Cerium oxide system

Fig.4.56. Comparison of UV detection with the cerium oxidation system for some organic acids. (From ref. 117 with permission of Marcel Dekker, New York.)...

Table I. Nonstoichiometry of Intermediate Phases in Cerium Oxide Systems...

High temperature vaporization studies have yielded the thermodynamic data shown in table 27.5 on the cerium oxide system. 

In addition to platinum and related metals, the principal active component ia the multiflmctioaal systems is cerium oxide. Each catalytic coaverter coataias 50—100 g of finely divided ceria dispersed within the washcoat. Elucidatioa of the detailed behavior of cerium is difficult and compHcated by the presence of other additives, eg, lanthanum oxide, that perform related functions. Ceria acts as a stabilizer for the high surface area alumina, as a promoter of the water gas shift reaction, as an oxygen storage component, and as an enhancer of the NO reduction capability of rhodium. 

In an actual exhaust system controlled by the signal of the oxygen sensor, stoichiometry is never maintained, rather, it cycles periodically rich and lean one to three times per second, ie, one-half of the time there is too much oxygen and one-half of the time there is too Httle. Incorporation of cerium oxide or other oxygen storage components solves this problem. The ceria adsorbs O2 that would otherwise escape during the lean half cycle, and during the rich half cycle the CO reacts with the adsorbed O2 (32,44,59—63). The TWC catalyst effectiveness is dependent on the use of Rh to reduce NO and... 

Fillers can also be used to promote or enhance the thermal stability of the silicone adhesive. Normal silicone systems can withstand exposure to temperatures of 200 C for long hours without degradation. However, in some applications the silicone must withstand exposure to temperatures of 280 C. This can be achieved by adding thermal stabilizers to the adhesive formulations. These are mainly composed of metal oxides such as iron oxide and cerium oxide, copper organic complexes, or carbon black. The mechanisms by which the thermal stabilization occurs are discussed in terms of radical chemistry. 

Methods for determination of thiol drugs (i.e., captopril [21-25], penicillamine [26-28], hydrochlorothiazide [24, 25, 29, 30], and tiopronin [31, 32]) have been developed. These methods are based on CL from a cerium (IV) oxidation system sensitized by adequate fluorophores such as quinine and rhodamine B. By using HPLC-coupled CL-flow-injection analysis method, tiopronin and its metabolite 2-mercaptopropionic acid in human urine were sensitively determined with the detection limits of 0.8 and 1 pM, respectively [32],... 

Catalyst systems for the WGS reaction that have recently received significant attention are the cerium oxides, mostly loaded with noble metals, especially platinum 42—46]. Jacobs et al. [44] even claim that it is probable that promoted ceria catalysts with the right development should realize higher CO conversions than the commercial Cu0-Zn0-Al203 catalysts. Ceria doped with transition metals such as Ni, Cu, Fe, and Co are also very interesting catalysts 37,43—471, especially the copper-ceria catalysts that have been found to perform excellently in the WGS reaction, as reported by Li et al. [37], They have found that the copper-ceria catalysts are more stable than other Cu-based LT WGS catalysts and at least as active as the precious metal-ceria catalysts. 

L. Kundakovic, and M. Rytzani-Stephanopoulos, Reduction characterization of copper oxide in cerium and zirconium oxide systems, Appl. Catal. A Gen. 171, 13—29 (1998). 

Nd2-xCexCu04, 112,427-45 band structure schematic, 717 cerium oxidation state, 431 comparison with La2CuO>4 systems, 320 composition range, 437 copper oxidation state, 427,442 crystal chemistry, 428-31 crystal growth, 244,436-7,442-4... 

Careful analyses of the thermodynamic data of the praseodymium and terbium oxides led to the construction of their RCL-O2 phase diagrams (Hyde et al., 1966 Hyde and Eyring, 1965). The cerium oxides were studied by means of X-ray powder diffraction (Bevan, 1955) and the CeOx-02 phase diagram was constructed from equilibrium reaction studies at oxygen pressures down to 10-24 atm and temperatures up to 1200 °C (Bevan and Kordis, 1964 Ricken et al., 1984). It is worth to notice that the phase diagrams of Ce0x-02, PrCb-Cb, and Tb0x-02 systems... 

