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The CeO2 and Ce x Zr1 - x O2 reduction by hydrogen was studied using IR spectroscopy to follow the evolution of the ν(OH) vibrational modes and a magnetic balance to estimate the global reduction percentage from the magnetic susceptibility. H2 was introduced between 298 and 873 K on activated samples. On ceria, different OH groups exist depending on cerium unsaturation. In particular, the band due to OH type II shifts toward higher frequencies when ceria is reduced. It is therefore possible to monitor the surface oxidation state of ceria or mixed oxides through the ν(OH) band wavenumber. For ceria, the surface reduction begins at around 573 K. That leads to the formation of OH(I) species and adsorbed H2O which are observed at the beginning of the reduction. Their elimination leads to the creation of surface O-vacancies. At higher temperatures, there is a surface/subsurface reorganization through the reverse migration of O-vacancies and O-ions from the bulk. However, the adsorption sites are conserved during the evacuation step, the bonded OH, OH(II−B), and OH(II-A) species disappearing by evacuation in the range 773−873 K through H2 (and not H2O) evolution. For mixed Ce x Zr1 - x O2 compounds, the most interesting OH species are those adsorbed on cerium ions. The results lead to the conclusion that the mechanism of reduction is the same as in the case of pure ceria but that an increased mobility of bulk oxygen (in relation with the Zr content) for mixed compounds allows surface oxygen vacancies to be faster filled from O migration in subsurface underlayers. The hydrogen reduction was also followed in a magnetic balance in the case of Ce0.5Zr0.5O2 mixed oxide. The Ce3+ content obtained at different temperatures confirms that the surface reduction is easier for the mixed oxide, the hydrogen chemisorption occurring for T > 373 K and the reduction of Ce4+ into Ce3+ ions beginning at 473 K. Moreover, the better reducibility of the bulk that is observed (76% of Ce3+ at 873 K for the mixed oxide instead of 17% for ceria) evidences the higher oxygen mobility in the bulk, in good agreement with the FTIR conclusions.

The objective of this study was to examine the mechanism of the reduction by hydrogen of ceria-zirconia (CZ) mixed oxides having a high BET surface area (100 m 2 g -1 ). Three methods were used in parallel to assess the Ce 3+ content, the surface and bulk oxygen vacancy concentrations, and the resulting oxygen storage capacity (OSC): temperature programmed reduction, Fourier transform infrared (FT-IR) measurements of methanol adsorbed on the reduced surfaces, and a Faraday microbalance to determine the magnetic susceptibility of the reduced oxides. The three methods conclude that the introduction of zirconium into the ceria lattice has a positive influence on the OSC. Compared to pure ceria, the CZ mixed oxides exhibit better redox properties, with a lower temperature of initial reduction and a higher reduction percentage for all compositions. The reducibility increases with the zirconium content, however the OSC per gram of solid is practically the same for Zr contents between 20% and 50%. The reduction process very rapidly involves the bulk, but a treatment at room temperature under oxygen of the reduced samples oxidizes them almost completely. However, the FT-IR results underline the differing behavior of ceria for the distinct surface and bulk reduction processes.

The present study concerns the characterization (by magnetic susceptibility measurements and temperature-programmed desorption (TPD) experiments) of the cerium fraction of a diesel soot (denoted Cec-DS) collected in the exhaust line of an engine using a fuel containing 50 ppm of cerium additive and 350 ppm of sulfur. The impact of this cerium fraction on the reactivity/ stability of the surface oxygenated complexes (denoted SOCs) is studied by comparison with (i) a diesel soot obtained with a fuel without additive and (ii) a commercial soot that is considered as a model of diesel soot. Magnetic susceptibility measurements indicate that 49% of the additive in Cec-DS is present as Ce 3+ , corresponding to cerium(III) sulfate (Ce 2 (SO 4 ) 3 ), and the remainder is present as Ce 4+ , which is associated with CeO 2 particles (average diameter of ∼23 nm, using X-ray diffractometry). The Ce 3+ ions of the as-prepared soot are very stable in air. During TPD of Cec-DS at a temperature of T > 1000 K, the production of SO 2 (decomposition of the Ce 2 (SO 4 ) 3 ), as well as large amounts of CO 2 and CO, is observed. The number of Ce 3+ ions in the solid is slightly decreased during the TPD. However, the Ce 3+ fraction is now able to activate O 2 at room temperature. In particular, all the Ce 3+ ions are oxidized to Ce 4+ ions by O 2 adsorption at 300 K while, in addition, a significant amount of SOC is formed on the soot (contrary to the observations of the two soots without cerium). Moreover, a sulfur mass balance during TPD indicates that a significant amount of sulfur remains associated to CeO x -containing particles. According to the literature data, this is tentatively ascribed to the formation of a very stable oxysulfidesCe 2 O 2 Ss during the course of the TPD. It is shown that, after the sulfate decomposition, the oxygen species from the cerium-containing particles are involved in the formation and removal of the SOC species. The decomposition of the Ce 2 (SO 4 ) 3 seems to be an important step for the catalytic oxidation of a Cec-DS soot.

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The redox behaviour of a Ce 0.68 Zr 0.32 O 2 mixed oxide is reversibly modified by alternating high temperature (1223 K) reduction with either mild (823 K) or high temperature (1223 K) re-oxidation treatments.