Synthesis of CuCe co-modified mesoporous ZSM-5 zeolite for the selective catalytic reduction of NO by NH3

  • Yuanyuan Ma
  • Yang Liu
  • Zhifang Li
  • Cui Geng
  • Xuefeng BaiEmail author
  • Dianxue CaoEmail author
Research Article


Mesoporous ZSM-5 zeolite (MZ) was used as support for Cu and Ce species, and the effects of structure and physical-chemical properties on selective catalytic reduction of NO with NH3 (NH3-SCR) were investigated. The characterization and experimental results show that the high activity of the Cu-Ce/MZ catalyst could be due to its high surface area, more and uniformly distributed active sites, and abundant oxidative species. Compared with the conventional ZSM-5 and SBA-15, the Cu-Ce/MZ possesses large amount of mesopores, and more accessible active sites, which are beneficial to accelerate the diffusion and improve the internal mass transfer in the denitration process. The Cu-Ce/MZ catalyst shows higher activity than Cu-Ce/ZSM-5 and Cu-Ce/SBA-15 at 200 °C.


Mesoporous ZSM-5 Selective catalytic reduction Surface area CuCe co-modified 


Funding information

This work has been supported by the National Natural Science Foundation of China (51708309), Heilongjiang Province (QC2017065), and the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province (UNPYSCT-2018106).

Supplementary material

11356_2019_7547_MOESM1_ESM.docx (78 kb)
ESM 1 (DOCX 78 kb)
11356_2019_7547_MOESM2_ESM.docx (155 kb)
ESM 2 (DOCX 154 kb)


