Skip to main content

Comparison of NOx Adsorption/Desorption Behaviors over Pd/CeO2 and Pd/SSZ-13 as Passive NOx Adsorbers for Cold Start Application

Emission Control Science and Technology volume 5, pages 172–182 (2019)Cite this article

Abstract

Passive NOx adsorber (PNA) is one of the promising technologies for reducing NOx emissions from vehicles during cold start periods. Precious metals supported on metal oxide and zeolite have been extensively investigated as PNA materials. Hence, it is worthwhile to compare two typical PNA materials, Pd/CeO2 and Pd/SSZ-13, so as to understand the differences between them. The NOx adsorption/desorption experiments were carried out under varying NO/NO2 ratios, and the result indicated that the NOx adsorption/desorption mechanisms on Pd/CeO2 and Pd/SSZ-13 are completely different. Specifically, NO and NO2 were competitively adsorbed on Pd/SSZ-13, while the NO adsorption on Pd/CeO2 was promoted by NO2. This difference is attributed to different adsorption sites: NOx is adsorbed on the ceria surface in Pd/CeO2, whereas it is adsorbed on atomic Pd2+ sites in Pd/SSZ-13, according to DRIFTS spectra in this study. In addition, the effect of sulfur poisoning was investigated as well. Pd/SSZ-13 showed moderate sulfur tolerance, while Pd/CeO2 completely lost its PNA ability after sulfur aging.

This is a preview of subscription content, access via your institution.

Access options

Buy single article

Instant access to the full article PDF.

USD 39.95

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

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

References

  1. Kim, C.H., Han, H.S.: Status of emission control science and technology in South Korea. Emiss. Control Sci. Technol. 4(1), 1–3 (2018)

    Article  Google Scholar 

  2. Vassallo, J.E.: Status of emission control science and technology in Argentina. Emiss. Control Sci. Technol. 4(2), 73–77 (2018)

    Article  Google Scholar 

  3. Wallington, T.J., Lambert, C.K., Ruona, W.C.: Diesel vehicles and sustainable mobility in the U.S. Energy Policy. 54, 47–53 (2013)

    Article  Google Scholar 

  4. Rexeis, M., Hausberger, S.: Trend of vehicle emission levels until 2020-prognosis based on current vehicle measurements and future emission legislation. Atmos. Environ. 43(31), 4689–4698 (2009)

    Article  Google Scholar 

  5. European Parliament and the Council of the European Union: Regulation (EC) No 715/2007 of the European Parliament and of the Council of 20 June 2007 on type approval of motor vehicles with respect to emissions from light passenger and commercial vehicles (Euro 5 and Euro 6) and on access to vehicle repair and maintenance information. Off. J. Eur. Union L Ser. 171, 1–16 (2007)

  6. Beatrice, C., Rispoli, N., Di Blasio, G., Konstandopoulos, A.G., Papaioannou, E., Imren, A.: Impact of emerging engine and after-treatment technologies for improved fuel efficiency and emission reduction for the future rail diesel engines. Emiss. Control Sci. Technol. 2(2), 99–112 (2016)

    Article  Google Scholar 

  7. Fino, D., Russo, N., Saracco, G., Specchia, V.: Catalytic removal of NOx and diesel soot over nanostructured spinel-type oxides. J. Catal. 242(1), 38–47 (2006)

    Article  Google Scholar 

  8. Li, J., Chang, H., Ma, L., Hao, J., 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. Yim, S.D., Kim, S.J., Baik, J.H., Nam, I.S., Mok, Y.S., Lee, J.-H., Cho, B.K., Oh, S.H.: Decomposition of urea into NH3 for the SCR process. Ind. Eng. Chem. Res. 43(16), 4856–4863 (2004)

    Article  Google Scholar 

  10. Neely, G.D., Sarlashkar, J.V., Mehta, D.: Diesel cold-start emission control research for 2015-2025 LEV III emissions. SAE Int. J. Engines. 6(2), 1009–1020 (2013)

    Article  Google Scholar 

  11. Cuelenaere, R., Ligterink, N.: Assessment of the strengths and weaknesses of the new real driving emissions (RDE) test procedure. TNO. 2016, R11227 (2016)

    Google Scholar 

  12. Gu, Y., Epling, W.S.: Passive NOx adsorber: an overview of catalyst performance and reaction chemistry. Appl. Catal., A. 570, 1–14 (2019)

