Crystal surfaces of platinum

Lang B, Joyner R W and Somorjai G A 1972 LEED studies of high index crystal surfaces of platinum Surf. Sc 30 440-53... 

In addition, the same studies that were carried out on the Pt(lll) crystal face result in reaction rates identical to those found on stepped crystal surfaces of platinum. These observations support the contention that well-defined crystal surfaces can be excellent models for polycrystalline supported metal catalysts. It also tends to verify Boudart s hypothesis that cyclopropane hydrogenolysis is an example of a structure-insensitive reaction. The initial specific reaction rates, which were reproducible.within 10%, are within a factor of two identical to published values for this reaction on highly dispersed platinum catalysts. The activation energies that were observed for this reaction, in addition to the turnover number, are similar enough on the various platinum surfaces so that we may call the agreement excellent. 

ELEMENTAL STEPS DURING THE CATALYTIC DECOMPOSITION OF NO OVER STEPPED SINGLE CRYSTAL SURFACES OF PLATINUM AND RUTHENIUM... 

B. Lang, R.W. Joyner, and G.A. Somoijai. Low Energy Electron Diffraction Studies of High Index Crystal Surfaces of Platinum. Surf. Sci. 30 440 (1972). 

N. Li, Ionic and molecular adsorption at the single crystal surfaces of platinum and gold . PhD thesis. University of Guelph, 2000. 

Surface science studies have generated much insight into how hydrocarbons react on the surfaces of platinum single crystals. We refer to Somorjai [G.A. Somor-jai. Introduction to Surface Chemistry and Catalysis (1994), Wiley, New York] for a detailed overview. Also, the reactions of hydrocarbons on acidic sites of alumina or on zeolites have been studied in great detail [H. van Bekkum, E.M. Flanigan and J.C. Jansen (Eds.), Introduction to Zeolite Science and Practice (1991), Elsevier, Amsterdam],... 

The kinetics of CO oxidation from HClOi, solutions on the (100), (111) and (311) single crystal planes of platinum has been investigated. Electrochemical oxidation of CO involves a surface reaction between adsorbed CO molecules and a surface oxide of Pt. To determine the rate of this reaction the electrode was first covered by a monolayer of CO and subsequently exposed to anodic potentials at which Pt oxide is formed. Under these conditions the rate of CO oxidation is controlled by the rate of nucleation and growth of the oxide islands in the CO monolayer. By combination of the single and double potential step techniques the rates of the nucleation and the island growth have been determined independently. The results show that the rate of the two processes significantly depend on the crystallography of the Pt surfaces. 

The shape of the single crystal obtained by the method described above is a sphere with several flat facets as drawn in Fig. 2-6. Usually seven large facets, which are assigned to seven of possible eight (111) surfaces, are seen on the apex positions of a cube. Five small facets, which are assigned to five of possible six (100) surfaces, are also seen on the center of the faces of a cube. The missing (111) and (100) facets are supposed to be located where the shaft is attached. Figure 2—7 shows the relative positions of the three low index surfaces of platinum, which is a face-centered cubic lattice. 

So far, only a very few adsorbed molecular structures have been analyzed by surface crystallography. The first system studied in detail was acetylene adsorbed on the (111) crystal face of platinum. We shall discuss the complex adsorption and structural characteristics of this small organic molecule in some detail as it reveals the unique surface bonding arrangements that are possible and points to the importance of the use of additional techniques to complement the diffraction information. 

Parts (a) and (d) of Fig. 9.16 are the 100 surface of tungsten and the 111 surface of platinum, respectively. The symmetry of these patterns characterizes the cubic and hexagonal packing of the crystal faces. 

Fig. 6. A stereographic triangle of a platinum crystal depicting the various high Miller index surfaces of platinum that were studied.

The chemisorption of over 25 hydrocarbons has been studied by LEED on four different stepped-crystal faces of platinum (5), the Pt(S)-[9(l 11) x (100)], Pt(S)-[6(l 11) x (100)], Pt(S)-[7(lll) x (310)], and Pt(S)-[4(l 11 x (100)] structures. These surface structures are shown in Fig. 7. The chemisorption of hydrocarbons produces carbonaceous deposits with characteristics that depend on the substrate structure, the type of hydrocarbon chemisorbed, the rate of adsorption, and the surface temperature. Thus, in contrast with the chemisorption behavior on low Miller index surfaces, breaking of C-H and C-C bonds can readily take place at stepped surfaces of platinum even at 300 K and at low adsorbate pressures (10 9-10-6 Torr). Hydrocarbons on the [9(100) x (100)] and [6(111) x (100)] crystal faces form mostly ordered, partially dehydrogenated carbonaceous deposits, while disordered carbonaceous layers are formed on the [7(111) x (310)] surface, which has a high concentration of kinks in the steps. The distinctly different chemisorption characteristics of these stepped-platinum surfaces can be explained by... 

In a series of studies, the dehydrogenation and hydrogenolysis of cyclohexane was studied on both the stepped and low Miller index (111) crystal faces of platinum at a surface temperature of 300°C and a hydrogen to cyclohexane ratio of 20 1. While the rates on the stepped and low Miller index surfaces were not very different for the formation of benzene and hexane, the formation of cyclohexene was very structure sensitive, its rate being 100 times greater on the stepped surface than on the (111) crystal face. In Table III mrnnare the initial turnover numbers for the various reactions at low... 

In the present work, the interaction of the ethylene molecule with the (100) surfaces of platinum, palladium and nickel is studied using the cluster model approach. All these metals have a face centered cubic crystal structure. The three metal surfaces are modelled by a two-layer M9(5,4) cluster of C4V symmetry, as shown in Fig. 6, where the numbers inside brackets indicate the number of metal atoms in the first and second layer respectively. In the three metal clusters, all the metal atoms are described by the large LANL2DZ basis set. This basis set treats the outer 18 electrons of platinum, palladium and nickel atoms with a double zeta basis set and treats all the remainder electrons with the effective core potential of Hay and Wadt... 

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... 

Figure 5 Surface structure of the (111), (755) and (10,8,7) crystal faces of platinum displayed with corresponding FEED images...

Molecular beam scattering is also a powerfiil tool for probing the structure-sensitive nature of reactive (dissociative) scattering events. In Figure 27 the production of HD from the surface reaction of a mixed H2 D2 molecular beam is plotted versus incident angle for two crystal faces of platinum. The close-packed Pt(l 11) surface shows a low reaction probabihty... 

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