  1. Beale AM, Gao F, Lezcano-Gonzalez I, Peden CHF, Szanyi J (2015) Recent advances in automotive catalysis for NOx emission control by small-pore microporous materials. Chem Soc Rev 44:7371–7405CrossRefGoogle Scholar
  2. Boningari T, Pappas DK, Ettireddy PR, Kotrba A, Smirniotis PG (2015) Influence of SiO2 on M/TiO2 (M = Cu, Mn, and Ce) formulations for low-temperature selective catalytic reduction of NOx with NH3: surface properties and key components in relation to the activity of NOx reduction. Ind Eng Chem Res 54:2261–2273CrossRefGoogle Scholar
  3. Brandenberger S, Kröcher O, Wokaun A, Tissler A, Althoff R (2009) The role of Brønsted acidity in the selective catalytic reduction of NO with ammonia over Fe-ZSM-5. J Catal 268:297–306CrossRefGoogle Scholar
  4. Busca G, Lietti L, Ramis G, Berti F (1998) Chemical and mechanistic aspects of the selective catalytic reduction of NOx by ammonia over oxide catalysts: a review. Appl Catal B Environ 18:1–36CrossRefGoogle Scholar
  5. Chal R, Gérardin C, Bulut M, van Donk S (2011) Overview and industrial assessment of synthesis strategies towards zeolites with mesopores. ChemCatChem 3:67–81CrossRefGoogle Scholar
  6. Dusselier M, Davis ME (2018) Small-pore zeolites: synthesis and catalysis. Chem Rev 118:5265–5329CrossRefGoogle Scholar
  7. Gao F, Walter E, Washton N, Szanyi J, Peden C (2013) Synthesis and evaluation of Cu-SAPO-34 catalysts for ammonia selective catalytic reduction. 1. Aqueous solution ion exchange. ACS Catal 3:2083–2093CrossRefGoogle Scholar
  8. Góra-Marek K, Brylewska K, Tarach KA, Rutkowska M, Jabłońska M, Choi M, Chmielarz L (2015) IR studies of Fe modified ZSM-5 zeolites of diverse mesopore topologies in the terms of their catalytic performance in NH3-SCR and NH3-SCO processes. Appl Catal B Environ 179:589–598CrossRefGoogle Scholar
  9. Heck RM (1999) Catalytic abatement of nitrogen oxides–stationary applications. Catal Today 53:519–523CrossRefGoogle Scholar
  10. Holm MS, Taarning E, Egeblad K, Christensen CH (2011) Catalysis with hierarchical zeolites. Catal Today 168:3–16CrossRefGoogle Scholar
  11. Iwamoto M, Furukawa H, Mine Y, Uemura F, S-i M, Kagawa S (1986) Copper(II) ion-exchanged ZSM-5 zeolites as highly active catalysts for direct and continuous decomposition of nitrogen monoxide. J Chem Soc Chem Commun 16:1272–1273CrossRefGoogle Scholar
  12. Iwasaki M, Yamazaki K, Banno K, Shinjoh H (2008) Characterization of Fe/ZSM-5 DeNOx catalysts prepared by different methods: relationships between active Fe sites and NH3-SCR performance. J Catal 260:205–216CrossRefGoogle Scholar
  13. Kustov AL, Hansen TW, Kustova M, Christensen CH (2007) Selective catalytic reduction of NO by ammonia using mesoporous Fe-containing HZSM-5 and HZSM-12 zeolite catalysts: an option for automotive applications. Appl Catal B-Environ 76:311–319CrossRefGoogle Scholar
  14. Li J, Wang G, Gao C, Lv X, Wang Z, Liu H (2013) Deoxy-liquefaction of laminaria japonica to high-quality liquid oil over metal modified ZSM-5 catalysts. Energy Fuel 27:5207–5214CrossRefGoogle Scholar
  15. Liu J, Yu F, Cui L, Zhao Z, Wei Y, Sun Q (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) 48:45–58CrossRefGoogle Scholar
  16. Ma J, Weng D, Wu X, Si Z, Wu Z (2013) Highly dispersed iron species created on alkali-treated zeolite for ammonia SCR. Prog in Nat Sci-Mater 23:493–500CrossRefGoogle Scholar
  17. Pang L, Fan C, Shao L, Song K, Yi J, Cai X, Wang J, Kang M, Li T (2014) The Ce doping Cu/ZSM-5 as a new superior catalyst to remove NO from diesel engine exhaust. Chem Eng J 253:394–401CrossRefGoogle Scholar
  18. Peng C, Liu Z, Horimoto A, Anand C, Yamada H, Ohara K, Sukenaga S, Ando M, Shibata H, Takewaki T, Mukti RR, Okubo T, Wakihara T (2018) Preparation of nanosized SSZ-13 zeolite with enhanced hydrothermal stability by a two-stage synthetic method. Micropor Mesopor Mat 255:192–199CrossRefGoogle Scholar
  19. Rutkowska M, Díaz U, Palomares AE, Chmielarz L (2015) Cu and Fe modified derivatives of 2D MWW-type zeolites (MCM-22, ITQ-2 and MCM-36) as new catalysts for DeNOx process. Appl Catal B Environ 168-169:531–539CrossRefGoogle Scholar
