Nucleation of isolated PO4 units on CeO2 driven by high temperatures and the effect on its oxygen storage and release properties

Abstract

The chemical nature of P-containing species of varying concentration present in CeO2 after impregnation with (NH4)2HPO4 and calcination at 1273 K, and their effects on the oxygen storage and release (OSR) properties of ceria are reported for the first time. The samples were characterized by different techniques and the results were compared with those recently reported on the same samples but calcined at 873 K. When P-containing ceria solids were calcined at 1273 K, CePO4 (monazite) was the predominant P-containing species on the surface of ceria, confirming previous studies that showed that monazite exists for those samples in which the surface P loading (P atoms per nm−2) is larger than 5.5. For lower surface P concentrations, isolated orthophosphate units are present at the surface and within the subsurface region of the solid. Severe sintering of CeO2 after calcination at 1273 K resulted in P concentrations >5.5 P atoms·nm−2 in all samples. Isolated PO4 units that could initially be present in the samples calcined at 873 K nucleated and CePO4 was formed when samples were calcined at 1273 K. OSR properties of CeO2 deteriorated progressively when P loading increased due to the presence of larger crystals of the very stable Ce(III) phase of CePO4 at the surface of the P-containing ceria solids.