Platinum stepped surfaces

Climent V, Attard GA, Feliu JM. 2002a. Potential of zero charge of platinum stepped surfaces a combined approach of CO charge displacement and N2O reduction. J Electroanal Chem 532 67-74. 

Macia MD, Campina JM, Herrero E, Feliu JM. 2004. On the kinetics of oxygen reduction on platinum stepped surfaces in acidic media. J Electroanal Chem 564 141 -150. 

The reactions of C labeled hydrocarbons on platinum catalysts under hydrogen atmosphere are structure-sensitive (14) and isomerization reactions are very sensitive to the crystallographic planes as observed on the platinum stepped surfaces where the bond shift mechanism is favored compared with the cyclic mechanism (15). 

Clavilier J, Armand D, Sun SG, Petit M. Electrochemical adsorption behaviour of platinum stepped surfaces in sulphuric acid solutions. J Electroanal Chem 1986 205 267-77. 

Schematic molecular pictures of the four steps for the conversion of NO to N2 and O2 on a platinum metal surface.

Shin J, Tomquist WJ, Korzeniewski C, Hoaglund CS. 1996. Elementary steps in the oxidation and dissociative chemisorption of ethanol on smooth and stepped surface planes of platinum electrodes. Surf Sci 364 122. 

Climent V, Garcia-Araez N, Henero E, Feliu JM. 2006. Potential of zero total charge of platinum single crystals A local approach to stepped surfaces vicinal to Pt(lll). Russ J Electrochem 42 1145-1160. 

Electrochemical Surface Characterization of Platinum Electrodes Using Elementary Electrosorption Processes at Basal and Stepped Surfaces... 

Hydrogen Electrosorption and Oxidation of Formic Acid on Platinum Single-Crystal Stepped Surfaces... 

Stepped surfaces withstand cyclic oxidation-reduction treatments (146) like [111] and some other low-index planes. Steps have either [311] or [110] structures. They are claimed to be the only places where orbital hybridization does not take place (136). No wonder that such platinum (138) and iridium (147) surfaces have enhanced activity in Cg dehydrocyclization of n-heptane. 

The similarity of the shape of the voltammetric curves of platinized system to those reported for electrodes treated by the fast repetitive potential perturbation technique or obtained by annealing electrodeposited platinum and the appearance of signs characteristic for stepped surfaces allows us to assume that these phenomena should be ascribed to the similarities in the surface structure. 

In some cases, the step sites have different chemistry, i.e., they break chemical bonds, thereby producing new chemical species on the surface. This happens for example during NO adsorption on a stepped platinum surface l In this circumstance the step effect on ordering is through the new types of chemistry introduced by the presence of steps. Hydrocarbons for example dissociate readily at stepped surfaces of platinum or nickel while this occurs much more slowly on the low Miller-Index surfaces in the absence of a large concentration of steps As a result ordered hydrocarbon surface structures cannot be formed on the stepped surfaces of these metals while they can be produced on the low Miller-Index surfaces. 

J. Clavilier, Characterization of Platinum at Stepped Surface, in Electrochemical Surface Sciences, M. Soriaga, ecL, Ch. 14, American Chemical Society, Washington, IX (1988). 

Noncarbonium-ion-type 1-2-methyl shifts have been described by Barron et al. (11), and by Anderson and Avery (34). The reaction proceeds through a-y-diasorbed intermediates over platinum on neutral supports and does not involve carbonium-ion intermediates. According to this mechanism, the n-butylbenzene isobutylbenzene reaction involves the following steps (surface sites are represented by ) ... 

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 a series of studies, the variation of the turnover number for the dehydrogenation reaction (the number of product molecules/platinum surface atoms/second) with the hydrogen to hydrocarbon ratio at a constant hydrocarbon pressure of 4 x 10"8 Torr was determined. The results are shown in Fig. 20 for the several stepped surfaces studied. The reaction rates increase with increasing hydrogen to hydrocarbon ratio. If no hydrogen is introduced into the reaction chamber, the catalyst behaves very differently. No benzene... 

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... 

Studies to correlate the reactivity and the surface structure and composition of platinum surfaces indicate that the active platinum crystal surface must be heterogeneous. The heterogeneity involves the presence of various atomic sites that are distinguishable by their number of nearest neighbors (atoms in terraces, steps, and kinks), and also variation in surface chemical composition. A model that depicts the active platinum surface is shown schematically in Fig. 28. Part of the surface is covered with a partially de-... 

Attempts have been made to mimic proposed steps in catalysis at a platinum metal surface using well-characterized binuclear platinum complexes. A series of such complexes, stabilized by bridging bis(diphenyl-phosphino)methane ligands, has been prepared and structurally characterized. Included are diplati-num(I) complexes with Pt-Pt bonds, complexes with bridging hydride, carbonyl or methylene groups, and binuclear methylplatinum complexes. Reactions of these complexes have been studied and new binuclear oxidative addition and reductive elimination reactions, and a new catalyst for the water gas shift reaction have been discovered. 

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