The NOx storage behavior of a series of Pt-Ba/Al2O3 catalysts, prepared by wet impregnation of Pt/Al2O3 with Ba(Ac)(2), has been investigated. The catalysts with Ba loadings in the range 4.5-28 wt.% were calcined at 500 degrees C in air and subsequently exposed to NO pulses in 5 vol.% O-2/He atmosphere. Catalysts were characterized by means of thermogravimetry (TG) combined with mass spectroscopy (MS) and XRD before and after exposure to NO pulses. Characterization of the calcined catalysts corroborated the existence of three Ba-containing phases which are discernible based on their different thermal stability: BaO, LT-BaCO3 and HT-BaCO3. Characterization after NOx exposure showed that the different Ba-containing phases present in the catalysts possess different reactivity for barium nitrate formation, depending on their interfacial contact. The different Ba(NO3)(2) species produced upon NOx exposure could be distinguished based on their thermal stability. The study revealed that during the NOx storage process a new thermally instable BaCO3 phase formed by reaction of evolved CO2 with active BaO. The fraction of Ba-containing species that were active in NOx storage depended on the Ba loading, showing a maximum at a Ba loading of about 17 wt.%. Lower and higher Ba loading resulted in a significant loss of the overall efficiency of the Ba-containing species in the storage process. The loss in efficiency observed at higher loading is attributed to the lower reactivity of the HT-BaCO3, which becomes dominant at higher loading, and the increased mass transfer resistance. (c) 2005 Elsevier B.V. All rights reserved.