    Article  Google Scholar 

  13. Lee, J., Theis, J.R., Kyriakidou, E.A.: Vehicle emissions trapping materials: successes, challenges, and the path forward. Appl. Catal., B. 243, 397–414 (2019)

    Article  Google Scholar 

  14. Cole, J.A.: System for reducing NOx from mobile source engine exhaust. U.S. Patent. 5, 656,244 (1997)

  15. Ryou, Y., Lee, J., Lee, H., Kim, C.H., Kim, D.H.: Low temperature NO adsorption over hydrothermally aged Pd/CeO2 for cold start application. Catal. Today. 307, 93–101 (2018)

    Article  Google Scholar 

  16. Ji, Y.Y., Bai, S.L., Crocker, M.: Al2O3-based passive NOx adsorbers for low temperature applications. Appl. Catal., B. 170, 283–292 (2015)

    Article  Google Scholar 

  17. Ji, Y., Xu, D., Bai, S., Graham, U., Crocker, M., Chen, B., Shi, C., Harris, D., Scapens, D., Darab, J.: Pt-and Pd-promoted CeO2–ZrO2 for passive NOx adsorber applications. Ind. Eng. Chem. Res. 56, 111–125 (2016)

    Article  Google Scholar 

  18. Ji, Y.Y., Xu, D.Y., Crocker, M., Theis, J.R., Lambert, C., Bueno-Lopez, A., Harris, D., Scapens, D.: Mn-based mixed oxides for low temperature NOx adsorber applications. Appl. Catal., A. 567, 90–101 (2018)

    Article  Google Scholar 

  19. Stakheev, A.Y., Mashkovsky, I.S., Bragina, G.O., Baeva, G.N., Telegina, N.S., Larsen, K.M., Kustov, A.L., Thogersen, J.R.: Mechanism of low-temperature NOx storage for reducing NOx cold start emission. Top. Catal. 59, 931–937 (2016)

    Article  Google Scholar 

  20. Theis, J.R.: An assessment of Pt and Pd model catalysts for low temperature NOx adsorption. Catal. Today. 267, 93–109 (2016)

    Article  Google Scholar 

  21. Trovarelli, A.: Catalytic properties of ceria and CeO2-containing materials. Catal. Rev. Sci. Eng. 38(4), 439–520 (1996)

    Article  Google Scholar 

  22. Yao, H.C., Yao, Y.F.Y.: Ceria in automotive exhaust catalysts: I. Oxygen storage. J. Catal. 86(2), 254–265 (1984)

    Article  Google Scholar 

  23. Sugiura, M.: Oxygen storage materials for automotive catalysts: ceria-zirconia solid solutions. Catal. Surv. Jpn. 7(1), 77–87 (2003)

    Article  Google Scholar 

  24. Zheng, Y., Kovarik, L., Engelhard, M.H., Wang, Y., Wang, Y., Gao, F., Szanyi, J.: Low-temperature Pd/zeolite passive NOx adsorbers: structure, performance, and adsorption chemistry. J. Phys. Chem. C. 121(29), 15793–15803 (2017)

    Article  Google Scholar 

  25. Porta, A., Pellegrinelli, T., Castoldi, L., Matarrese, R., Morandi, S., Dzwigaj, S., Lietti, L.: Low temperature NOx adsorption study on Pd-promoted zeolites. Top. Catal. 61(18-19), 2021–2034 (2018)

    Article  Google Scholar 

  26. Lee, J., Ryou, Y., Cho, S.J., Lee, H., Kim, C.H., Kim, D.H.: Investigation of the active sites and optimum Pd/Al of Pd/ZSM–5 passive NO adsorbers for the cold-start application: evidence of isolated-Pd species obtained after a high-temperature thermal treatment. Appl. Catal., B. 226, 71–82 (2018)

    Article  Google Scholar 

  27. Ryou, Y., Lee, J., Lee, H., Kim, C.H., Kim, D.H.: Effect of various activation conditions on the low temperature NO adsorption performance of Pd/SSZ-13 passive NOx adsorber. Catal. Today. 320, 175–180 (2019)

    Article  Google Scholar 

  28. Mihai, O., Trandafilović, L., Wentworth, T., Torres, F.F., Olsson, L.: The effect of Si/Al ratio for Pd/BEA and Pd/SSZ-13 used as passive NOx adsorbers. Top. Catal. 61(18-19), 2007–2020 (2018)

