Rhodium-platinum surfaces, structure

A variety of model catalysts have been employed we start with the simplest. Single-crystal surfaces of noble metals (platinum, rhodium, palladium, etc.) or oxides are structurally the best defined and the most homogeneous substrates, and the structural definition is beneficial both to experimentalists and theorists. Low-energy electron diffraction (LEED) facilitated the discovery of the relaxation and reconstruction of clean surfaces and the formation of ordered overlayers of adsorbed molecules (3,28-32). The combined application of LEED, Auger electron spectroscopy (AES), temperature-programmed desorption (TPD), field emission microscopy (FEM), X-ray and UV-photoelectron spectroscopy (XPS, UPS), IR reflection... 

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-... 

In the case of the catalytic destraction of ozone, the catalyst speeds up a reaction that we do not want to happen. Most of the time, however, catalysts are used to speed up reactions that we do want to happen. For example, your car most likely has a catalytic converter in its exhaust system. The catalytic converter contains solid catalysts, such as platinum, rhodium, or palladium, dispersed on an underlying high-surface-area ceramic structure. These catalysts convert exhaust pollutants such as nitrogen monoxide and carbon monoxide into less harmful substances ... 

The adsorption of sulfur at platinum,40 rhodium,41 rhenium42 and ruthenium43 has been studied predominantly at fcc(lll) and hcp(0001) surfaces and shows many similar characteristics. Adsorption is initially into fee hollow sites of the fee metals and hep sites of the hep metals at higher coverages, mixed site occupancy occurs. A (2 x 2) structure is the first to be recorded appearing in the... 

Pellistors are used to detect flammable gases like CO, NH3, CH4 or natural gas. Some flammable gases, their upper and lower explosion limits and the corresponding self-ignition temperatures are listed in Tab. 5.1. This kind of gas sensor uses the exothermicity of gas combustion on a catalytic surface. As the combustion process is activated at higher temperatures, a pellistor is equipped with a heater coil which heats up the active catalytic surface to an operative temperature of about 500 °C. Usually a Platinum coil is used as heater, embedded in an inert support structure which itself is covered by the active catalyst (see Fig. 5.33). The most frequently used catalysts are platinum, palladium, iridium and rhodium. 

Field emission microscopy was the first technique capable of imaging surfaces at resolution close to atomic dimensions. The pioneer in this area was E.W. Muller, who published the field emission microscope in 1936 and later the field ion microscope in 1951 [23]. Both techniques are limited to sharp tips of high melting metals (tungsten, rhenium, rhodium, iridium, and platinum), but have been extremely useful in exploring and understanding the properties of metal surfaces. We mention the structure of clean metal surfaces, defects, order/disorder phenomena,... 

The processes classified in the third group are of primary importance in elucidating the significance of electric variables in electrosorption and in the double layer structure at solid electrodes. These processes encompass interactions of ionic components of supporting electrolytes with electrode surfaces and adsorption of some organic molecules such as saturated carboxylic acids and their derivatives (except for formic acid). The species that are concerned here are weakly adsorbed on platinum and rhodium electrodes and their heat of adsorption is well below 20 kcal/mole (25). Due to the reversibility and significant mobility of such weakly adsorbed ions or molecules, the application of the i n situ methods for the surface concentration measurements is more appropriate than that of the vacuum... 

With the advent of sophisticated experimental techniques for studying surfaces, it is becoming apparent that the structure of chemisorbed species may be very different from our intuitive expectations.10 For example, ethylene (ethene, H2C=CH-2) chemisorbs on platinum, palladium, or rhodium as the ethylidyne radical, CH3—C= (Fig. 6.2). The carbon with no hydrogens is bound symmetrically to a triangle of three metal atoms of a close-packed layer [known as the (111) plane of the metal crystal] the three carbon-metal bonds form angles close to the tetrahedral value that is typical of aliphatic hydrocarbons. The missing H atom is chemisorbed separately. Further H atoms can be provided by chemisorption of H2, and facile reaction of the metal-bound C atom with three chemisorbed H atoms dif-... 

Khulbe and Mann [155] have obtained infrared spectra of allene adsorbed on silica-supported cobalt, nickel, palladium, platinum and rhodium. The spectra were similar for all the metals, although variations in band intensity from metal to metal were observed. Addition of hydrogen to the allene-precovered surface resulted in similar spectra to those found for chemisorbed and hydrogenated propene in which the surface species was thought to be an adsorbed prop-1-yl group. The authors concluded that the initial allene spectrum was consistent with the adsorbed species being a 1 2-di-o-bonded allene (structure K)... 

Other workers (165) used X-ray photoelectron spectroscopy (XPS) to examine the influence of ammonia oxidation on the surface composition of alloy gauzes. After several months on stream, the surface was covered by the same types of highly faceted structures noted by others. As illustrated in Fig. 14, XPS analysis provides evidence that the top microns, and in particular the top 100 A of the surface, were enriched in rhodium. This enrichment was attributed to the preferential volatilization of platinum oxide. The rhodium in the surface layers was present in the oxide form. Other probes confirm the enrichment of the surface in rhodium after ammonia oxidation (166). Rhodium enrichment has been noted by others (164, 167), and it has been postulated that in some cases it leads to catalyst deactivation (168). 

Figures 4.30(c) and 4.31(c) show HREM images representative of the catalysts reduced at 1173 K and further oxidised in pure O2 at 1173 K. The structure of both catalysts is clearly different from that observed after re-oxidation at 773 K. Notice that in this case both materials seem to be formed by small, crystalline, metal particles dispersed over the ceria surface. Fringe analysis confirms that these crystallites consist of metallic rhodium and platinum, respectively. Thus, the DDPs of the larger particles observed in the image of the Pt catalyst show 0.8 nm Moire-type fringes aligned with the (111 )-Ce02 reflections. These spots arise from double diffraction in the (lll)-Pt and (Ill)-Ce02 planes under a parallel orientation relationship. Therefore this result, in addition to confirm the presence of metallic Pt particles in the sample oxidised at 1173 K, suggest that these particles are epitaxially grown on the support. A detailed inspection also reveals that the exposed surfaces of these particles are clean, i.e. free from support overlayers.

Marsh AL, Somorjai GA (2005) Structure, reactivity, and mobility of carbonaceous overlayers during olefin hydrogenation on platinum and rhodium single crystal surfaces. Top Catal 34 121... 

Inside the catalytic converter is a porous ceramic structure with a surface coating of platinum and rhodium particles. 

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