Mixed oxides redox properties

We shall mainly consider, in the present chapter, non-precious transition metals, but the model can be extended to precious metals presenting an oxidation state higher than zero [10,11], such as Rhx+, Pdx+, Ptx+ and tix+. The model also applies to some oxides alone, such as ceria (Ce02) [19] or mixed oxides such as ceria-zirconia (CeZr02) able to present redox properties and oxygen vacancies during catalytic reactions. 

Zhang, RD Alamdari, H Kaliaguine, S. Crystal structure, redox properties and catalytic performance of Ga-based mixed oxides for NO reduction by CsHg, Catalysis Communications, 2008, Volume 9, 111-116. 

It is interesting to note that the CD spectrum of 11 can be tuned by changing the oxidation states of the TTF units in the side-chains of 11. Polymer 11 shows reversible interconversion between three univalent and two very broad mixed-valence redox states that have different chiroptical properties. 

The mixed-addenda atoms affect the redox properties mixed-addenda heteropoly compounds are used as industrial oxidation catalysts. For example, the rate of reduction by H2 is slower and less reversible for solid PMO 2-,VJto m+, than for solid PM012O40, although the former are stronger oxidants than the latter in solution (279, 280). The effects of substituting V for Mo on the catalytic activity are controversial (279, 281-284). Differences in redox processes between solutions and solids, the thermal or chemical stability of the heteropoly compounds, and the effects of countercations in solids have been suggested to account for the discrepancies. 

It is well known that redox properties of oxides can be modified by the formation of mixed oxides (12). Effect of mixed oxide formation on AG° of M-0 dissociation is illustrated in Figure 1. The free energy changes of the following reactions, AGA° and AGp°, are calculated from thermodynamic data (13, 14). 

The redox properties of ceria-zirconia mixed oxides are interesting, because these materials find applications as electrolytes for solid oxide fuel cells, supports for catalysts for H2 production, and components in three-way automobile exhaust conversion catalysts. The group of Kaspar and Fornasiero (Montini et al., 2004, 2005) used TPR/TPO-Raman spectroscopy to identify the structural features of more easily reducible zirconia-ceria oxides and the best method for their preparation by suitable treatments. TPR/TPO experiments and Raman spectra recorded during redox cycles demonstrated that a pyrochlore-type cation ordering in Ce2Zr2Og facilitates low temperature reduction. 

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