Environmental Science and Pollution Research

, Volume 25, Issue 35, pp 35276–35286 | Cite as

Novel ceramic paper structures for diesel exhaust purification

  • Sabrina A. Leonardi
  • Fernando E. Tuler
  • Eric M. Gaigneaux
  • Damien P. DebeckerEmail author
  • Eduardo E. Miró
  • Viviana G. MiltEmail author
Research Article


The catalytic combustion of diesel soot is addressed with flexible and structured “paper catalysts”. Two different series of catalysts were prepared either by drip impregnation or by a spray method to deposit a mixture of Co, Ba, and K or a mixture of Co and Ce onto SiO2-Al2O3 ceramic paper matrixes. In every case, CeO2 nanoparticles were added to bind the ceramic fibers. SEM images showed that the impregnation method generated catalytic particles concentrated as large chunks (> 10 μm), mainly at ceramic fiber crossings, whereas the spray method produced smaller catalytic particles (< 1 μm) well distributed throughout the ceramic paper. Besides, Co-Ba-K particles appeared better dispersed on the surface of ceramic fibers than Co-Ce due to the presence of K. Additionally, FTIR spectra showed the formation of O22− and O2 species associated with CeO2 (binder) on the samples containing potassium which gave the Co-Ba-K-ceramic paper good catalytic properties, thus making the Co-Ba-K drop impregnated the best catalyst both considering activity and stability. Successive temperature programmed oxidation (TPO) runs up to 700 °C caused the formation of cobalt silicates in the catalytic ceramic paper prepared by the spray method, as indicated by TPR. The formation of these species was probably favored by the smaller size of cobalt particulates and their higher dispersion in the catalysts prepared by the spray method. This provoked the partial loss of the redox properties of Co3O4. TPR experiments also indicated the formation of BaCoO3 in Ba-containing ceramic paper, which could help in maintaining the catalyst activity after several TPO runs through the capacity of this mixed perovskite-type oxide to trap and release NOx.


Cobalt, barium, potassium Cerium Catalytic ceramic paper Structured catalysts Diesel soot combustion Spray deposition 


Funding information

This study received financial support from ANPCyT, CONICET, SECTEI Santa Fe and UNL (Argentina) and Program for Scientific and Technological Cooperation between the Ministry of Science, Technology and Productive Innovation of Argentina (MINCyT), and the Fonds de la Recherche Scientifique (FNRS) of the French Community of Belgium, BE/12/02.

Supplementary material

11356_2018_3439_MOESM1_ESM.pptx (511 kb)
Fig 1S Distribution of components throughout ceramic paper prepared either by drip impregnation or by the spray technique after stability runs (EDS mapping). (PPTX 511 kb)
11356_2018_3439_MOESM2_ESM.pptx (140 kb)
Fig 2S Convolution of TPR profiles from the corresponding reduction peaks of Co-Ce catalytic ceramic paper. (PPTX 139 kb)
11356_2018_3439_MOESM3_ESM.pptx (182 kb)
Fig 3S Convolution of TPR profiles from the corresponding reduction peaks of Co-Ba-K catalytic ceramic paper. (PPTX 181 kb)


