Platinum surface structure

In order to assess the role of the platinum surface structure and of CO surface mobility on the oxidation kinetics of adsorbed CO, we carried out chronoamperometry experiments on a series of stepped platinum electrodes of [n(l 11) x (110)] orientation [Lebedeva et al., 2002c]. If the (110) steps act as active sites for CO oxidation because they adsorb OH at a lower potential than the (111) terrace sites, one would expect that for sufficiently wide terraces and sufficiently slow CO diffusion, the chronoamperometric transient would display a CottreU-hke tailing for longer times owing to slow diffusion of CO from the terrace to the active step site. The mathematical treatment supporting this conclusion was given in Koper et al. [2002]. 

The potential of the stripping peak, and hence the activity of the electrode for CO oxidation, also depends on the platinum surface structure in general and on the step density in particular. Based on the chronoamperometry experiments described in Section 6.2.1.1, one would expect the stripping peak to shift to lower potential with increasing step density. That this is indeed the case is shown in Fig. 6.6. Again, this... 

The presence of o-qulnone surface waves seems, at the present time, to be coincidental to activation particularly In the case of ascorbic acid oxidation. On the other hand. Its presence may serve as a criterion of cleanliness and activation. Thus, the surface waves at 0.250 and 0.190 are Indicators or signatures for active GCE electrodes and should be used as diagnostic for a clean GCE surface as Is the hydrogen fine structure for platinum (31). It Is unfortunate that the o-qulnone peaks do not appear to be proportional to the surface area as Is the platinum fine structure. 

The molecular modelling approach, taking into account the pyruvate—cinchona alkaloid interaction and the steric constraints imposed by the adsorption on the platinum surface, leads to a reasonable explanation for the enantio-differentiation of this system. Although the prediction of the complex formed between the methyl pyruvate and the cinchona modifiers have been made for an ideal case (solvent effects and a quantum description of the interaction with the platinum surface atoms were not considered), this approach proved to be very helpful in the search of new modifiers. The search strategy, which included a systematic reduction of the cinchona alkaloid structure to the essential functional parts and validation of the steric constraints imposed to the interaction complex between modifier and methyl pyruvate by means of molecular modelling, indicated that simple chiral aminoalcohols should be promising substitutes for cinchona alkaloid modifiers. Using the Sharpless symmetric dihydroxylation as a key step, a series of enantiomerically pure 2-hydroxy-2-aryl-ethylamines... 

Platinum Nanoclusters Size and Surface Structure Sensitivity of Catalytic Reactions... 

We have also discussed two applications of the extended ab initio atomistic thermodynamics approach. The first example is the potential-induced lifting of Au(lOO) surface reconstmction, where we have focused on the electronic effects arising from the potential-dependent surface excess charge. We have found that these are already sufficient to cause lifting of the Au(lOO) surface reconstruction, but contributions from specific electrolyte ion adsorption might also play a role. With the second example, the electro-oxidation of a platinum electrode, we have discussed a system where specific adsorption on the surface changes the surface structure and composition as the electrode potential is varied. 

Wang H, Baltruschat H. 2007. DEMS study on methanol oxidation at poly- and monocrystalline platinum electrodes The effect of anion, temperature, surface structure, Ru adatom, and potential. J Phys Chem C 111 7038-7048. 

Chemisorption of oxygen at Pt(lll) has been studied in detail by Ertl s group25 and the STM evidence is for complex structural features present in the temperature range 54M60K (Figure 4.14). The limitations of the Langmuir model, frequently invoked for reactions at platinum surfaces, is obvious from... 

We and others have been involved in the study of such systems including Cu/Au(lll),85 86 Ag/Au(lll),87 Pb/Ag(lll),88 and Cu/Pt(lll).89 The first three systems involved the use of epitaxially deposited metal films on mica as electrodes.90 92 Such deposition gives rise to electrodes with well-defined single-crystalline structures. In the last case a bulk platinum single crystal was employed. Because of the single-crystalline nature of the electrodes, polarization dependence studies could be used to ascertain surface structure. 

Subsequent to the discovery of skeletal rearrangement reactions on plati-num/charcoal catalysts, the reality of platinum-only catalysis for reactions of this sort was reinforced with the observation of the isomerization of C4 and C5 aliphatic hydrocarbons over thick continuous evaporated platinum films (68,108, 24). As we have seen from the discussion of film structure in previous sections, films of this sort offer negligible access of gas to the substrate beneath. Furthermore, these reactions were often carried out under conditions where no glass, other than that covered by platinum film, was heated to reaction temperature that is, there was essentially no surface other than platinum available at reaction temperature. Studies have also been carried out (109, 110) using platinum/silica catalysts in which the silica is catalytically inert, and the reaction is undoubted confined to the platinum surface. 

The relative rate of isobutane isomerization has been shown by Anderson and Avery 24) to be markedly increased by using a (111) platinum film surface. On the other hand, this did not occur with n-butane, nor did it occur with either iso- or n-butane over a (100) platinum surface (cf. Table II). A triangular array of adjacent sites on a (111) platinum surface can be readily fitted by an adsorbed isohydrocarbon, and this structure also fits to allow the carbon orbitals to be directed normally to the surface. On simple geometric grounds, this adsorbed structure is specific to the (111)/... 

API Project 44 thermochemical data). In fact, the proportion of Ce product observed under these conditions over various platinum film catalysts tends to be rather irreproducible for reasons that are not at all apparent it is probably associated with some variable feature of catalyst surface structure. 

As previously mentioned, Davis (8) has shown that in model dehydrocyclization reactions with a dual function catalyst and an n-octane feedstock, isomerization of the hydrocarbon to 2-and 3-methylheptane is faster than the dehydrocyclization reaction. Although competitive isomerization of an alkane feedstock is commonly observed in model studies using monofunctional (Pt) catalysts, some of the alkanes produced can be rationalized as products of the hydrogenolysis of substituted cyclopentanes, which in turn can be formed on platinum surfaces via free radical-like mechanisms. However, the 2- and 3-methylheptane isomers (out of a total of 18 possible C8Hi8 isomers) observed with dual function catalysts are those expected from the rearrangement of n-octane via carbocation intermediates. Such acid-catalyzed isomerizations are widely acknowledged to occur via a protonated cyclopropane structure (25, 28), in this case one derived from the 2-octyl cation, which can then be the precursor... 

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