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 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.
SYNOPSISThe surface chemistry of plasma-deposited films created from amine-functionalized saturated (propylamine) and unsaturated (allylamine and propargylamine) precursors has been investigated by high-energy resolution XPS, chemical derivatization, elemental analysis, and HREELS. XPS results show that nitrogen-rich deposits are obtained from unsaturated precursors at low power or at high power in the postdischarge region. Quantitative information on the chemical groups in the polymers is obtained by simulating the XPS C l s and N l s core levels and by performing derivatization reactions. The proportion of primary amine functions deduced from tagging reactions with pentafluorobenzaldehyde in the liquid phase and with 4-trifluoromethylbenzaldehyde in the vapor phase varies between 10 and 33%. These groups are converted into imine (more than 50%) in polypropylamine and polyallylamine, while imine and nitrile functions were found in polypropargylamine. HREELS has allowed us to distinguish between different nitrogen-containing functionalities present at the extreme surface of the polymers. The comparison of the HREELS and TIR spectra shows that the chemical composition a t the extreme surface of the samples is representative of that of the bulk. To explain the conversion of the chemical groups in the plasma, polymerization mechanisms are proposed for each of the monomers.
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