  1. Aneggi E, Wiater D, de Leitenburg C, Llorca J, Trovarelli A (2014) Shape-dependent activity of ceria in soot combustion. ACS Catal 4:172–181CrossRefGoogle Scholar
  2. Colbeau-Justin F, Boissière C, Chaumonnot A, Bonduelle A, Sanchez C (2014) Aerosol route to highly efficient (Co) Mo/SiO2 mesoporous catalysts. Adv Funct Mater 24:233–239CrossRefGoogle Scholar
  3. Debecker DP, Stoyanova M, Colbeau-Justin F, Rodemerck U, Boissière C, Gaigneaux EM, Sanchez C (2012) One-pot aerosol route to MoO3-SiO2-Al2O3 catalysts with ordered super microporosity and high olefin metathesis activity. Angew Chem Int Ed 15:2129–2131CrossRefGoogle Scholar
  4. Debecker DP, Stoyanova M, Rodemerck U, Colbeau-Justin F, Boissère C, Chaumonnot A, Bonduelle A, Sanchez C (2014) Aerosol route to nanostructured WO3-SiO2-Al2O3 metathesis catalysts: toward higher propene yield. Appl Catal A Gen 470:458–466CrossRefGoogle Scholar
  5. Debecker DP, Le Bras S, Boissiere C, Chaumonnot A, Sanchez C (2018) Aerosol processing: a wind of innovation in the field of advanced heterogeneous catalysts. Chem Soc Rev 47:4112–4155CrossRefGoogle Scholar
  6. Ernst B, Libs S, Chaumette P, Kiennemann A (1999) Preparation and characterization of Fischer–Tropsch active Co/SiO2 catalysts. Appl Catal A Gen 186:145–168CrossRefGoogle Scholar
  7. Gómez LE, Múnera JF, Sollier BM, Miró EE, Boix AV (2016) Raman in situ characterization of the species present in Co/CeO2 and Co/ZrO2 catalysts during the COPrOx reaction. Int J Hydrog Energy 41:4993–5002CrossRefGoogle Scholar
  8. Gross MS, Ulla MA, Querini CA (2009) Catalytic oxidation of diesel soot: new characterization and kinetic evidence related to the reaction mechanism on K/CeO2 catalyst. Appl Catal A Gen 360:81–88CrossRefGoogle Scholar
  9. Gross MS, Ulla MA, Querini CA (2012) Diesel particulate matter combustion with CeO2 as catalyst. Part I: system characterization and reaction mechanism. J Mol Catal A Chem 352:86–94CrossRefGoogle Scholar
  10. Han J-K, Jia L-T, Hou B, Li D-B, Liu Y, Liu Y-C (2015) Catalytic properties of CoAl2O4/Al2O3 supported cobalt catalysts for Fischer-Tropsch synthesis. J Fuel Chem Technol 43(7):846–851CrossRefGoogle Scholar
  11. Ishihara H, Koga H, Kitaoka T, Wariishi H, Tomoda A, Suzuki R (2010) Structured catalyst for catalytic NOx removal from combustion exhaust gas. Chem Eng Sci 65:208–213CrossRefGoogle Scholar
  12. Jin Q, Shen Y, Zhu S, Liu Q, Li X, Yan W (2016) Effect of praseodymium additive on CeO2(ZrO2)/TiO2 for selective catalytic reduction of NO by NH3. J Rare Earths 34(11):1111–1120CrossRefGoogle Scholar
  13. Kaplin IY, Lokteva ES, Golubina EV, Maslakov KI, Chernyak SA, Lunin VV (2017) Promoting effect of potassium and calcium additives to cerium–zirconium oxide catalysts for the complete oxidation of carbon monoxide. Kinet Catal 58:585–592CrossRefGoogle Scholar
  14. Khalaji AD, Nikookar M, Fejfarova K, Dusek M (2014) Synthesis of new cobalt(III) Schiff base complex: a new precursor for preparation Co3O4 nanoparticles via solid-state thermal decomposition. J Mol Struct 1071:6–10CrossRefGoogle Scholar
  15. Koga H, Fukahori S, Kitaoka T, Tomoda A, Suzuki R, Wariishi H (2006) Autothermal reforming of methanol using paper-like Cu/ZnO catalyst composites prepared by a papermaking technique. Appl Catal A Gen 309:263–269CrossRefGoogle Scholar
  16. Koga H, Fukahori S, Kitaoka T, Nakamura M, Wariishi H (2008a) Structured catalyst with porous fiber-network microstructure for autothermal hydrogen production. Chem Eng J 139:408–415CrossRefGoogle Scholar
  17. Koga H, Kitaoka T, Wariishi H (2008b) In situ synthesis of Cu nanocatalysts on ZnO whiskers embedded in a microstructured paper composite for autothermal hydrogen production. Chem Commun 43:5616–5618CrossRefGoogle Scholar
  18. Koga H, Umemura Y, Ishihara H, Kitaoka T, Tomoda A, Suzuki R, Wariishi H (2009) Structured fiber composites impregnated with platinum nanoparticles synthesized on a carbon fiber matrix for catalytic reduction of nitrogen oxides. Appl Catal B Environ 90:699–704CrossRefGoogle Scholar
  19. Liotta LF, Di Carlo G, Pantaleo G, Venezia AM, Deganello G (2006) Co3O4/CeO2 composite oxides for methane emissions abatement: relationship between Co3O4–CeO2 interaction and catalytic activity. Appl Catal B Environ 66:217–227CrossRefGoogle Scholar
  20. Liu S, Wu X, Weng D, Li M, Ran R (2015) Roles of acid sites on Pt/H-ZSM5 catalyst in catalytic oxidation of diesel soot. ACS Catal 5:909–919CrossRefGoogle Scholar
