Cerium redox properties

Sardar, K., Playford, H.Y., Darton, R.J., Barney, E.R., Hannon, A.C., Tompsett, D., Fisher, J., Kashtiban, R.J., Sloan, J., Ramos, S., Cibin, G. and Walton, R.I. (2010) Nanocrystalline cerium-bismuth oxides synthesis, structural characterization, and redox properties. Chemistry of Materials, 22 6191-6201. 

R G. Harrison, I. K. Ball, W. Azelee, W. Daniell, and D. Goldfarb, Nature and surface redox properties of copper(ll)-promoted cerium(lV) oxide CO oxidation catalysts, Chem. Mater. 12, 3715-3725 (2000). 

In order to improve the resistance of Ni/Al203-based catalysts to sintering and coke formation, some workers have proposed the use of cerium compounds [36]. Ceria, a stable fluorite-type oxide, has been studied for various reactions due to its redox properties [37]. Zhu and Flytzani-Stephanopoulos [38] studied Ni/ceria catalysts for the POX of methane, finding that the presence of ceria, coupled with a high nickel dispersion, allows more stability and resistance to coke deposition. The synergistic effect of the highly dispersed nickel/ceria system is attributed to the facile transfer of oxygen from ceria to the nickel interface with oxidation of any carbon species produced from methane dissociation on nickel. 

More recently, infrared studies on the adsorption of NO and the coadsorption of NO and O2 onto Ce,Na-mordenite zeolite indicate that the redox properties of cerium (Ce3+/Ce4+) may contribute to the easier desorption of oxidized NO species (Ito et al. I995a,b, 1996). In this way, the formation of NO+ is associated with zeolite acid sites, and NO3 species associated to La cations, both NO+ and NO were found to desorb more easily from Ce,Na-mordenite than from La,Na-mordenite (Ito et al. 1995a). 

The simultaneous formation of nitrites and hyponitrites can be imderstood on the basis of the redox properties of Ce ions. Thus nitrites may form when NO is adsorbed on Ce " " ions with anion vacancies in their coordination spheres, leading to reduction of the cerium cation ... 

DeganeUo F, Liotta LF, Longo A, Casaletto MP, Scopelletti M. Cerium effect on the phase stmeture, phase stability and redox properties fo ce-doped strontium ferrates. Solid State Chem. 2006 179 3406. 

Most kinetic determinations of anions involve the iodide ion, which exhibits a strong catalytic effect on the reaction between cerium(IV) and arsenic(III) and a few others as a result of the redox properties of the I2/ I couple. Other anions that can be determined using their intrinsic catalytic effect include sulfur-containing species such as sulfite, sulfide, and thiosulfate, which are quantified by means of the iodine/sodium azide system, and phosphates, which are measured through their effect on the formation of molybdenum blue. Table 5 gives illustrative examples of determinations for these anions and a few others. 

Rynkowski, J.M., Szynkowska, M.I., Paryjczak, T., and Lewiscki, A. Redox properties of AI2O3-supported cerium oxides. Chem. Environ. Res. 1999, 8, 261-270. 

The four catalysts have different redox properties, the redox potentials being 1.31 V, 1. V, 1.23 V and 1.10 V for manganese, cerium, Ru(bpy) ... 

Cerium(IV) oxide-based heterogeneous catalysts are of interest in oxidation owing to the unique redox properties of cerium, i.e., if the crystallite size of ceria decreases, an increase in the oxygen vacancy defect concentration occurs leading to attractive catalytic properties.On the other hand, due to peculiar catalytic activity of gold, its combination with other materials is also appealing, especially when the combination promotes the... 

A predominant feature of the atomic structure of the lanthanide group is the sequential addition of 14 electrons to the 4f subshell (Table 1). The /"electrons do not participate in bond formation and in ordinary aqueous solutions all of the lanthanides exhibit a principal (III) state. The common (III) state confers a similarity in chemical properties to all lanthanide elements. Some of the lanthanides can also exist in the (II) state (Nd, Sm, Eu, Tm, Yh) or in the (IV) state (Ce, Pr, Nd, Tb, Dy). Except for Ce(IV), Eu(II), and Yb(II), these unusual lanthanide oxidation states can only be prepared under drastic redox pressure and temperature conditions, and they are not stable in aqueous solutions. Cerium (IV) is a strong oxidizing agent... 

The main usefulness of Eh-pH diagrams consists in the immediacy of qualitative information about the effects of redox and acid-base properties of the system on elemental solubility. Concerning, for instance, cerium, figure 8.20 immediately shows that, within the stability field of water, delimited upward by oxidation boundary curve o and downward by reduction boundary curve r, the element (in the absence of other anionic ligands besides OH groups) is present in solution mainly as trivalent cerium Ce and as soluble tetravalent hydroxide Ce(OH)2. It is also evident that, with increasing pH, cerium precipitates as trivalent hydroxide Ce(OH)3. 

Unstabilized chrome yellow pigments have poor lightfastness, and darken due to redox reactions. Recent developments have led to improvements in the fastness properties of chrome yellow pigments, especially toward sulfur dioxide and temperature. This has been achieved by coating the pigment particles with compounds of titanium, cerium, aluminum, antimony, and silicon [3.134] — [3.142]. 

Polyhydroxy compounds are oxidized by such metal ions as vanadium(V), chromium(VI), cerium(IV), iridium(IV), and gold(III), among others. These oxidations were found to be catalyzed by acids.171 173 Vanadium(V) and chromium(VI) are closely related in their chemical properties, but the reduction of V(V) is difficult compared with that of Cr(VI) because of its lower redox potential [V(V)-V(IV) = 1.00 V Cr(VI)-Cr(III) = 1.20 V], However, the redox potential increases at lower pH values, facilitating the oxidation of sugars. 

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