Abstract
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 (∼3.6 keV) under high temperature oxidation reaction conditions. X-ray absorption near edge structure analysis of K2CO3/Al2O3 catalysts during heating shows that, at temperatures between 100 and 200 °C, potassium species undergo a structural change from an initial hydrated K2CO3·xH2O and KHCO3 mixture to well-defined K2CO3. As the catalyst is heated from 200 °C to 600 °C, a feature associated with multiple scattering shifts to lower energy, indicating increased K2CO3 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 K2CO3 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 situ characterisation 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.
Highlights
Alkali metal compounds, such as potassium, have a longestablished role in heterogeneous catalysis as promotors[1,2,3,4,5,6] or act as catalytic poisons.[7,8,9,10] These properties are attributed to a Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, UKLiverpool L69 7ZE, UK f Diamond Light Source Ltd, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK † Electronic supplementary information (ESI) available
Prior to testing within the operando XAFS cell, the catalytic performance of K/a-Al2O3 was studied by performing soot oxidation via thermalgravimetric analysis (TGA) and characterised using ex situ XRD and X-ray photoelectron spectroscopy (XPS)
When soot was mixed with K/a-Al2O3, the profile of the combustion peak changed markedly and was shifted to lower temperature, confirming current literature which shows that the presence of a potassium compound provides oxidation pathways with lower activation energy.[33,35]
Summary
Alkali metal compounds, such as potassium, have a longestablished role in heterogeneous catalysis as promotors[1,2,3,4,5,6] or act as catalytic poisons.[7,8,9,10] These properties are attributed to a Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, UKLiverpool L69 7ZE, UK f Diamond Light Source Ltd, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK † Electronic supplementary information (ESI) available. When soot was mixed with K/a-Al2O3, the profile of the combustion peak changed markedly and was shifted to lower temperature, confirming current literature which shows that the presence of a potassium compound provides oxidation pathways with lower activation energy.[33,35]
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