Cu Loading Dependence of Fast NH3-SCR on Cu/SSZ-13


The fast NH3-SCR kinetics are studied on Cu/SSZ-13 with different Cu loadings, under reaction conditions (temperature and space velocity) where both steady-state and differential NOx conversions are readily achieved. Cu loading is found to greatly influence low-temperature NOx turnover rates, however not to substantially affect apparent activation energies. The high reaction apparent activation energies (~ 160 kJ/mol) suggest that the rate-limiting kinetics for fast SCR involve the participation of NH4NO3, an intermediate that is of considerable stability in small-pore zeolites. The energetically demanding NH4NO3 + NO reactions make low-temperature fast SCR much slower than standard SCR over Cu-exchanged small-pore zeolite catalysts, in drastic contrast to vanadium and medium/large pore zeolite-based SCR catalysts.

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5


  1. 1.

    Johnson, T.V.: Review of diesel emissions and control. Int. J. Engine Res. 10(5), 275–285 (2009)

    Article  Google Scholar 

  2. 2.

    Kamasamudram, K., Currier, N.W., Chen, X., Yezerets, A.: Overview of the practically important behaviors of zeolite-based urea-SCR catalysts, using compact experimental protocol. Catal. Today. 151(3-4), 212–222 (2010)

    Article  Google Scholar 

  3. 3.

    Koebel, M., Elsener, M., Kleemann, M.: Urea-SCR: a promising technique to reduce NOx emissions from automotive diesel engines. Catal. Today. 59(3-4), 335–345 (2000)

    Article  Google Scholar 

  4. 4.

    Iwasaki, M., Shinjoh, H.: A comparative study of “standard”, “fast” and “NO(2)” SCR reactions over Fe/zeolite catalyst. Appl. Catal. A Gen. 390(1-2), 71–77 (2010)

    Article  Google Scholar 

  5. 5.

    Brandenberger, S., Krocher, O., Tissler, A., Althoff, R.: The state of the art in selective catalytic reduction of NOx by ammonia using metal-exchanged zeolite catalysts. Catal. Rev. 50(4), 492–531 (2008)

    Article  Google Scholar 

  6. 6.

    Parvulescu, V.I., Grange, P., Delmon, B.: Catalytic removal of NO. Catal. Today. 46(4), 233–316 (1998)

    Article  Google Scholar 

  7. 7.

    Colombo, M., Nova, I., Tronconi, E.: A comparative study of the NH(3)-SCR reactions over a cu-zeolite and a Fe-zeolite catalyst. Catal. Today. 151(3-4), 223–230 (2010)

    Article  Google Scholar 

  8. 8.

    Li, J.H., Chang, H.Z., Ma, L., Hao, J.M., Yang, R.T.: Low-temperature selective catalytic reduction of NOx with NH3 over metal oxide and zeolite catalysts—a review. Catal. Today. 175(1), 147–156 (2011)

    Article  Google Scholar 

  9. 9.

    Gao, F., Kwak, J.H., Szanyi, J., Peden, C.H.F.: Current understanding of cu-exchanged Chabazite molecular sieves for use as commercial diesel engine DeNO(x) catalysts. Top. Catal. 56(15-17), 1441–1459 (2013)

    Article  Google Scholar 

  10. 10.

    Beale, A.M., Gao, F., Lezcano-Gonzalez, I., Peden, C.H.F., Szanyi, J.: Recent advances in automotive catalysis for NOx emission control by small-pore microporous materials. Chem. Soc. Rev. 44(20), 7371–7405 (2015)

    Article  Google Scholar 

  11. 11.

    Borfecchia, E., Beato, P., Svelle, S., Olsbye, U., Lamberti, C., Bordiga, S.: Cu-CHA—a model system for applied selective redox catalysis. Chem. Soc. Rev. 47(22), 8097–8133 (2018)

    Article  Google Scholar 

  12. 12.

    Gao, F., Peden, C.H.F.: Recent progress in atomic-level understanding of Cu/SSZ-13 selective catalytic reduction catalysts. Catalysts. 8, 140 (2018)

    Article  Google Scholar 

  13. 13.

    Kwak, J.H., Zhu, H.Y., Lee, J.H., Peden, C.H.F., Szanyi, J.: Two different cationic positions in Cu-SSZ-13? Chem. Commun. 48(39), 4758–4760 (2012)

    Article  Google Scholar 

  14. 14.

    Andersen, C.W., Bremholm, M., Vennestrøm, P.N.R., Blichfeld, A.B., Lundegaard, L.F., Iversen, B.B.: Location of Cu2+ in CHA zeolite investigated by X-ray diffraction using the Rietveld/maximum entropy method. IUCrJ. 1(6), 382–386 (2014)

    Article  Google Scholar 

  15. 15.

