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

被引:64
作者
Huang, SJ [1 ]
Walters, AB [1 ]
Vannice, MA [1 ]
机构
[1] Penn State Univ, Dept Chem Engn, University Pk, PA 16802 USA
基金
美国国家科学基金会;
关键词
NO desorption; NO reduction; La2O3/Al2O3; catalysts; CH4; DRIFTS; TPD; TPR;
D O I
10.1016/S0926-3373(00)00115-6
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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. Optimum 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 possibly allow its use in combined-cycle power plants. TPD with La2O3/gamma-Al2O3 and pure gamma-Al2O3 after exposure to NO at 300 K gave three NO desorption 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 La2O3/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 the following order: NOdelta+ (on Al2O3)approximate to bridged nitrate (on La2O3)<linear and chelated nitrito complexes (on Al2O3)approximate to NO- (on La2O3)<bidentate nitrate (on Al2O3)approximate to unidentate nitrate (on La2O3). The distribution of the adsorbed species between La2O3 and Al2O3 surfaces depends on the La2O3 loading. temperature-programmed reaction (TPR) experiments in which adsorbed NO reacted with either CH4 or CH4+O-2 showed that 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 are responsible for the activation of CH4. (C) 2000 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:101 / 118
页数:18
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