Operando potassium K-edge X-ray absorption spectroscopy: investigating potassium catalysts during soot oxidation

摘要

The chemical and structural nature of potassium compounds involved in catalytic soot oxidation have been studied by a combination of temperature programmed oxidation and operando potassium K-edge X-ray absorption spectroscopy experiments. These experiments are the first known operando studies using tender X-rays (similar to 3.6 keV) under high temperature oxidation reaction conditions. X-ray absorption near edge structure analysis of K2CO3/Al(2)O(3)catalysts during heating shows that, at temperatures between 100 and 200 degrees C, potassium species undergo a structural change from an initial hydrated K2CO3 center dot xH(2)O and KHCO(3)mixture to well-defined K2CO3. As the catalyst is heated from 200 degrees C to 600 degrees C, a feature associated with multiple scattering shifts to lower energy, indicating increased K(2)CO(3)dispersion, due to its mobility at high reaction temperature. This shift was noted to be greater in samples containing soot than in control experiments without soot and can be attributed to enhanced mobility of the K2CO3, due to the interaction between soot and potassium species. No potassium species except K(2)CO(3)could be defined during reactions, which excludes a potential reaction mechanism in which carbonate ions are the active soot-oxidising species. Simulations of K-edge absorption near edge structures were performed to rationalise the observed changes seen. Findings showed that cluster size, unit cell distortions and variation in the distribution of potassium crystallographic sites influenced the simulated spectra of K2CO3. While further simulation studies are required for a more complete understanding, the current results support the hypothesis that changes in the local structure on dispersion can influence the observed spectra.Ex situcharacterisation was carried out on the fresh and used catalyst, by X-ray diffraction and X-ray photoelectron spectroscopy, which indicated changes to the carbonate species, in line with the X-ray absorption spectroscopy experiments.