RESUMO
The effect of Pd loading on the redox characteristics of a ceria support was examined using in situ Pd K-edge XAS, Ce L3-edge XAS and in situ X-ray diffraction techniques. Analysis of the data obtained from these techniques indicates that the onset temperature for the partial reduction of Ce(IV) to Ce(III), by exposure to H2, varies inversely with the loading of Pd. Whilst the onset and completion temperatures of the reduction of Ce(IV) to Ce(III) are different, both samples yield the same maximal fraction of Ce(III) formation independent of Pd loading. Furthermore, the partial reduction of Ce is found to be concurrent with the reduction of PdO and demonstrated that the presence of metallic Pd is necessary for the reduction of the CeO2 support. Upon passivation by room temperature oxidation, a full oxidation of the reduced ceria support was observed. However, only a mild surface oxidation of Pd was identified. The mild passivation of the Pd is found to lead to a highly reactive sample upon a second reduction by H2. The onset of the reduction of Pd and Ce has been demonstrated to be independent of the Pd loading after a mild passivation with both samples exhibiting near room temperature reduction in the presence of H2.
RESUMO
Mechanochemistry offers a solventless, 'waste free' route to preparing metal oxide catalysts, however, there is limited information on the chemical steps involved. In this work, the perovskite LaMnO3 has been successfully synthesized via mechanochemistry from metal oxide powders, La2O3 and Mn2O3, at room temperature, using a planetary ball mill. Separate ex situ'time slices' were taken during the milling procedure to provide insights into the underlying chemistry. The crystalline material was assessed using XRD, which identified 100% perovskite phase after 3 h of milling. Conversely, characterization by X-ray absorption spectroscopy (XAS) at both the Mn K-edge and La L3-edge provides a very different picture. The XAS data shows that there are significant structural alterations as early as 30 min of milling, with the La precursor dispersed over Mn2O3. Increasing milling time then allows for mechanical activation of both precursors and the formation of powdered LaMnO3, with no calcination step required. The XAS highlights that there is a significant amount of amorphous, oxygen deficient, content even when XRD has identified 100% perovskite phase. The samples were tested for the decomposition of the environmental pollutant N2O; at a milling time of 3 h, the LaMnO3 catalyst displays a much early onset production of N2 compared to a traditional sol-gel synthesized LaMnO3, resulting from increased oxygen deficiency at the surface, confirmed by XPS and STEM-EELS. This is an encouraging sign that mechanochemical routes can be harnessed to provide a sustainable route to preparing mixed metal oxide catalysts with enhanced catalytic performance.
RESUMO
The structure of several nano-sized ceria, CeO2 , systems was investigated using neutron and X-ray diffraction and X-ray absorption spectroscopy. Whilst both diffraction and total pair distribution functions (PDFs) revealed that in all of the samples the occupancy of both Ce4+ and O2- are very close to the ideal stoichiometry, the analysis using Reverse Monte Carlo technique revealed significant disorder around oxygen atoms in the nano-sized ceria samples in comparison to the highly crystalline NIST standard. In addition, the analysis revealed that the main differences observed in the pair correlations from various X-ray and neutron diffraction techniques were attributable to the particle size of the CeO2 prepared by the reported three methods. Furthermore, detailed analysis of the Ce L3 - and K-edge EXAFS data support this finding; in particular the decrease in higher shell coordination numbers with respect to the NIST standard, is attributed to differences in particle size.
