Rhodium surface

Although there is a severe paucity of vibrational data for the molecular form of O2 chemisorbed on rhodium surfaces, it is possible to visualize the dinuclear and trinuclear complexes as models for the associative chemisorption of O2 on rhodium. The pq-o values of the complexes Rh2(02)i,2 show little... 

Table 6.2. Activation energies for NO dissociation and N2 desorption from two rhodium surfaces.

The right-hand part of Fig. 7.7 corresponds to the second-order desorption of nitrogen atoms from a rhodium surface. As the desorption reaction corresponds to N -I- N —> N2 -I- 2 the rate is indeed expected to vary with A characteristic feature of second-order desorption kinetics is that the peaks shift to lower temperature with increasing coverage, because of the strong dependence of the rate on coverage. 

Figure 10.7 shows the temperature dependence of CO oxidation rate on a rhodium surface, as reported by Bowker et al. It shows that the rate of reaction maximizes when both reactants, adsorbed CO and O, are present in comparable quantities at a temperature where the activation barrier of the reaction can be overcome. 

CO oxidation is often quoted as a structure-insensitive reaction, implying that the turnover frequency on a certain metal is the same for every type of site, or for every crystallographic surface plane. Figure 10.7 shows that the rates on Rh(lll) and Rh(llO) are indeed similar on the low-temperature side of the maximum, but that they differ at higher temperatures. This is because on the low-temperature side the surface is mainly covered by CO. Hence the rate at which the reaction produces CO2 becomes determined by the probability that CO desorbs to release sites for the oxygen. As the heats of adsorption of CO on the two surfaces are very similar, the resulting rates for CO oxidation are very similar for the two surfaces. However, at temperatures where the CO adsorption-desorption equilibrium lies more towards the gas phase, the surface reaction between O and CO determines the rate, and here the two rhodium surfaces show a difference (Fig. 10.7). The apparent structure insensitivity of the CO oxidation appears to be a coincidence that is not necessarily caused by equality of sites or ensembles thereof on the different surfaces. 

The undoubtedly structure-sensitive reaction NO -r CO has a rate that varies with rhodium surface structure. A temperature-programmed analysis (Fig. 10.8) gives a good impression of the individual reaction steps CO and NO adsorbed in relatively similar amounts on Rh(lll) and Rh(lOO) give rise to the evolution of CO, CO2, and N2, whereas desorption of NO is not observed at these coverages. Hence, the TPRS experiment of Fig. 10.8 suggests the following elementary steps ... 

Breaking of the N-O bond by the rhodium surface is the most essential step in the catalytic reduction of NO (see also Chapter 7). Although rhodium is sufficiently reactive to achieve this (even without promoters), dissociation can nevertheless be severely impeded if the surface coverage is too high (as Fig. 7.12 shows). In the low coverage regime, however, such effects play no role. 

NO is now chemisorbed on the Rh particles at a temperature where it does not adsorb on the AI2O3. The saturation coverage of NO on Rh(lOO) corresponds to one NO molecule per two rhodium surface atoms, with NO sitting in a c(2x2) surface structure. After having saturated the catalyst with NO, a temperature-programmed desorption experiment (TPD) is performed with a heating rate of 2 K min". NO is seen to desorb with a maximal rate at 460 K. The total NO gas that desorbs amounts to 18.5 mL per gram catalyst (P = 1 bar and T = 300 K). It can be assumed that NO does not dissociate on the Rh(lOO) surface. 

The effect of oxidizing atmospheres on the reduction of NO over rhodium surfaces has been investigated by kinetic and IR characterization studies with NO + CO + 02 mixtures on Rh(lll) [63], Similar kinetics was observed in the absence of oxygen in the gas phase, and the same adsorbed species were detected on the surface as well. This result contrasts with that from the molecular beam work [44], where 02 inhibits the reaction, perhaps because of the different relative adsorption probabilities of the three gas-phase species in the two types of experiments. On the other hand, it was also determined that the consumption of 02 is rate limited by the NO + CO adsorption-desorption... 

Bustos, V., Ufiac, R., Zaera, F. et al. (2003) Lattice-gas study of the kinetics of the catalytic NO-CO reaction on rhodium surfaces. II. The effect of nitrogen surface islands , J. Chem. Phys., 118, 9372. 

Temperature programmed desorption (TPD) or thermal desorption spectroscopy (TDS), as it is also called, can be used on technical catalysts, but is particularly useful in surface science, where one studies the desorption of gases from single crystals and polycrystalline foils into vacuum [2]. Figure 2.9 shows a set of desorption spectra of CO from two rhodium surfaces [14]. Because TDS offers interesting opportunities to interpret desorption in terms of reaction kinetic theories, such as the transition state formalism, we will discuss TDS in somewhat more detail than would be justified from the point of view of practical catalyst characterization alone. 

Figure 2.9 Thermal desorption of carbon monoxide from two rhodium surfaces in ultrahigh vacuum, as measured with the experimental set-up of Fig. 2,10. Each curve corresponds to a different surface coverage of CO. At low coverages CO desorbs in a single peak indicating that all CO molecules bind in a similar configuration to the surface. At higher coverages, an additional desorption peak appears, indicative of a different adsorption geometry (courtesy of M.J.P. Hopstaken and W.E. van Gennip [141).

Carbon monoxide oxidation is a relatively simple reaction, and generally its structurally insensitive nature makes it an ideal model of heterogeneous catalytic reactions. Each of the important mechanistic steps of this reaction, such as reactant adsorption and desorption, surface reaction, and desorption of products, has been studied extensively using modem surface-science techniques.17 The structure insensitivity of this reaction is illustrated in Figure 10.4. Here, carbon dioxide turnover frequencies over Rh(l 11) and Rh(100) surfaces are compared with supported Rh catalysts.3 As with CO hydrogenation on nickel, it is readily apparent that, not only does the choice of surface plane matters, but also the size of the active species.18-21 Studies of this system also indicated that, under the reaction conditions of Figure 10.4, the rhodium surface was covered with CO. This means that the reaction is limited by the desorption of carbon monoxide and the adsorption of oxygen. 

In pulsed-laser field desorption of helium from rhodium surfaces, if the... 

This is a vital component of the system of reactions involved in treating the exhaust from internal combustion engines (see Chapter 11). The methodology of surface science has been extensively applied to this problem, mainly using platinum and rhodium surfaces," as these are high on the list of components of choice for practical use,100 but it is only recently that gold has come to be seen as having a possible role to play. 

Diazene can be detected by chemical reactions such as the stereospecific, highly selective cis-hydrogenation of C C bonds by hydrazine and an oxidant, and by mass spectrometry in the gas phase decomposition of both NH3 and N2H4 on rhodium surfaces.25... 

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