Figure 5 shows the isobar data of CeOx-C>2 system. At one atmosphere with a 150 torr oxygen partial pressure, the cerium oxide almost is dioxide, CeC>2, and there is no phase transition until the temperature increases up 1200 °C. However, when the oxygen partial pressure is about 10-9 torr the oxygen content of the... 

The formation of a rare earth metal oxide on the metal surface, impedes the cathodic reduction of oxygen and thus cathodic inhibition is achieved by the addition of a rare earth metal salt to a system. The surface atom concentration ratio, [Ce/Ce + M], where M is Fe, Al or Zn, is a function of cerium oxide film thickness determined by AES depth profiles as shown in Fig. 12.2. 

Answer 3.6 As with V2O5 in the Contact process for making sulfuric acid, the ability of cerium to adopt transition-metal-like behaviour in switching oxidation states means that the cerium oxide can effectively act as an oxygen-storage system. 

In Figure 8 we have plotted the lanthanum oxide, cerium oxide, and thorium oxide concentrations for sherds excavated in the Dominican Republic and Venezuela and sherds from the Metro excavations using a computer system developed for this purpose at Brookhaven National Laboratory (8). On the basis of these three oxides there is a distinct separation between the sherds from the Dominican Republic and Venezuela and those from Mexico City. Unlike the sherds from the Dominican Republic and Venezuela, the sherds from Mexico City appear not to have originated in Spain, at least at that specific source. There is further evidence of this distinction between the two sets of sherds. X-ray diffraction analysis of the samples from Jerez and from the New World showed that the sherds from Jerez, the Dominican Republic, and Venezuela had intense quartz peaks whereas the sherds from Mexico City did not. This constitutes additional evidence that the majolica from Mexico City came from a different source than the majolica from the Caribbean sites. 

In conclusion, there is overwhelming evidence for the beneficial effect of cerium oxide on the activity of the noble metal catalyst. However, the nature of the promoter effect of ceria is not fully understood. Most likely, the noble metal-cerium oxide interface is of crucial importance for some of the effects observed. More studies with model systems are needed for a better understanding of the promoter effects of ceria. 

Cerium also has minor uses in other commercial catalysts [17]. The dominant catalyst for the production of styrene from ethylbenzene is an alkali-promoted iron-oxide based material. The addition of a few percent of cerium oxide to this system improves activity for styrene formation. The ammoxidation of propylene to produce acrylonitrile is carried out over catalytically active complex molybdates. Cerium, a component of several patented compositions [18], supports the chemical reaction. 

With a few exceptions, most research applying the surface science approach to study ceria based systems has been performed in about the last five years. As evidence for this statement consider that in a 1995 book which presents a comprehesive review of surface science of oxide surfaces only a single reference to cerium oxide surfaces is cited or that in a 1997 review of structural, electronic and chemisorptive properties of metal films and particles on oxide surfaces there are six references to ceria surfaces or that in a 1998 review of surface studies of supported model catalysts there are only six references to ceria as a support. The... 

Our recent work on the bismuth-cerium molybdate catalyst system has shown that it can serve as a tractable model for the study of the solid state mechanism of selective olefin oxidation by multicomponent molybdate catalysts. Although compositionally and structurally quite simple compared to other multiphase molybdate catalyst systems, bismuth-cerium molybdate catalysts are extremely effective for the selective ammoxidation of propylene to acrylonitrile (16). In particular, we have found that the addition of cerium to bismuth molybdate significantly enhances its catalytic activity for the selective ammoxidation of propylene to acrylonitrile. Maximum catalytic activity was observed for specific compositions in the single phase and two phase regions of the phase diagram (17). These characteristics of this catalyst system afford the opportunity to understand the physical basis for synergies in multiphase catalysts. In addition to this previously published work, we also include some of our most recent results on the bismuth-cerium molybdate system. As such, the present account represents a summary of our interpretations of the data on this system. 

The complex solid state relations of the cerium-molybdenum- tellurium oxide system were studied to determine the boundaries of single phase regions and phase distributions of a typical multicomponent ammoxidation catalyst. Between 400 and 600 C in air the (Ce,Mo,Te)0 system contains the following phases ... 

BART ET AL. Cerium-Molybdenum-Tellurium Oxide System... 

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