  20. Rutkowska M et al (2017) Catalytic performance of commercial Cu-ZSM-5 zeolite modified by desilication in NH3-SCR and NH3-SCO processes. Microporous Mesoporous Mater 246:193–206CrossRefGoogle Scholar
  21. Serrano DP, Escola JM, Pizarro P (2013) Synthesis strategies in the search for hierarchical zeolites. Chem Soc Rev 42:4004–4035CrossRefGoogle Scholar
  22. Shan J-H, Liu X-Q, Sun L-B, Cui R (2008) Cu−Ce bimetal ion-exchanged Y zeolites for selective adsorption of thiophenic sulfur. Energy Fuel 22:3955–3959CrossRefGoogle Scholar
  23. Shi A, Wang X, Yu T, Shen M (2011) The effect of zirconia additive on the activity and structure stability of V2O5/WO3-TiO2 ammonia SCR catalysts. Appl Catal B Environ 106:359–369CrossRefGoogle Scholar
  24. Song H, Chang Y, Song H (2015) Deep adsorptive desulfurization over Cu, Ce bimetal ion-exchanged Y-typed molecule sieve. Adsorption 22:139–150CrossRefGoogle Scholar
  25. Song L, Chao J, Fang Y, He H, Li J, Qiu W, Zhang G (2016) Promotion of ceria for decomposition of ammonia bisulfate over V2O5-MoO3/TiO2 catalyst for selective catalytic reduction. Chem Eng J 303:275–281CrossRefGoogle Scholar
  26. Takata T, Tsunoji N, Takamitsu Y, Sadakane M, Sano T (2016) Nanosized CHA zeolites with high thermal and hydrothermal stability derived from the hydrothermal conversion of FAU zeolite. Microporous Mesoporous Mater 225:524–533CrossRefGoogle Scholar
  27. Vennestrøm PNR, Grill M, Kustova M, Egeblad K, Lundegaard LF, Joensen F, Christensen CH, Beato P (2011) Hierarchical ZSM-5 prepared by guanidinium base treatment: understanding microstructural characteristics and impact on MTG and NH3-SCR catalytic reactions. Catal Today 168:71–79CrossRefGoogle Scholar
  28. Wang D, Zhang L, Li J, Kamasamudram K, Epling WS (2014) NH3-SCR over Cu/SAPO-34 – zeolite acidity and Cu structure changes as a function of Cu loading. Catal Today 231:64–74CrossRefGoogle Scholar
  29. Wang T, Liu H, Zhang X, Guo Y, Zhang Y, Wang Y, Sun B (2017) A plasma-assisted catalytic system for NO removal over CuCe/ZSM-5 catalysts at ambient temperature. Fuel Process Technol 158:199–205CrossRefGoogle Scholar
  30. Worch D, Suprun W, Gläser R (2011) Supported transition metal-oxide catalysts for HC-SCR DeNOx with propene. Catal Today 176:309–313CrossRefGoogle Scholar
  31. Wu S, Huang J, Wu T, Song K, Wang H, Xing L, Xu H, Xu L, Guan J, Kan Q (2006) Synthesis, characterization, and catalytic performance of mesoporous Al-SBA-15 for -butylation of phenol. Chin J Catal 27:9–14CrossRefGoogle Scholar
  32. Xie Z, Zhou X, Wu H, Chen L, Zhao H, Liu Y, Pan L, Chen H (2016) One-pot hydrothermal synthesis of CuBi co-doped mesoporous zeolite Beta for the removal of NOx by selective catalytic reduction with ammonia. Sci Rep 6:30132CrossRefGoogle Scholar
  33. Xu C, Liu J, Zhao Z, Yu F, Cheng K, Wei Y, Duan A, Jiang G (2015) NH3-SCR denitration catalyst performance over vanadium–titanium with the addition of Ce and Sb. J Environ Sci 31:74–80CrossRefGoogle Scholar
  34. Yan ZF, Li Z, He K, Zhao JS, Lou XR, Zhang JS, Huang W (2016) Hierarchical Fe-ZSM-5 with nano-single-unit-cell for removal of nitrogen oxides. Energ Source Part A 38:315–321CrossRefGoogle Scholar
  35. Yue Y, Liu H, Yuan P, Yu C, Bao X (2015) One-pot synthesis of hierarchical FeZSM-5 zeolites from natural aluminosilicates for selective catalytic reduction of NO by NH3. Sci Rep 5:9270CrossRefGoogle Scholar
  36. Zhang R, Liu N, Lei Z, Chen B (2016) Selective transformation of various nitrogen-containing exhaust gases toward N2 over zeolite catalysts. Chem Rev 116:3658–3721CrossRefGoogle Scholar
  37. Zhu L, Qu H, Zhang L, Zhou Q (2016) Direct synthesis, characterization and catalytic performance of Al–Fe-SBA-15 materials in selective catalytic reduction of NO with NH3. Catal Commun 73:118–122CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2020

Authors and Affiliations

  1. 1.Institute of Petrochemistry, Heilongjiang Academy of SciencesHarbinChina
  2. 2.College of Chemistry and Chemical EngineeringQiqihar UniversityQiqiharChina
  3. 3.College of Materials Science and EngineeringQiqihar UniversityQiqiharChina
  4. 4.College of Material Science and Chemical EngineeringHarbin Engineering UniversityHarbinChina

Personalised recommendations