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

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posted on 03.08.2020 by Catherine J Davies, Alex Mayer, Jess Gabb, Jake M Walls, Volkan Degirmenci, Paul BJ Thompson, Giannantonio Cibin, Stan Golunski, Simon Kondrat
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.

Funding

EPSRC-funded XMaS Mid-Range facility at BM28 in the European Synchrotron Radiation Facility (ESRF), Grenoble, France where the XAFS measurements were performed (28-01-1223).

Environment theme of the UK Catalysis Hub (EPSRC grant EP/K014854/1).

Diamond Lightsource.

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School

  • Science

Department

  • Chemistry

Published in

Physical Chemistry Chemical Physics

Publisher

Royal Society of Chemistry

Version

VoR (Version of Record)

Rights holder

© the Owner Societies

Publisher statement

This is an open access article. It is published by the Royal Society of Chemistry under the Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0). Full details of this licence are available at: https://creativecommons.org/licenses/by/3.0/

Acceptance date

02/07/2020

Publication date

2020-07-02

Copyright date

2020

ISSN

1463-9076

eISSN

1463-9084

Language

en

Depositor

Dr Simon Kondrat. Deposit date: 3 August 2020

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