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Free keywords:
diffuse reflectance, polyoxometallate, deactivated, in situ, thermal analysis, EXAFS, XRD, UV-vis-NIR spectroscopy, semi-empirical theory, FTIR spectroscopy, CO adsorption
Project 5: Acid-base & redox properties of heteropoly compounds; Project 7: HPA's preparation, solid state chemistry & catalysis
Abstract:
The present study focuses on the evidence about the existence of Keggin ions under various reactive conditions. The stability of the hydrated parent HPA phases is probed in water, by thermal methods in the gas phase, by in situ X-ray diffraction and in situ EXAFS. An extensive analysis of the in situ optical spectra as UV-Vis-NIR in diffuse reflectance yields detailed information about the activated species that are clearly different from Keggin ions but are also clearly no fragments of binary oxides in crystalline or amorphous form. Infrared spectroscopy with CO as probe molecule is used to investigate active sites for their acidity. Besides –OH groups evidence for electron-rich Lewis acid sites was found in activated HPA. All information fit into a picture of a metastable defective polyoxometallate anion that is oligomerised to prevent crystallisation of binary oxides as the true nature of the “active HPA” catalyst. The as-synthesized HPA crystal is thus a pre catalyst and the precursor oxide mixture is the final deactivated state of the catalyst.
