Mohamed H.M. Ahmed

Characterization of Chromia/Alumina Catalysts by X-Ray Photoelectron Spectroscopy, Proton Induced X-Ray Emission and Thermogravimetric Analysis

Chromia/alumina catalysts with different metal loading were characterized using X-ray photoelectron spectroscopy (XPS), proton induced X-ray emission (PIXE) and thermogravimetric (TG) techniques to elucidate the surface structure of these catalysts. XPS studies on calcined samples show a sharp increase of the Cr/Al ratio at calcination temperatures up to 500°C while the ratio remains relatively unchanged at higher calcination temperature. The surface state of chromium shows predominantly Cr6+. At calcination temperatures higher than 500°C, calcination-induced reduction is observed of the Cr6+ to Cr3+, where the fraction of chromia in Cr3+ oxidation state increases with increasing temperature. A progressive increase of the intensity of the peak due to Cr 2p of the Cr3+ oxidation state is also observed with increasing amount of metal loading. The calcination-induced reduction of the alumina-supported chromia was found to be less than the corresponding reduction of bulk CrO3. Also, the size of the spin-orbit splitting of the Cr 2p level of chromia catalysts which had undergone calcination-induced reduction was found to be smaller than would be expected for bulk Cr3+. The XPS spectra of chromium on the Cr/Al catalysts were found to be time dependent. Photoreduction of Cr6+ on Cr/Al samples was found for irradiation times longer than 4.0 min. It was found from PIXE analysis that at higher calcination temperature, the Cr/Al atomic ratio approaches the values obtained by XPS. For all samples, the chromium particles were found to be homogeneously distributed on the alumina support for calcination temperatures up to 800°C. Thermogravimetric results on uncalcined bulk CrO3 agree well with the XPS observation as to the fact that the main phase transformation of Cr6+ compounds occurs at about 500°C, resulting in reduction to Cr3+.