Adsorption and reactivity of nitrogen oxides (NO 2, NO, N 2O) on Fe–zeolites

• Published in: Journal of catalysis Vol. 264; no. 2; pp. 104 - 116
• Main Authors: Rivallan, Mickaël, Ricchiardi, Gabriele, Bordiga, Silvia, Zecchina, Adriano
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier Inc 10.06.2009; Elsevier; Elsevier BV
• Subjects: Catalysis; Chemical Sciences; Chemistry; Decomposition; Exact sciences and technology; Fe(II) active sites; Fe–zeolite; General and physical chemistry; Ion-exchange; MFI; N 2O decomposition; N 2O, NO, and NO 2 probe molecules; Nitrogen; Spectrum analysis; Surface physical chemistry; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Zeolites: preparations and properties; Fe(II) active sites; MFI; Fe–zeolite; N 2O, NO, and NO 2 probe molecules; N 2O decomposition; Binary compound; Iron oxide; Hydrogen; Active site; Decomposition; Iron; O decomposition; Molecular sieve; Mechanism; N; Catalytic conversion; Particle; probe molecules; Chemical reactivity; Structure; Deposition; Nitrogen oxide; Oxygen; Catalytic reaction; Transition element compounds; Thermodesorption; Transition metal; Zeolite; O, NO, and NO; Bronsted site; Complexes; Infrared spectrometry; Heterogeneous catalysis; Chemistry; Adsorption; Fe―zeolite; Preparation; Environment; Nitrogen protoxide; Catalyst
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2009.03.012

Kinetic results of N 2O decomposition reaction on Fe–MFI zeolites combined with the IR spectroscopy of the surface sites titration with N 2O, NO, and NO 2 show that low coordinated and isolated Fe 2+ sites are the most active in N 2O decomposition. The cooperation between Fe 2+ and Brønsted sites is also demonstrated for Fe–ZSM-5. Nitrous oxide decomposition and temperature programmed desorption tests on Fe–ZSM-5 and Fe–silicalite show that the catalytic conversion mechanism of N 2O into N 2 and O 2 over Fe–zeolites is more complex than expected. Nitrogen oxides are formed as byproducts of the catalytic process with the major part consisting in NO 2 species adsorbed on the iron sites. FTIR spectroscopy of adsorbed N 2O, NO, and NO 2 has been used to investigate the structure and environment of the iron active species of the Fe–MFI catalysts before and after atomic oxygen deposition. The interactions of NO and N 2O probes on activated Fe–ZSM-5 have evidenced two families of mononuclear Fe(II) centers (Fe A and Fe B) differing in the coordination state of Fe. N 2O also interacts with Brønsted sites of Fe–ZSM-5 via hydrogen bonding. This type of interaction is nearly absent in Fe–silicalite. Polynuclear species (clusters) and iron oxide particles, whose concentrations are strongly influenced by the iron content and by the preparation methods are also present. When oxidized samples (by N 2O) are considered, the ability of Fe A and Fe B centers to adsorb N 2O and NO is strongly depressed. On the contrary, the surface chemistry of iron particles is not appreciably influenced. These results represent an indirect proof of the preferential presence of adsorbed oxygen on isolated Fe centers. NO titration of oxidized Fe–ZSM-5 results in the formation of a complex network of interplaying neutral (NO, NO 2, N 2O 4) and ionic species (NO +, NO 2 - , NO 3 - ). The cooperation of sites between Brønsted and iron active sites is demonstrated. The last observation is fully confirmed by the experiments performed using NO 2 probe that titrates both Brønsted and iron sites. On the basis of the comparison of catalytic results of N 2O decomposition and of spectroscopic results concerning the titration of surface sites with N 2O, NO, and NO 2 obtained on the same samples (which form the main scope of the paper), it clearly emerges that mononuclear sites characterized by lowest coordination are the most active in N 2O decomposition. Under the adopted conditions, low or negligible activity is shown by Fe x O y clusters and Fe 2O 3 particles.