    Bates, S.A., Verma, A.A., Paolucci, C., Parekh, A.A., Anggara, T., Yezerets, A., Schneider, W.F., Miller, J.T., Delgass, W.N., Ribeiro, F.H.: Identification of the active Cu site in standard selective catalytic reduction with ammonia on Cu-SSZ-13. J. Catal. 312, 87–97 (2014)

    Article  Google Scholar 

  16. 16.

    Gao, F., Washton, N.M., Wang, Y.L., Kollar, M., Szanyi, J., Peden, C.H.F.: Effects of Si/Al ratio on Cu/SSZ-13 NH3-SCR catalysts: implications for the active Cu species and the roles of Bronsted acidity. J. Catal. 331, 25–38 (2015)

    Article  Google Scholar 

  17. 17.

    Paolucci, C., Parekh, A.A., Khurana, I., Di Iorio, J.R., Li, H., Caballero, J.D.A., Shih, A.J., Anggara, T., Delgass, W.N., Miller, J.T., Ribeiro, F.H., Gounder, R., Schneider, W.F.: Catalysis in a cage: condition-dependent speciation and dynamics of exchanged Cu cations in SSZ-13 zeolites. J. Am. Chem. Soc. 138(18), 6028–6048 (2016)

    Article  Google Scholar 

  18. 18.

    Gao, F., Mei, D.H., Wang, Y.L., Szanyi, J., Peden, C.H.F.: Selective catalytic reduction over cu/SSZ-13: linking homo- and heterogeneous catalysis. J. Am. Chem. Soc. 139(13), 4935–4942 (2017)

    Article  Google Scholar 

  19. 19.

    Paolucci, C., Khurana, I., Parekh, A.A., Li, S.C., Shih, A.J., Li, H., Di Iorio, J.R., Albarracin-Caballero, J.D., Yezerets, A., Miller, J.T., Delgass, W.N., Ribeiro, F.H., Schneider, W.F., Gounder, R.: Dynamic multinuclear sites formed by mobilized copper ions in NOx selective catalytic reduction. Science. 357(6354), 898–903 (2017)

    Article  Google Scholar 

  20. 20.

    Koebel, M., Elsener, M., Madia, G.: Reaction pathways in the selective catalytic reduction process with NO and NO2 at low temperatures. Ind. Eng. Chem. Res. 40(1), 52–59 (2001)

    Article  Google Scholar 

  21. 21.

    Grossale, A., Nova, I., Tronconi, E., Chatterjee, D., Weibel, M.: The chemistry of the NO/NO2-NH3 "fast" SCR reaction over Fe-ZSM5 investigated by transient reaction analysis. J. Catal. 256(2), 312–322 (2008)

    Article  Google Scholar 

  22. 22.

    Velez, R.P., Ellmers, I., Huang, H.M., Bentrup, U., Schunemann, V., Grunert, W., Bruckner, A.: Identifying active sites for fast NH3-SCR of NO/NO2 mixtures over Fe-ZSM-5 by operando EPR and UV-vis spectroscopy. J. Catal. 316, 103–111 (2014)

    Article  Google Scholar 

  23. 23.

    Forzatti, P., Nova, I., Tronconi, E.: Enhanced NH3 selective catalytic reduction for NOx abatement. Angew. Chem. Int. Ed. 48(44), 8366–8368 (2009)

    Article  Google Scholar 

  24. 24.

    Grossale, A., Nova, I., Tronconi, E.: Role of nitrate species in the “NO(2)-SCR” mechanism over a commercial Fe-zeolite catalyst for SCR mobile applications. Catal. Lett. 130(3-4), 525–531 (2009)

    Article  Google Scholar 

  25. 25.

    Grossale, A., Nova, I., Tronconi, E., Chatterjee, D., Weibel, M.: NH(3)-NO/NO(2) SCR for diesel exhausts Aftertreatment: reactivity, mechanism and kinetic modelling of commercial Fe- and Cu-promoted zeolite catalysts. Top. Catal. 52, 1837–1841 (2009)

    Article  Google Scholar 

  26. 26.

    Hao, T., Wang, J., Yu, T., Wang, J.Q., Shen, M.Q.: Effect of NO2 on the selective catalytic reduction of NO with NH3 over cu/SAPO-34 molecular sieve catalyst. Acta Phys. -Chim. Sin. 30, 1567–1574 (2014)

    Google Scholar 

  27. 27.

    Xie, L.J., Liu, F.D., Liu, K., Shi, X.Y., He, H.: Inhibitory effect of NO2 on the selective catalytic reduction of NOx with NH3 over one-pot-synthesized Cu-SSZ-13 catalyst. Catal. Sci. Technol. 4(4), 1104–1110 (2014)

    Article  Google Scholar 

  28. 28.

