Skip to main content
SpringerLink
Log in

Labeled 15NO Study on N2 and N2O Formation Over Pt–Ba/Al2O3 NSR Catalysts

  • Original Paper
  • Published:
Topics in Catalysis Aims and scope Submit manuscript

Abstract

Mechanistic aspects involved in the formation of N2 and of N2O during the reduction of NO, stored nitrites and stored nitrates in the presence of NO are investigated in this work by means of isotopic labeling experiments over a model PtBa/Al2O3 NSR catalyst. The reduction of gaseous labeled NO with unlabelled NH3 leads to the formation of N2O at low temperature (below 180 °C), and of N2 at high temperature. All N2 possible isotopes are observed, whereas only labeled molecules have been detected in the case of N2O. Hence the formation of nitrous oxide involves undissociated NO molecules, whereas that of N2 can be explained on the basis of the statistical coupling of 15N- and 14N-adatoms on Pt. However, due to a slight excess of the mixed 15N14N isotope, a SCR-like pathway likely operates as well. The reduction of the stored labelled nitrates is very selective to N2 and all isotopes are observed, confirming the occurrence of the recombination pathway. However also in this case a SCR-like pathway likely occurs and this explains the abundance of the 14N15N species. When the reduction of the stored nitrates is carried out in the presence of NO, this species is preferentially reduced pointing out the higher reactivity of gaseous NO if compared to the nitrates.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Johnson TV (2011) Diesel emission review. SAE Int J of Engines 4:143

    Google Scholar 

  2. Granger P, Parvulescu VI (2011) Catalytic NOx abatement systems for mobile sources: from three-way to lean burn after-treatment technologies 111:3155

    CAS  Google Scholar 

  3. Baiker RS (2009) NOx Storage-reduction catalysis: from mechanism and materials properties to storage-reduction performance. Chem Rev 109:4054

    Article  Google Scholar 

  4. Takahashi N, Shinjoh H, Iijima T, Suzuki T, Yamazaki K, Yokota K, Suzuki H, Miyoshi N, Matsumoto S, Tanizawa T, Tanaka T, Tateishi S, Kasahara K (1996) The new concept 3-way catalyst for automotive lean-burn engine: NOx storage and reduction catalyst. Catal Today 27:63

    Article  CAS  Google Scholar 

  5. Epling W, Campbell L, Yezerets A, Currier N, Parks J (2004) Overview of the fundamental reactions and degradation mechanism of NOx storage/reduction catalysts. Catal Rev Sci Eng 46:163

    Article  Google Scholar 

  6. Miyoshi N, Matsumoto S, Katoh K, Tanaka T, Harada J, Takahashi N, Yokota K, Sugiura M, Kasahara K (1995) Development of new concept three-way catalyst for automotive lean-burn engines. SAE Technical Paper 950809

  7. Castoldi L, Bonzi R, Lietti L, Forzatti P (2011) Catalytic behaviour of hybrid LNT/SCR systems: reactivity and in situ FTIR study. J Catal 1:128

    Article  Google Scholar 

  8. Toops TJ, Smith DB, Partridge WP (2008) NOx adsorption on Pt/K/Al2O3. Catal Today 114:112

    Article  Google Scholar 

  9. Konsolakis M, Yentekakis IV (2001) Strong promotional effects of Li, K, Rb and Cs on the Pt-catalysed reduction of NO by propene. Appl Catal B 29:103

    Article  CAS  Google Scholar 

  10. Nova I, Lietti L, Castoldi L, Tronconi E, Forzatti P (2006) New insights in the NOx reduction mechanism with H2 over Pt-Ba/γ-Al2O3 lean NOx trap catalysts under near-isothermal conditions. J Catal 239:244

    Article  CAS  Google Scholar 

  11. Breen JP, Burch R, Fontaine-Gautrelet C, Hardacre C, Rioche C (2008) Insight into the key aspects of the regeneration process in the NOx storage reduction (NSR) reaction probed using fast transient kinetics coupled with isotopically labelled 15NO over Pt and Rh-containing Ba/Al2O3 catalysts. Appl Catal B Environ 81:150

    Article  CAS  Google Scholar 

  12. Lietti L, Nova I, Forzatti P (2008) Role of ammonia in the reduction by hydrogen of NOx stored over Pt–Ba/Al2O3 lean NOx trap catalysts. J Catal 257:270

    Article  CAS  Google Scholar 

  13. Cumaranatunge L, Mulla SS, Yezerets A, Currier NW, Delgass WN, Ribeiro FH (2007) Ammonia is a hydrogen carrier in the regeneration of Pt/BaO/Al2O3 NOx traps with H2. J Catal 246, 29

    Google Scholar 

  14. Bhatia D, Harold MP, Balakotaiah V (2010) Modeling the effect of Pt dispersion and temperature during anaerobic regeneration of a lean NOx trap catalyst. Catal Today 151:314

