NOx uptake mechanism on Pt/BaO/Al2O3 catalysts

The NOx adsorption mechanism on Pt/BaO/Al2O3 catalysts was investigated by performing NOx storage/reduction cycles, NO2 adsorption and NO + O2 adsorption on 2%Pt/(x)BaO/Al2O3 (x = 2, 8, and 20 wt%) catalysts. NOx uptake profiles on 2%\Pt/20%BaO/Al2O3 at 523 K show complete uptake behavior for almost 5 min, and then the NOx level starts gradually increasing with time and it reaches 75% of the inlet NOx concentration after 30 min time-on-stream. Although this catalyst shows fairly high NOx conversion at 523 K, only ~2.4 wt% out of 20 wt% BaO is converted to Ba(NO3)2. Adsorption studies by using NO2 and NO + O2 suggest two different NOx adsorption mechanisms. The NO2 uptake profile on 2%Pt/20%BaO/Al2O3 shows the absence of a complete NOx uptake period at the beginning of adsorption and the overall NOx uptake is controlled by the gas–solid equilibrium between NO2 and BaO/Ba(NO3)2 phase. When we use NO + O2, complete initial NOx uptake occurs and the time it takes to convert ~4% of BaO to Ba(NO3)2 is independent of the NO concentration. These NOx uptake characteristics suggest that the NO + O2 reaction on the surface of Pt particles produces NO2 that is subsequently transferred to the neighboring BaO phase by spill over. At the beginning of the NOx uptake, this spill-over process is very fast and so it is able to provide complete NOx storage. However, the NOx uptake by this mechanism slows down as BaO in the vicinity of Pt particles are converted to Ba(NO3)2. The formation of Ba(NO3)2 around the Pt particles results in the development of a diffusion barrier for NO2, and increases the probability of NO2 desorption and consequently, the beginning of NOx slip. As NOx uptake by NO2 spill-over mechanism slows down due to the diffusion barrier formation, the rate and extent of NO2 uptake are determined by the diffusion rate of nitrate ions into the BaO bulk, which, in turn, is determined by the gas phase NO2 concentration.