by S. Morandi, F. Prinetto, G. Ghiotti, L. Castoldi, L. Lietti, P. Forzatti, M. Daturi, V. Blasin-Aubé
Catalysis Today, Volume 231, 1 August 2014, Pages 116–124
DOI: 10.1016/j.cattod.2013.12.036
Highlights
• The effect of CO2 and H2O on the NOx storage on PtBa/Al2O3 is investigated.
• NOx are stored on PtBa catalysts as nitrites and nitrates.
• CO2 inhibits nitrite formation mostly at high temperatures.
• The dead time for NOx breakthrough is significantly shortened.
• Nitrite and carbonate thermal stability as key to the reading CO2 inhibition effect.
Abstract
The effect of CO2 and H2O on the NO/O2 storage over a Pt-Ba/Al2O3 LNT catalyst was investigated in the temperature range 150–350 °C by combining FT-IR spectroscopy and microreactor flow experiments. It is found that the presence of water shows negligible effect on the NOx storage at all the temperatures studied. Otherwise, the presence of CO2 inhibits the “nitrite route” (initial formation of surface nitrites and their subsequent evolution to nitrates), whereas the “nitrate route” (involving NO oxidation to NO2 over Pt and its subsequent adsorption on Ba in the form of nitrates) proceeds as in the absence of CO2. The inhibition effect of CO2 on nitrite formation increases on increasing the temperature. This behavior is likely related to the different thermal stability of nitrites and carbonates and, in particular, to the decreasing ability of nitrites to displace carbonates on increasing temperature. Simultaneously, the presence of CO2 in the feed significantly shortens or eliminates the dead time in the NOx breakthrough at the reactor outlet. As a consequence, the presence of dead time in the absence of CO2 has been correlated to the occurrence of the nitrite route.
Graphical abstract
Keywords
Pt-Ba/Al2O3; NOx storage; CO2; operando FT-IR; Transient microreactor experiments
