Micro-calorimetric studies of NO2 adsorption on Pt/BaO-supported on Γ-Al2O3 NOx storage and reduction (NSR) catalysts—Impact of CO2

The adsorption of NO2 on Pt/BaO/γAl2O3 catalyst has been investigated by micro calorimetry at atmospheric pressure, NOx storage tests and temperature-programmed desorption (TPD). The heat of adsorption of NO2 (ΔHads(NO2)) was determined over a wide range of NOx coverages, as the catalyst was exposed to 500/900 ppm NO2 in the absence/presence of 5% CO2 in the range of 423–773 K. The temperature dependent changes of ΔHads(NO2) verified the presence of energetically different NOx storage sites with different binding strength. The ΔHads(NO2) was found to follow a linear correlation versus temperature, ranging for example from −134.5 to −178.8 kJ/mol for NOx storage over Pt/BaO/γAl2O3 at 423–673 K. Thus, at high temperature mostly strongly bound nitrates were formed, while at lower temperature more loosely bound species were also present. Interestingly, the heat of adsorption was higher when using higher NO2 concentration, indicating more bulk barium nitrate formation. This is consistent with the TPD data where a clear high temperature peak was visible after adsorption using 900 ppm NO2 at 423 and 473 K, which was not the case for 500 ppm NO2. Moreover, the micro-calorimetric data also provided evidence in support of the detrimental effect of CO2 on the NOx uptake process. The heat released during the NOx storage in 500 ppm NO2 + 5% CO2 was determined to be significantly reduced ca. −97.8 kJ mol−1 at 423 K, but ca. −134.5 kJ mol−1 without CO2. Furthermore, our results show that it is critical to measure heat of adsorption for surface compounds since they are significantly different compared to thermodynamic data for bulk materials.