Nanostructural and Chemical Characterization of Supported Metal Oxide Catalysts by Aberration Corrected Analytical Electron Microscopy

In this thesis, aberration corrected STEM imaging and chemical analysis techniques have been extensively applied in the structural and chemical characterization of supported tungsten oxide catalysts in an attempt to reveal the structure-activity relationships at play in these catalyst systems.;The supported WO3/ZrO2 solid acid catalyst system is a major focal point of this thesis, and detailed aberration-corrected STEM-HAADF imaging studies were performed on a systematic set of catalysts showing different level of catalytic performance. The nature of the catalytically most active WOx species was identified by correlating structural information, obtained from STEM-HAADF and in-situ optical spectroscopy studies, with catalytic testing results. Specifically, ∼1nm distorted Zr-WOx mixed oxide clusters were identified to be the most active species for both the methanol dehydration and n-pentane isomerization reactions in the WO3/ZrO2 catalyst system. The use of amorphous zirconia as a precursor support material makes it much easier to extract and incorporate Zr cations into the surface WOx clusters during calcination. The calcination temperature was also identified to also play an important role in the formation of these most active Zr-WOx clusters. When the calcination temperature is comparable to or higher than the 896K Huttig temperature of ZrO2 (at which surface ZrO x species have sufficient mobility to agglomerate and sinter), the chance for successful surface WOx and ZrOx intermixing is significantly increased.;Based on this perceived structure-activity relationship, several new catalyst synthesis strategies were developed in an attempt to optimize the catalytic performance of WOx-based catalysts. We have demonstrated in Chapter 3 that co-impregnation of WOx and ZrOx precursors onto an inactive model WO3/ZrO2 catalyst, followed by a calcination treatment above the 896K Huttig temperature of ZrO 2, promotes the surface diffusion of ZrO2 and intermixing of ZrOx with WOx. As a consequence, the catalytic activity of the co-impregnated material is dramatically increased by more than two orders of magnitude. We further showed in Chapter 5 that the Keggin structure based on phosphotungstic acid hydrate (i.e. an ∼ 1nm P-WOx mixed oxide cluster) can be successfully immobilized on an amorphous SiO2 support surface. Such catalyst design experiments further support our postulated structure-activity model, in which WO x clusters mixed with some low valence heteroatoms are the most active entities for the methanol dehydration and n-pentane isomerization reactions.;Another major theme of this thesis is the analysis of model double-supported metal oxide catalysts, in which a high surface area oxide support material (amorphous SiO2) is modified by the presence of a second metal oxide surface species (TiO2 or ZrO2) added to control the distribution and activity of the active surface WOx component. These complex double-supported metal oxide catalysts represent a very significant challenge in terms of structural characterization. A new electron microscopy characterization strategy was developed for this purpose which combined aberration corrected STEM imaging with concurrent EELS and XEDS analysis. We demonstrated that the various components in a double-supported WO3/TiO 2/SiO2 catalyst system can be effectively visualized using complementary HAADF and STEM-BF imaging within an aberration corrected STEM. Furthermore, when combined with chemical analysis by STEM-EELS and XEDS within the same STEM instrument, it is possible to map out the relative spatial distribution of all the metal oxide components within the WO3/TiO2/SiO 2 catalyst. By comparing the structures of a systematic set of WO 3/TiO2/SiO2 samples displaying high, intermediate and low activity for the methanol dehydration reaction, we showed that the acidic catalytic activity seems to benefit from having (i) a more localized electron density on the TiOx support and (ii) a larger WOx domain that can better disperse the electron density.;The results presented in this thesis clearly demonstrate the power of aberration corrected STEM imaging and chemical analysis techniques in the study of supported metal oxide catalysts. Many valuable insights into the structure-activity relationships existing in these supported WOx catalyst systems have been obtained as described above. In order to better understand the nature of these fascinating catalyst materials and further develop catalysts with even better catalytic performance, several suggestions for future work on these supported WOx catalysts are also discussed in the last chapter of this thesis. In particular, in-situ electron microscopy techniques that allow samples to be imaged in HAADF mode under reaction condition need to be further developed. Such an advance could potentially provide unprecedented insights into the structure-activity relationships that exist in these catalyst systems and open up new opportunities for structural and chemical characterization of catalyst materials under realistic working conditions.