Topics in Catalysis

, Volume 62, Issue 1–4, pp 63–71 | Cite as

Cu SAPO 34 One Pot Hydrothermal Preparation Method for Particular Copper Configuration

  • Guillaume Pétaud
  • Sonia GilEmail author
  • Anne Giroir FendlerEmail author
Original Paper


Two different routes of synthesis were followed in order to compare the surface properties of two Cu-SAPO-34 catalysts. The direct copper incorporation during the hydrothermal synthesis, compared to the conventional impregnation method, allowed us to study the impact of active centers location on the catalytic activity during both the selective catalytic reduction of NOx by NH3 and the NH3 oxidation. X-ray diffraction, ex-situ diffuse reflectance infrared spectroscopy and X-ray photoelectron spectroscopy analysis were performed to know the copper location and its state for each catalysts. A unique location of the copper oxide at the surface of the synthesized catalyst was observed when the hydrothermal process was used. For similar Cu contents in the catalysts, different catalytic behaviors during the selective catalytic reduction of NOx by NH3 and during the NH3 oxidation were observed as a consequence of the specific activity of the copper clusters. Indeed, some cations in exchanged position were detected when the impregnation method was used, allowing high SCR performance at low temperature. On the other hand, the small copper clusters at the surface and the exchanged cations exhibited a certain NH3 oxidation at low temperature, hindering DeNOx activity. Catalyst with mainly large copper clusters and no appreciable occurrence of exchanged Cu2+ present in a range of temperatures, limited NH3 oxidation and high SCR performance.





The authors gratefully acknowledge the French government, the University Claude Bernard Lyon 1 and the National Scientific Research Center for funding. The authors would like to thank the scientific services of IRCELYON for catalyst characterizations and for stimulating discussions.