  21. Luo JY, Meng M, Li X, Li XG, Zha YQ, Hu TD, Xie YN, Zhang J (2008) Mesoporous Co3O4–CeO2 and Pd/Co3O4–CeO2 catalysts: synthesis, characterization and mechanistic study of their catalytic properties for low-temperature CO oxidation. J Catal 254:310–324CrossRefGoogle Scholar
  22. Maksasithorn S, Praserthdam P, Suriye K, Debecker DP (2015) Preparation of super-microporous WO3–SiO2 olefin metathesis catalysts by the aerosol-assisted sol–gel process. Microporous Mesoporous Mater 213:125–133CrossRefGoogle Scholar
  23. Marrero-Jerez J, Larrondo S, Rodriguez-Castellón E, Núñez P (2014) TPR, XRD and XPS characterisation of ceria-based materials synthesized by freeze-drying precursor method. Ceram Int 40:6807–6814CrossRefGoogle Scholar
  24. Milt VG, Ulla MA, Miro EE (2005) NOx trapping and soot combustion on BaCoO3-y perovskite: LRS and FTIR characterization. Appl Catal B Environ 57:13–21CrossRefGoogle Scholar
  25. Mosconi S, Lick ID, Carrascull A, Ponzi MI, Ponzi EN (2007) Catalytic combustion of diesel soot: deactivation by SO2 of copper and potassium nitrate catalysts supported on alumina. Catal Commun 8:1755–1758CrossRefGoogle Scholar
  26. Pega S, Boissiere C, Grosso D, Azais T, Chaumonnot A, Sanchez C (2009) Direct aerosol synthesis of large-pore amorphous mesostructured aluminosilicates with superior acid-catalytic properties. Angew Chem Int Ed 48:2784–2787CrossRefGoogle Scholar
  27. Piumetti M, Bensaid S, Russo N, Fino D (2016) Investigations into nanostructured ceria–zirconia catalysts for soot combustion. Appl Catal B Environ 180:271–282CrossRefGoogle Scholar
  28. Potoczna-Petru D, Kepinski L (2001) Reduction study of Co3O4 model catalyst by electron microscopy. Catal Lett 73:41–46CrossRefGoogle Scholar
  29. Quiles-Díaz S, Giménez-Mañogil J, García-García A (2015) Catalytic performance of CuO/Ce0.8Zr0.2O2 loaded onto SiC-DPF in NOx-assisted combustion of diesel soot. RSC Adv 5(170):18–17029Google Scholar
  30. Reichelt E, Heddrich MP, Jahn M, Michaelis A (2014) Fiber based structured materials for catalytic applications. Appl Catal A Gen 476:78–79CrossRefGoogle Scholar
  31. Santos GA, Santos CMB, da Silva SW, Urquieta-González EA, Confessori PP, Sartoratto (2012) Sol–gel synthesis of silica–cobalt composites by employing Co3O4 colloidal dispersions. Colloids Surf A Physicochem Eng Asp 395:217–224CrossRefGoogle Scholar
  32. Tarka A, Zyberta M, Kindler Z, Szmurlo J, Mierzwa B, Raróg-Pilecka W (2017) Effect of precipitating agent on the properties of cobalt catalysts promoted with cerium and barium for NH3 synthesis obtained by co-precipitation. Appl Catal A Gen 532:19–25CrossRefGoogle Scholar
  33. Tuler FE, Banús ED, Zanuttini MA, Miró EE, Milt VG (2014) Ceramic papers as flexible structures for the development of novel diesel soot combustion catalysts. Chem Eng J 246:287–298CrossRefGoogle Scholar
  34. Tuler FE, Portela R, Ávila P, Banús ED, Miró EE, Milt VG (2015a) Structured catalysts based on sepiolite with tailored porosity to remove diesel soot. Appl Catal A Gen 498:41–53CrossRefGoogle Scholar
  35. Tuler FE, Gaigneaux EM, Miró EE, Milt VG, Debecker DP (2015b) Catalytic ceramic papers for diesel soot oxidation: a spray method for enhanced performance. Catal Commun 72:116–120CrossRefGoogle Scholar
  36. Xu W, Cai J, Zhou J, Ou Y, Long W, You Z, Lou Y (2016) Highly effective direct decomposition of nitric oxide by microwave catalysis over BaMeO3 (Me= Mn, Co, Fe) mixed oxides at low temperature under excess oxygen. ChemCatChem 8:417–425CrossRefGoogle Scholar
  37. Yang X-L, Zhang W-Q, Xia C-G, Xiong X-M, Mu X-Y, Hu B (2010) Low temperature ruthenium catalyst for ammonia synthesis supported on BaCeO3 nanocrystals. Catal Commun 11:867–870CrossRefGoogle Scholar
  38. Zhang H, Li S, Lin Q, Feng X, Chen Y, Wang J (2018) Study on hydrothermal deactivation of Pt/MnOx-CeO2 for NOx-assisted soot oxidation: redox property, surface nitrates, and oxygen vacancies. Environ Sci Pollut Res 25:16061–16070. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Instituto de Investigaciones en Catálisis y Petroquímica, INCAPE, CONICET, Facultad de Ingeniería QuímicaUniversidad Nacional del Litoral3000 Santa FeArgentina
  2. 2.Institute of Condensed Matter and Nanosciences (IMCN)UCLouvainLouvain-La-NeuveBelgium

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