    Chen, H.Y., Wei, Z.H., Kollar, M., Gao, F., Wang, Y.L., Szanyi, J., Peden, C.H.F.: A comparative study of N2O formation during the selective catalytic reduction of NOx with NH3 on zeolite supported Cu catalysts. J. Catal. 329, 490–498 (2015)

    Article  Google Scholar 

  29. 29.

    Janssens, T.V.W., Falsig, H., Lundegaard, L.F., Vennestrom, P.N.R., Rasmussen, S.B., Moses, P.G., Giordanino, F., Borfecchia, E., Lomachenko, K.A., Lamberti, C., Bordiga, S., Godiksen, A., Mossin, S., Beato, P.: A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia. ACS Catal. 5(5), 2832–2845 (2015)

    Article  Google Scholar 

  30. 30.

    McEwen, J.S., Anggara, T., Schneider, W.F., Kispersky, V.F., Miller, J.T., Delgass, W.N., Ribeiro, F.H.: Integrated operando X-ray absorption and DFT characterization of Cu-SSZ-13 exchange sites during the selective catalytic reduction of NOx with NH3. Catal. Today. 184(1), 129–144 (2012)

    Article  Google Scholar 

  31. 31.

    Bendrich, M., Scheuer, A., Hayes, R.E., Votsmeier, M.: Unified mechanistic model for standard SCR, fast SCR, and NO2 SCR over a copper chabazite catalyst. Appl. Catal. B Environ. 222, 76–87 (2018)

    Article  Google Scholar 

  32. 32.

    Gao, F., Walter, E.D., Karp, E.M., Luo, J.Y., Tonkyn, R.G., Kwak, J.H., Szanyi, J., Peden, C.H.F.: Structure-activity relationships in NH3-SCR over Cu-SSZ-13 as probed by reaction kinetics and EPR studies. J. Catal. 300, 20–29 (2013)

    Article  Google Scholar 

  33. 33.

    Kim, Y.J., Lee, J.K., Min, K.M., Hong, S.B., Nam, I.S., Cho, B.K.: Hydrothermal stability of CuSSZ13 for reducing NOx by NH3. J. Catal. 311, 447–457 (2014)

    Article  Google Scholar 

  34. 34.

    Xie, L.J., Liu, F.D., Shi, X.Y., Xiao, F.S., He, H.: Effects of post-treatment method and Na co-cation on the hydrothermal stability of Cu-SSZ-13 catalyst for the selective catalytic reduction of NOx with NH3. Appl. Catal. B Environ. 179, 206–212 (2015)

    Article  Google Scholar 

  35. 35.

    Luo, J.Y., Gao, F., Kamasamudram, K., Currier, N.W., Peden, C.H.F., Yezerets, A.: New insights into Cu/SSZ-13 SCR catalyst acidity. Part I: nature of acidic sites probed by NH3 titration. J. Catal. 348, 291–299 (2017)

    Article  Google Scholar 

  36. 36.

    Gao, F., Wang, Y.L., Kollar, M., Washton, N.M., Szanyi, J., Peden, C.H.F.: A comparative kinetics study between Cu/SSZ-13 and Fe/SSZ-13 SCR catalysts. Catal. Today. 258, 347–358 (2015)

    Article  Google Scholar 

  37. 37.

    Vannice, M.A.: Kinetics of Catalytic Reactions. Springer ScienceþBusiness Media, Inc., New York (2005)

    Google Scholar 

  38. 38.

    Gao, F., Walter, E.D., Kollar, M., Wang, Y.L., Szanyi, J., Peden, C.H.F.: Understanding ammonia selective catalytic reduction kinetics over Cu/SSZ-13 from motion of the Cu ions. J. Catal. 319, 1–14 (2014)

    Article  Google Scholar 

  39. 39.

    Paolucci, C., Verma, A.A., Bates, S.A., Kispersky, V.F., Miller, J.T., Gounder, R., Delgass, W.N., Ribeiro, F.H., Schneider, W.F.: Isolation of the copper redox steps in the standard selective catalytic reduction on Cu-SSZ-13. Angew. Chem. Int. Ed. 53(44), 11828–11833 (2014)

    Article  Google Scholar 

Download references


The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

Author information



Corresponding author

Correspondence to Feng Gao.

Ethics declarations

Conflict of interest

The authors declare that they have no competing interests.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Cui, Y., Gao, F. Cu Loading Dependence of Fast NH3-SCR on Cu/SSZ-13. Emiss. Control Sci. Technol. 5, 124–132 (2019).

Download citation


  • Ammonia SCR
  • Standard SCR
  • Fast SCR
  • Cu/SSZ-13
  • Reaction kinetics
  • Reaction mechanism