  1. 1.
    Niu C, Shi X, Liu F et al (2016) High hydrothermal stability of Cu-SAPO-34 catalysts for the NH3-SCR of NOx. Chem Eng J 294:254–263. CrossRefGoogle Scholar
  2. 2.
    Mees FDP, Martens LRM, Janssen MJG et al (2003) Improvement of the hydrothermal stability of SAPO-34. Chem Commun 9:44–45. CrossRefGoogle Scholar
  3. 3.
    Beasley MM, Bartelink EJ, Taylor L, Miller RM (2014) Comparison of transmission FTIR, ATR, and DRIFT spectra: implications for assessment of bone bioapatite diagenesis. J Archaeol Sci 46:16–22. CrossRefGoogle Scholar
  4. 4.
    Arstad B, Lind A, Cavka JH et al (2016) Structural changes in SAPO-34 due to hydrothermal treatment. A NMR, XRD, and DRIFTS study. Microporous Mesoporous Mater 225:421–431. CrossRefGoogle Scholar
  5. 5.
    Wang J, Zhao H, Haller G, Li Y (2017) Recent advances in the selective catalytic reduction of NOx with NH3 on Cu-Chabazite catalysts. Appl Catal B Environ 202:346–354. CrossRefGoogle Scholar
  6. 6.
    Fickel DW, D’Addio E, Lauterbach JA, Lobo RF (2011) The ammonia selective catalytic reduction activity of copper-exchanged small-pore zeolites. Appl Catal B Environ 102:441–448. CrossRefGoogle Scholar
  7. 7.
    Yahiro H, Iwamoto M (2001) Copper ion-exchanged zeolite catalysts in deNOx reaction. Appl Catal A Gen 222:163–181. CrossRefGoogle Scholar
  8. 8.
    Beale AM, Gao F, Lezcano-Gonzalez I et al (2015) Recent advances in automotive catalysis for NOx emission control by small-pore microporous materials. Chem Soc Rev 44:7371–7405. CrossRefGoogle Scholar
  9. 9.
    Korhonen ST, Fickel DW, Lobo RF et al (2011) Isolated Cu2+ ions: active sites for selective catalytic reduction of NO. Chem Commun 47:800–802. CrossRefGoogle Scholar
  10. 10.
    Yang G, Ran J, Du X et al (2018) Different copper species as active sites for NH3-SCR reaction over Cu-SAPO-34 catalyst and reaction pathways: a periodic DFT study. Microporous Mesoporous Mater 266:223–231. CrossRefGoogle Scholar
  11. 11.
    Gao F, Walter ED, Washton NM et al (2013) Synthesis and evaluation of Cu-SAPO-34 catalysts for ammonia selective catalytic reduction. 1. Aqueous solution ion exchange. ACS Catal 3:2083–2093. CrossRefGoogle Scholar
  12. 12.
    Godiksen A, Stappen FN, Nicolai P et al (2014) Coordination environment of copper in Cu-CHA zeolite investigated by EPR. J Phys Chem 118:23126–23138. Google Scholar
  13. 13.
    Schiavoni M, Campisi S, Gervasini A (2017) Effect of Cu deposition method on silico aluminophosphate catalysts in NH3-SCR and NH3-SCO reactions. Appl Catal A Gen 543:162–172. CrossRefGoogle Scholar
  14. 14.
    Shwan S, Skoglundh M, Lundegaard LF et al (2015) Solid-state ion-exchange of copper into zeolites facilitated by ammonia at low temperature. ACS Catal 5:16–19. CrossRefGoogle Scholar
  15. 15.
    Xie L, Liu F, Ren L et al (2014) Excellent performance of one-pot synthesized Cu-SSZ-13 catalyst for the selective catalytic reduction of NOx with NH3. Environ Sci Technol 48:566–572. CrossRefGoogle Scholar
  16. 16.
    Fan S, Xue J, Yu T et al (2013) The effect of synthesis methods on Cu species and active sites over Cu/SAPO-34 for NH3-SCR reaction. Catal Sci Technol 3:2357–2364. CrossRefGoogle Scholar
  17. 17.
    Liu J, Yu F, Liu J et al (2016) Synthesis and kinetics investigation of meso-microporous Cu-SAPO-34 catalysts for the selective catalytic reduction of NO with ammonia. J Environ Sci (China) 48:45–58. CrossRefGoogle Scholar
  18. 18.
    Woo J, Leistner K, Bernin D et al (2018) Effect of various structure directing agents (SDAs) on low-temperature deactivation of Cu/SAPO-34 during NH3-SCR reaction. Catal Sci Technol 8:3090–3106. CrossRefGoogle Scholar
  19. 19.
    Zhang R, Helling K, McEwen JS (2016) Ab initio X-ray absorption modeling of Cu-SAPO-34: characterization of Cu exchange sites under different conditions. Catal Today 267:28–40. CrossRefGoogle Scholar
  20. 20.
    Deka U, Lezcano-Gonzalez I, Warrender SJ et al (2013) Changing active sites in Cu-CHA catalysts: DeNOx selectivity as a function of the preparation method. Microporous Mesoporous Mater 166:144–152. CrossRefGoogle Scholar
  21. 21.
    Clemens AKS, Shishkin A, Carlsson P-A et al (2015) Reaction-driven ion exchange of copper into zeolite SSZ-13. ACS Catal 5:6209–6218. CrossRefGoogle Scholar
  22. 22.
    Wang L, Gaudet JR, Li W, Weng D (2013) Migration of Cu species in Cu/SAPO-34 during hydrothermal aging. J Catal 306:68–77. CrossRefGoogle Scholar
  23. 23.
    Wang D, Zhang L, Li J et al (2014) NH3-SCR over Cu/SAPO-34: zeolite acidity and Cu structure changes as a function of Cu loading. Catal Today 231:64–74. CrossRefGoogle Scholar
  24. 24.
    Wang J, Yu T, Wang X et al (2012) The influence of silicon on the catalytic properties of Cu/SAPO-34 for NOx reduction by ammonia-SCR. Appl Catal B Environ 127:137–147. CrossRefGoogle Scholar
  25. 25.
    Lin C, Cao Y, Feng X et al (2017) Effect of Si islands on low-temperature hydrothermal stability of Cu/SAPO-34 catalyst for NH3-SCR. J Taiwan Inst Chem Eng 81:288–294. CrossRefGoogle Scholar
  26. 26.
    Fjermestad T, Svelle S, Swang O (2013) Mechanistic comparison of the dealumination in SSZ-13 and the desilication in SAPO-34. J Phys Chem C 117:13442–13451. CrossRefGoogle Scholar
  27. 27.
    Su W, Li Z, Peng Y, Li J (2015) Correlation of the changes in the framework and active Cu sites for typical Cu/CHA zeolites (SSZ-13 and SAPO-34) during hydrothermal aging. Phys Chem Chem Phys 17:29142–29149. CrossRefGoogle Scholar
  28. 28.
    Xu M, Wang J, Yu T et al (2018) New insight into Cu/SAPO-34 preparation procedure: Impact of NH4-SAPO-34 on the structure and Cu distribution in Cu-SAPO-34 NH3-SCR catalysts. Appl Catal B Environ 220:161–170. CrossRefGoogle Scholar
  29. 29.
    Chen Z, Fan C, Pang L et al (2018) Direct synthesis of submicron Cu-SAPO-34 as highly efficient and robust catalyst for selective catalytic reduction of NO by NH3. Appl Surf Sci 448:671–680. CrossRefGoogle Scholar
  30. 30.
    Wang L, Li W, Qi G, Weng D (2012) Location and nature of Cu species in Cu/SAPO-34 for selective catalytic reduction of NO with NH3. J Catal 289:21–29. CrossRefGoogle Scholar
  31. 31.
    Wang L, Li W, Schmieg SJ, Weng D (2015) Role of Brønsted acidity in NH3 selective catalytic reduction reaction on Cu/SAPO-34 catalysts. J Catal 324:98–106. CrossRefGoogle Scholar
  32. 32.
    Shi L, Yu T, Wang XQ et al (2013) Properties and roles of adsorbed NH3 and NOX over Cu/SAPO-34 zeolite catalyst in NH3-SCR process. Acta Phys 29:1550–1557. Google Scholar
  33. 33.
    Sjövall H, Fridell E, Blint RJ, Olsson L (2007) Identification of adsorbed species on Cu-ZSM-5 under NH3 SCR conditions. Top Catal 42:113–117. CrossRefGoogle Scholar
  34. 34.
    Dang TTH, Zubowa H-L, Bentrup U et al (2009) Microwave-assisted synthesis and characterization of Cu-containing AlPO4-5 and SAPO-5. Microporous Mesoporous Mater 123:209–220. CrossRefGoogle Scholar
  35. 35.
    Fanning PE, Vannice MA (2002) A DRIFTS study of Cu–ZSM-5 prior to and during its use for N2O decomposition. J Catal 207:166–182. CrossRefGoogle Scholar
  36. 36.
    Onida B, Gabelica Z, Lourenço J, Garrone E (1996) Spectroscopic characterization of hydroxyl groups in SAPO-40. 1. Study of the template-free samples and their interaction with ammonia. J Phys Chem 100:11072–11079. CrossRefGoogle Scholar
  37. 37.
    Bing L, Wang G, Yi K et al (2018) One-pot synthesis of Cu-SAPO-34 catalyst using waste mother liquid and its application in the selective catalytic reduction of NO with NH3. Catal Today 316:37–42. CrossRefGoogle Scholar

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Authors and Affiliations

  1. 1.Univ Lyon, Université Lyon 1, CNRS, UMR 5256, IRCELYONVilleurbanneFrance

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