Platinum stepped face

The idea that catalyst surfaces possess a distribution of sites of different energies has been around since the 1920s, but it has not been possible until fairly recently to show that adsorption sites on terraces, steps, and kinks differ in energy. For example, hydrogen shows stronger bonding to steps and kinks on platinum than on the 111 terraces. In addition, the activation energy for H2 dissociation is about zero on the step face and about 8.4 kJ mole-1 on the terrace plane. In addition, carbon monoxide is adsorbed with dissociation on the kinks of Pt, but in the molecular form on the steps and terraces. 

Although it is attractive to directly convert chemical energy to electricity, PEM fuel cells face significant practical obstacles. Expensive heavy metals like platinum are typically used as catalysts to reduce energy barriers associated with the half-cell reactions. PEM fuel cells also cannot use practical hydrocarbon fuels like diesel without complicated preprocessing steps. Those significantly increase the complexity of the overall system. At this time, it appears likely that PEM fuel cells will be confined to niche applications where high cost and special fuel requirements are tolerable. 

Fig. 3. LEED patterns and schematic representations of the surface configurations of platinum single-crystal surfaces, (a) Pt(Ill) containing less than 1012 defects/cm2, (b) Pt(557) face containing 2.5 x 1014 step atoms/cm2 with an average spacing between steps of 6 atoms, and (c) Pt(679) containing 2.3 x 10 4 step atoms/cm2 and 7 x 1014 kink atoms/cm2 with an average spacing between steps of 7 atoms and between kinks of 3 atoms.

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... 

The chemisorption of hydrocarbons, ethylene, cyclohexene, n-heptane, benzene and naphthalene at room temperature and above were studied on both the Au(l 11) and Au[6(l 11) x (100)] stepped surfaces (29). The difference in the adsorption characteristics of hydrocarbons on gold surfaces and on platinum surfaces is striking. The various light hydrocarbons studied (ethylene, cyclohexene, n-heptane, and benzene) chemisorb readily on the Pt(lll) surface. These molecules, on the other hand, do not adsorb on the Au(lll) surface under identical experimental conditions as far as can be judged by changes that occur in the Auger spectra. Naphthalene, which forms an ordered surface structure on the Pt(lll) face, forms a disordered layer on adsorption on the Au(l 11)surface. 

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. 

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... 

We have been able to identify two types of structural features of platinum surfaces that influence the catalytic surface reactions (a) atomic steps and kinks, i.e., sites of low metal coordination number, and (b) carbonaceous overlayers, ordered or disordered. The surface reaction may be sensitive to both or just one of these structural features or it may be totally insensitive to the surface structure, The dehydrogenation of cyclohexane to cyclohexene appears to be a structure-insensitive reaction. It takes place even on the Pt(l 11) crystal face, which has a very low density of steps, and proceeds even in the presence of a disordered overlayer. The dehydrogenation of cyclohexene to benzene is very structure sensitive. It requires the presence of atomic steps [i.e., does not occur on the Pt(l 11) crystal face] and an ordered overlayer (it is poisoned by disorder). Others have found the dehydrogenation of cyclohexane to benzene to be structure insensitive (42, 43) on dispersed-metal catalysts. On our catalyst, surfaces that contain steps, this is also true, but on the Pt(lll) catalyst surface, benzene formation is much slower. Dispersed particles of any size will always contain many steplike atoms of low coordination, and therefore the reaction will display structure insensitivity. Based on our findings, we may write a mechanism for these reactions by identifying the sequence of reaction steps ... 

Harting et al. reported the results of DFT and AIMD studies for the oxidation of methanol on the Pt(l 1 1) face in aqueous solution.122 Their work reveals that the oxidation of methanol is initiated at the moment when a hydrogen bond forms between the OH group of the methanol and a water molecule. The initial step of the reaction is the cleavage of a CH bond with the bond direction points towards the platinum surface. This is followed by a rapid dissociation of the methanol OH bond, which leads to formation of a formaldehyde as a stable intermediate within the timescale of the simulation. Charge delocalization is achieved by the formation of a Zundel ion H502+ in the aqueous phase. 

Surface Crystallography and Composition. Platinum (11) and nickel (8,9,12) have been the metal surfaces examined in our surface science studies to date. The surface coordination chemistry has been examined as a function of surface crystallography and surface composition. Surfaces specifically chosen for an assay of metal coordination number and of geometric effects were the three low Miller index planes (111), (110) and (100) as well as the stepped 9(lll)x(lll) and stepped-kinked 7(lll)x(310) surfaces (both platinum and nickel are face centered cubic). 

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