XRPD/TEM studies of model high-temperature shift catalysts

The combination of transmission electron microscopy (TEM) and in situ X-ray powder diffraction (XRPD) for the investigation of four model high-temperature shift catalysts makes it possible to obtain and compare information concerning the crystallite and particle shapes and sizes before, during and after the reduction of the synthesized hematite-based model catalyst to the active magnetite-based catalyst. Two chromium-containing iron oxide model catalysts and two pure iron oxide model catalysts were synthesized from hydrated chloride or nitrate salts, resulting in particles with different shapes and sizes. The average crystallite sizes of four model catalysts were determined by XRPD using the Scherrer equation before and after the reduction. The crystallite sizes determined before the reduction were compared with particles sizes determined from TEM images of the same samples. These sizes were generally in good agreement. By using the Rietveld method combined with the Scherrer equation and the Lorentzian Scherrer broadening parameters, the development of the average crystallite size during the in situ reduction was demonstrated. This showed that the average crystallite size of the remaining hematite increases when the reduction begins. Additionally, the average crystallite sizes of the reduced samples showed that the chromium-containing model catalysts have the smallest increase in the overall crystallite size.