Issue 22, 1997

IR spectroscopic study of NOxadsorption and NOx–O2coadsorption on Co2+/SiO2catalysts

Abstract

Adsorption of nitrogen oxides (NO, NO2) and their coadsorption with oxygen on Co2+/SiO2 samples has been investigated by IR spectroscopy with a view to elucidating the mechanism of selective catalytic reduction (SCR) of NOx with hydrocarbons. A Co2+/SiO2 sample synthesized by ion exchange is characterized by a highly dispersed cobalt and a very weak surface acidity: CO is adsorbed only at low temperature (100 K) forming Co2+–CO carbonyls [ν(CO) = 2180 cm−1]. Adsorption of NO on Co2+/SiO2 leads to the formation of Co2+(NO)2 dinitrosyl complexes (1872 and 1804 cm−1) which are decomposed upon evacuation. Adsorption of NO2, as well as coadsorption of NO and O2, produce NO2 species weakly bound to the support (a band at 1681 cm−1) and N2O4 (a band at 1744 cm−1 with a shoulder at 1710 cm−1), the latter being adsorbed reversibly on both the support and the Co2+ ions. In the second case N2O4 is transformed into surface monodentate nitrates of Co2+ (a band at 1550–1526 cm−1) and partly into bridged nitrates (a band at ca. 1640 cm−1). The monodentate nitrates are stable with respect to evacuation up to 125 °C and act as strong oxidising agents: they are reduced by NO, even at room temperature, and by methane at 100 °C. In the latter case, organic nitro-compounds and isocyanate groups are registered as reaction products (probably intermediate compounds in SCR). The surface species obtained after NO and NO2 adsorption on Co2+/SiO2 prepared from cobalt acetate (active SCR catalyst) are essentially the same as those observed with the ion-exchanged sample. No monodentate nitrates, however, are formed during NO2 adsorption on a Co2+/SiO2 sample synthesized by impregnation with cobalt nitrate, which accounts for the lack of activity of this sample in the SCR.

Article information

Article type
Paper

J. Chem. Soc., Faraday Trans., 1997,93, 4055-4063

IR spectroscopic study of NOxadsorption and NOx–O2coadsorption on Co2+/SiO2catalysts

B. Djonev, B. Tsyntsarski, D. Klissurski and K. Hadjiivanov, J. Chem. Soc., Faraday Trans., 1997, 93, 4055 DOI: 10.1039/A703955G

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