Supported Pt surfaces

An overview of literature data concerning CO and H2 adsorption over supported Pt surfaces, as well as data on oxygen adsorption over various Pt surfaces, has been compiled by Uner et al. [69]. 

Table 12.2 Literature data of CO adsorption over supported Pt surfaces...

Fig. 3. Metal surface areas of supported Pt catalysts as a function of metal loading.

In figure 3 and show that the relative thermal motion of the surface atoms is significantly greater than in the bulk metal over the range from 100 - 800 K, This result is expected considering the partial coordination, hence lack of constraint of the surface atoms. A similar result has been found from LEED measurements on a Pt surface. ( ) Significantly, the surface atom disorder when extrapolated to 0 K remains sizable. This static disorder or strain appears to be a result of the interaction of the Ft atoms with the support, a kind of epitaxy to the oxygen (or hydroxyl) surface of the support. 

The role played by the support of influencing the surface composition of supported bimetallic clusters has only recently begun to receive some attention. Miura, a ( ) have shown that the nature of the support can play an important role in determining not only the surface composition of the supported bimetallic clusters but also the morphology of the particles. For silica-supported Pt-Ru... 

In order to verify the presence of bimetallic particles having mixed metal surface sites (i.e., true bimetallic clusters), the methanation reaction was used as a surface probe. Because Ru is an excellent methanation catalyst in comparison to Pt, Ir or Rh, the incorporation of mixed metal surface sites into the structure of a supported Ru catalyst should have the effect of drastically reducing the methanation activity. This observation has been attributed to an ensemble effect and has been previously reported for a series of silica-supported Pt-Ru bimetallic clusters ( ). 

The surface-catalyst composition data for the silica-supported Ru-Rh cuid Ru-Ir catalyst are shown in Figure 1. A similcir plot for the series of silica-supported Pt-Ru bimetallic catalysts taken from ref. P) is included for comparison purposes. Enthalpies of sublimation for Pt, Ru, Rh and Ir are 552, 627, 543, and 648 KJ/mole. Differences in enthalpies of sublimation (a<75 KJ/mole) between Pt and Ru cind between Rh and Ru are virtually identical, with Pt euid Rh having the lower enthalpies of sublimation. For this reason surface enrichment in Pt for the case of the Pt-Ru/Si02 bimetallic clusters cannot be attributed solely to the lower heat of sublimation of Pt. Other possibilities must also be considered. 

Steady state and non steady state kinetic measurements suggest that methane carbon dioxide reforming proceeds in sequential steps combining dissociation and surface reaction of methane and CO2 During admission of pulses of methane on the supported Pt catalysts and on the oxide supports, methane decomposes into hydrogen and surface carbon The amount of CH, converted per pulse decreases drastically after the third pulse (this corresponds to about 2-3 molecules of CH< converted per Pt atom) indicating that the reaction stops when Pt is covered with (reactive) carbon CO2 is also concluded to dissociate under reaction conditions generating CO and adsorbed... 

Under 50 mbar of H2 and 50 °C, SnBu4 reacts selectively on the Pt surface to form surface complexes of average formula Pts[SnBux] /. The empirical formula (values of x and y) depend on the reaction time and on the Snint/Pts ratio (Fig. 6). Note that under these conditions SnBu4 does not chemically react with the silica surface, but it is fully physisorbed on the support [114]. In fact, when silica is contacted with SnBu4, IR spectroscopy shows a shift of the v(0 - H) band of silica to lower wave numbers, i.e. from 3747 cm to ca. 3700 cm which results from van der Waals interactions between the hydroxyl groups of the support and the butyl chains of adsorbed SnBu4 (Scheme 32). 

The first step of the grafting process is probably the physisorption of Bu4Sn on the surface of the support (higher surface area), which then migrates from the support to the metal surface. Then, when the physisorbed complex interacts with the surface Pt atoms covered by hydrogen atoms (Pts-H ), there is... 

The kinetics of ethylene hydrogenation on small Pt crystallites has been studied by a number of researchers. The reaction rate is invariant with the size of the metal nanoparticle, and a structure-sensitive reaction according to the classification proposed by Boudart [39]. Hydrogenation of ethylene is directly proportional to the exposed surface area and is utilized as an additional characterization of Cl and NE catalysts. Ethylene hydrogenation reaction rates and kinetic parameters for the Cl catalyst series are summarized in Table 3. The turnover rate is 0.7 s for all particle sizes these rates are lower in some cases than those measured on other types of supported Pt catalysts [40]. The lower activity per surface... 

Figure 9.15 Kinetic current density (squares) at 0.8 V for O2 reduction on supported Pt monolayers in a 0.1 M HCIO4 solution, and the calculated activation energy barriers for O2 dissociation (filled circles) and OH formation (open circles) on PtML/Au(lll), Pt(lll), PtML/ Pd(lll), and PtML/lT(lll). as a function of the calculated binding energy of atomic oxygen (BEo). The current density data for Pt(lll) were obtained fiom [Maikovic et al., 1999] and ate included for comparison. Key 1, Pt]y[L/Ru(0001) 2, Pb /bllll) 3, PtML/Rh(lH)i 4, Ptim,/ Au(lll) 5, Pt(lll) 6, PtML/Pd(lll). Surface coverage is ML O2 in O2 dissociation and ML each for O and H in OH formation. (Reproduced with permission fiom Zhang et al. [2005a].)...

One of the critical issues with regard to low temperamre fuel cells is the gradual loss of performance due to the degradation of the cathode catalyst layer under the harsh operating conditions, which mainly consist of two aspects electrochemical surface area (ECA) loss of the carbon-supported Pt nanoparticles and corrosion of the carbon support itself. Extensive studies of cathode catalyst layer degradation in phosphoric acid fuel cells (PAECs) have shown that ECA loss is mainly caused by three mechanisms ... 

Murthi VS, Urian RC, Mukeijee S. 2004. Oxygen reduction kinetics in low and medium temperature acid environment Correlation of water activation and surface properties in supported Pt and Pt alloy electrocatalysts. J Phys Chem B 108 11011-11023. 

The mass activity MA (in A g ) of the Pt catalyst is, of course, the product of the specific activity js (in A m ) and the specitic surface area 5mass (in ni g ) MA = js mass- Because S ass is inversely proportional to the particle diameter dpt, the use of supported Pt nanoparticles is effective for increasing MA, if js is a constant independent of dpt- However, even at pure Pt, conflicting results on the values of js and P(H202) have been reported, suggesting the presence of differences in electrochemical properties between bulk and supported nanoparticles. For example, Bregoli [1978]... 

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