Operando and Postreaction Diffraction Imaging of the La–Sr/CaO Catalyst in the Oxidative Coupling of Methane Reaction

• Published in: Journal of physical chemistry. C 2019-01, Vol.123 (3), p.1751-1760
• Main Authors: Matras, Dorota, Jacques, Simon D. M, Poulston, Stephen, Grosjean, Nicolas, Estruch Bosch, Cristina, Rollins, Benjamin, Wright, Jonathan, Di Michiel, Marco, Vamvakeros, Antonios, Cernik, Robert J, Beale, Andrew M
• Format: Article
• Language: English
• Subjects: Chemical Sciences
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.8b09018

A La–Sr/CaO catalyst was studied operando during the oxidative coupling of methane (OCM) reaction using the X-ray diffraction computed tomography technique. Full-pattern Rietveld analysis was performed in order to track the evolving solid-state chemistry during the temperature ramp, OCM reaction, as well as after cooling to room temperature. We observed a uniform distribution of the catalyst main components: La2O3, CaO–SrO mixed oxide, and the high-temperature rhombohedral polymorph of SrCO3. These were stable initially in the reaction; however, doubling the gas hourly space velocity resulted in the decomposition of SrCO3 to SrO, which subsequently led to the formation of a second CaO–SrO mixed oxide. These two mixed CaO–SrO oxides differed in terms of the extent of Sr incorporation into their unit cell. By applying Vegard’s law during the Rietveld refinement, it was possible to create maps showing the spatial variation of Sr occupancy in the mixed CaO–SrO oxides. The formation of the Sr-doped CaO species is expected to have an important role in this system through the enhancement of the lattice oxygen diffusion as well as increased catalyst basicity.