    Article  CAS  Google Scholar 

  15. Nova I, Lietti L, Forzatti P (2008) Mechanistic aspects of the reduction of stored NOx over Pt–Ba/Al2O3 lean NOx trap systems. Catal Today 136:128

    Article  CAS  Google Scholar 

  16. Forzatti P, Lietti L, Nova I (2008) On board catalytic NOx control: mechanistic aspects of the regeneration of lean NOx traps with H2. Energy Environ Sci 1:236

    Article  CAS  Google Scholar 

  17. Lietti L, Artioli N, Righini L, Castoldi L, Forzatti P (2012) Ind Eng Chem Res 51:7597

    Article  CAS  Google Scholar 

  18. Pereda-Ayo B, González-Velasco JR, Burch R, Hardacre C, Chansai S (2012) J Catal 285:177

    Article  CAS  Google Scholar 

  19. Miyoshi N, Tanizawa T, Kasahara K, Tateishi S (1995) European Patent Application 0 669 157 A1

  20. Nova I, Castoldi L, Prinetto F, Dal SantoV, Lietti L, Tronconi E, Forzatti P, Ghiotti G, Psaro R, Recchia S (2004) NOx adsorption study over Pt–Ba/alumina catalysts: FT-IR and reactivity study. Top Catal 30/31, 181

  21. Prinetto F, Ghiotti G, Nova I, Castoldi L, Lietti L, Tronconi E, Forzatti P (2003) In situ Ft-IR and reactivity study of NOx storage over Pt–Ba/γ-Al2O3 catalysts. Phys Chem Chem Phys 5:4428

    Article  CAS  Google Scholar 

  22. Nova I, Castoldi L, Lietti L, Tronconi E, Forzatti P, Prinetto F, Ghiotti G (2004) NOX adsorption study over Pt–Ba/alumina catalysts: fT-IR and pulse experiments. J Catal 222:377

    Article  CAS  Google Scholar 

  23. Lietti L, Daturi M, Blasin-Aubé V, Ghiotti G, Prinetto F, Forzatti P (2012) Relevance of nitrite route in the NOx adsorption mechanism over Pt–Ba/Al2O3, NSR catalysts investigated by FT-IR operando spectroscopy. Chem Catal Chem 4:55

    CAS  Google Scholar 

  24. Kumar A, Harold MP, Balakotaiah V (2010) Isotopic studies of NOX storage and reduction on Pt/BaO/Al2O3 catalyst using temporal analysis of products. J Catal 270:214

    Article  CAS  Google Scholar 

  25. Kondraratenko VA, Baerns M (2007) Mechanistic insights into the formation of N2O and N2 in NO reduction by NH3 over a polycrystalline platinum catalyst. Appl Catal B 70:111

    Article  Google Scholar 

  26. Van Tol MFH, Siera J, Cobden PD, Nieuwenhuys BE (1992) Oscillatory behaviour of the reduction of NO by H2 over Rh. Surf Sci 274:63

    Article  Google Scholar 

  27. Nova I, Castoldi L, Lietti L, Tronconi E, Forzatti P, Prinetto F, Ghiotti G (2005) The Pt–Ba interaction in Lean NOx Trap systems. SAE Technical Paper 2005-01-1085

  28. Nova I, Castoldi L, Lietti L, Tronconi E, Forzatti P A low temperature pathway operating the reduction of stored nitrates in Pt-Ba/Al2O3 Lean NOx Trap Systems. SAE Technical Paper 2006-01-1368

  29. Perez-Ramirez J, Kondratenko EV, Kondratenko VA, Baerns M (2005) Selectivity-directing factors of ammonia oxidation over PGM gauzes in the temporal analysis of products reactor: secondary interactions of NH3 and NO. J Catal 229:303

    Article  CAS  Google Scholar 

  30. Burch R, Shestov AA, Sullivan JA (1999) A Steady-state isotopic transient kinetic analysis of the NO/O2/H2 reaction over Pt/SiO2 catalysts. J Catal 188:69

    Article  CAS  Google Scholar 

  31. Cant NW, Chambers DC, Liu IOY (2011) The reduction of 15N14NO by CO and by H2 over Rh/SiO2: a test of a mechanistic proposal. J Catal 278:162

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Dipartimento di Energia, Laboratory of Catalysis and Catalytic Processes and NEMAS, Centre of Excellence, Politecnico di Milano, P.zza L. da Vinci 32, Milano, Italy

    L. Lietti, L. Righini, L. Castoldi, N. Artioli & P. Forzatti

Authors
  1. L. Lietti
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. L. Righini
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. L. Castoldi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. N. Artioli
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. P. Forzatti
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to L. Lietti.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Lietti, L., Righini, L., Castoldi, L. et al. Labeled 15NO Study on N2 and N2O Formation Over Pt–Ba/Al2O3 NSR Catalysts. Top Catal 56, 7–13 (2013). https://doi.org/10.1007/s11244-013-9920-9

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11244-013-9920-9

Keywords

Search

Navigation