Rhodium surface structure

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 ... 

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. 

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. 

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. 

An ideal study of support effects requires model catalysts with metal particles that are identical in size and shape (so that only the support oxide varies). This is difficult to achieve for impregnated catalysts, but identical metal particles can be prepared via epitaxial model catalysts [36]. Well-faceted Rh nanocrystals were grown on a 100-cm area NaCl(OOl) thin film at 598 K. One half of a Rh/NaCl sample was covered with Al Oj, and the other half with TiO. The preparation of Rh particles for both Al Oj- and TiO -supported model catalysts in a single step prevents any differences in particle size, shape, and surface structure which could occur if the samples were prepared in separate experiments. Three model catalysts were prepared, with a mean Rh particle size of 7.8, 13.3, and 16.7 mn (the films were finally removed from the NaCl substrate by flotation in water). Activation was performed by O /H treatments, with the structural changes followed by TEM (Fig. 15.6). Oxidation was carried out in 1 bar O at 723 K prodncing an epitaxially grown rhodium oxide shell on a Rh core (cf Fig. 15.5e), whereas the hydrogen reduction temperature was varied. 

Concerning the results of Figure Id (Sn/Rhs = 0.3 and reaction time =12 hours) the lower activity can only be explained by a progressive structural change of the tin-rhodium surface perhaps the tin atoms slowly migrate on the most active sites of the particle. 

A surface structure of the type discussed for the rhodium-silica system, where two CO molecules adsorb on one surface metal atom, appears to be possible for some metals existing in certain ranges of crystallite sizes. Guerra and Schulman (112) have, in fact, questioned the existence of this adsorption complex on their rhodium-silica samples, but have suggested a similar type of adsorption mechanism occurring on their rhenium and ruthenium silica supported samples. 

Oxygen structures on rhodium surfaces deduced by Tucker (279) have been criticized by Bauer (181). 

B.E. Koel, J.E. Crowell, C.M. Mate, and G.A. Somoijai. A High Resolution Electron Energy Loss Spectroscopy Study of the Surface Structure of Benzene Adsorbed on the Rhodium (111) Crystal Face. J. Chem. Phys. 88 1988 (1984). 

M.A. Van Hove, R.F. Lin, and G.A. Somorjai. Surface Structure Determination of Coadsorbed Benzene and Carbon Monoxide on the Rhodium (111) Single Crystal Surface Analyzed with Low-Energy Electron Diffraction Intensities. J. Am. Chem. Soc. 108 2532 (1986). 

Recent single-crystal studies reveal the surface-structure sensitivity and anisotropy of self-diffusion (70, 71]. Depending on the structure of the crystal face, diffusion coefficients may vary by orders of magnitude. This is shown for rhodium adatom diffusion on various rhodium crystal faces in Figure 4.14. Diffusion rates parallel to steps are greater than diffusion rates perpendicular to them. 

Surface-science studies using nickel single-crystal surfaces revealed that the methanation reaction is surface-structure-insensitive. Both the (111) and (100) crystal faces yield the same reaction rates over a wide temperature range. These specific rates are also the same as those found for alumina-supported nickel, further proving the structure insensitivity of the process. This is also the case for the reaction over ruthenium, rhodium, molybdenum, and iron. 

Let us turn our attention to the bonding of organic molecules in organic monolayers on solid surfaces. The first molecule whose surface structure was solved was ethylene on flat metal surfaces such as platinum (111) and rhodium (111) [18,19]. The structure of the chemisorbed ethylene molecule at room temperature is shown in figure 21. Ethylene loses a hydrogen, be-... 

Zhang Y et al (2007) One-step polyol synthesis and langmuir-blodgett monolayer formation of size-tunable monodisperse rhodium nanocrystals with catalytically active (111) surface structures. J Phys Chem C 111 12243-12253... 

---