TPD, TPR and DRIFTS studies of adsorption and reduction of NO on La2O3 dispersed on Al2O3

The surface properties of La2O3 supported on gamma-Al2O3, as characterized by DRIFTS or temperature-programmed desorption (TPD), showed features more and more similar to unsupported La2O3 as the La2O3 loading increased. Optim um rates (mole/s g) were obtained when the bulk-like La2O3 surface area was maximized, and the 40% La2O3/Al2O3 catalyst had a rate high enough to poss ibly allow its use in combined-cycle power plants. TPD with La2O3/gamma-Al2 O3 and pure gamma-Al2O3 after exposure to NO at 300 K gave three NO desorpt ion peaks and the only O-2 desorbed coincided with the high-temperature NO peak near 800 K. TPD after (NO)-N-15-O-16 adsorption on O-18-exchanged La2O 3/gamma-Al2O3 and gamma-Al2O3 surfaces showed that a very small amount of ( NO)-N-15-O-18 desorbed from the middle-temperature sites near 700 K, while (NO)-N-15-O-18 and (OO)-O-16-O-18 desorbed from the high-temperature sites. Adsorption of NO on supported La2O3 resulted in the formation of nitrosyl, nitrite and nitrate species, and their thermal stabilities increased in th e following order: NOdelta+ (on Al2O3)approximate to bridged nitrate (on La 2O3)<linear and chelated nitrito complexes (on Al2O3)approximate to NO- (on La2O3)<bidentate nitrate (on Al2O3)approximate to unidentate nitrate (on L a2O3). The distribution of the adsorbed species between La2O3 and Al2O3 sur faces depends on the La2O3 loading. temperature-programmed reaction (TPR) e xperiments in which adsorbed NO reacted with either CH4 or CH4+O-2 showed t hat the nitrate species which are stable at high temperatures are unlikely to be active intermediates in the catalytic reduction of NO with CH4. It is proposed that either O atoms or NO2 species adsorbed on oxygen vacancies a re responsible for the activation of CH4. (C) 2000 Elsevier Science B.V. Al l rights reserved.