation, ion exchange, and deposition of colloids). At a given resonance position, one always finds the same relaxation rate, independent of particle size or support. The shape of the spectrum is related to the sample dispersion. The same is true lor particles protected in fihiis of PVP. [However, samples prepared under conditions giving strong SMSIs behave differently 171)]... 

The Pti samples (182) were prepared as colloids, protected by a PVP polymer film. Layer statistics according to the NMR layer model (Eqs. 28-30) for samples with x = 0,0.2, and 0.8 are shown in Fig. 63. The metal/ polymer films were loaded into glass tubes and closed with simple stoppers. The NMR spectrum and spin lattice relaxation times of the pure platinum polymer-protected particles are practically the same as those in clean-surface oxide-supported catalysts of similar dispersion. This comparison implies that the interaction of the polymer with the surface platinums is weak and/or restricted to a small number of sites. The spectrum predicted by using the layer distribution from Fig. 63 and the Gaussians from Fig. 48 show s qualitative agreement w ith the observed spectrum for x = 0 (Fig. 64a). 

In order to demonstrate the importance of a local ensemble in the promotion by ruthenium of the L-H oxidation of CO, a number of experiments were carried out on stepped platinum surfaces [98]. The results of these experiments also provide an interesting comparison between surfaces modified by MVD ruthenium and through deposition from solution. Experiments were carried out [98] on Pt(lll), Pt(533), and Pt(311) single-crystal surfaces. Ruthenium was dosed from an aged solution of 5 X 10 RuCls in 0.5 M H2SO4 (believed to contain the complex Ru0(H20)] by spontaneous deposition at open-circuit potential) [80]. Experiments were carried out on the clean surfaces, following the spontaneously deposition of ruthenium, and on surfaces where the deposited ruthenium was reduced in a 10% H2 in Ar gas mixture. CO was adsorbed on the variously prepared surfaces from solution and stripped in CO-free H2SO4 electrolyte. 

Figure 20 Correlation between the total iif-LDOS found on clean platinum catalyst surfaces and the Knight shift of chemisorbed afterward. 

This is a specialised technique which has been applied in field emission and field ion microscopy (see Section 2.1.5c). It is achieved by giving the tip a positive potential. Tungsten can then be removed at liquid helium temperatures with an applied field of 5.7 x 10 V.cm Perfectly regular surface structures are exposed containing many different lattice planes. Clean surfaces have been produced on tungsten, nickel, iron, platinum, copper, silicon and germanium. It is potentially applicable to a wide range of materials, but the area of clean surface exposed is only about 10 ° cm . 

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