    Article  Google Scholar 

  29. Chen, H.Y., Collier, J.E., Liu, D.X., Mantarosie, L., Duran-Martin, D., Novak, V., Rajaram, R.R., Thompsett, D.: Low temperature NO storage of zeolite supported Pd for low temperature diesel engine emission control. Catal. Lett. 146(9), 1706–1711 (2016)

    Article  Google Scholar 

  30. Ye, Q., Wang, L.F., Yang, R.T.: Activity, propene poisoning resistance and hydrothermal stability of copper exchanged chabazite-like zeolite catalysts for SCR of NO with ammonia in comparison to Cu/ZSM-5. Appl. Catal., A. 427, 24–34 (2012)

    Article  Google Scholar 

  31. Fickel, D.W., D’Addio, E., Lauterbach, J.A., Lobo, R.F.: The ammonia selective catalytic reduction activity of copper-exchanged small-pore zeolites. Appl. Catal., B. 102(3-4), 441–448 (2011)

    Article  Google Scholar 

  32. Ryou, Y., Lee, J., Cho, S.J., Lee, H., Kim, C.H., Kim, D.H.: Activation of Pd/SSZ-13 catalyst by hydrothermal aging treatment in passive NO adsorption performance at low temperature for cold start application. Appl. Catal., B. 212, 140–149 (2017)

    Article  Google Scholar 

  33. Khivantsev, K., Jaegers, N.R., Kovarik, L., Hanson, J.C., Tao, F.F., Tang, Y., Zhang, X., Koleva, I.Z., Aleksandrov, H.A., Vayssilov, G.N., Wang, Y., Gao, F., Szanyi, J.: Achieving atomic dispersion of highly loaded transition metals in small-pore zeolite SSZ-13: high-capacity and high-efficiency low-temperature CO and passive NOx adsorbers. Angew. Chem. Int. Ed. 57(51), 16672–16677 (2018)

    Article  Google Scholar 

  34. Adelman, B.J., Sachtler, W.M.H.: The effect of zeolitic protons on NOx reduction over Pd/ZSM-5 catalysts. Appl. Catal., B. 14(1-2), 1–11 (1997)

    Article  Google Scholar 

  35. Kaspar, J., Fornasiero, P., Graziani, M.: Use of CeO2-based oxides in the three-way catalysis. Catal. Today. 50(2), 285–298 (1999)

    Article  Google Scholar 

  36. Zhou, Y., Lawrence, N.J., Wu, T.-S., Liu, J., Kent, P., Soo, Y.-L., Cheung, C.L.: Pd/CeO2−xNanorod catalysts for CO oxidation: insights into the origin of their regenerative ability at room temperature. ChemCatChem. 6(10), 2937–2946 (2014)

    Article  Google Scholar 

  37. Luo, M.F., Hou, Z.Y., Yuan, X.X., Zheng, X.M.: Characterization study of CeO2 supported Pd catalyst for low-temperature carbon monoxide oxidation. Catal. Lett. 50(3/4), 205–209 (1998)

    Article  Google Scholar 

  38. Jeong, H., Bae, J., Han, J.W., Lee, H.: Promoting effects of hydrothermal treatment on the activity and durability of Pd/CeO2 catalysts for CO oxidation. ACS Catal. 7(10), 7097–7105 (2017)

    Article  Google Scholar 

  39. Stolz, C., Sauvage, A., Massiani, P., Kramer, R.: Solid-state exchange of palladium in zeolite NaX. Appl. Catal., A. 167(1), 113–121 (1998)

    Article  Google Scholar 

  40. Setiabudi, A., Makkee, M., Moulijn, J.A.: The role of NO2 and O2 in the accelerated combustion of soot in diesel exhaust gases. Appl. Catal., B. 50(3), 185–194 (2004)

    Article  Google Scholar 

  41. Twigg, M.V.: Progress and future challenges in controlling automotive exhaust gas emissions. Appl. Catal., B. 70(1-4), 2–15 (2007)

    Article  Google Scholar 

  42. 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 

  43. Theis, J.R., Lambert, C.K.: Mechanistic assessment of low temperature NOx adsorbers for cold start NOx control on diesel engines. Catal. Today. 320, 181–195 (2019)

    Article  Google Scholar 

  44. Filtschew, A., Hess, C.: Unravelling the mechanism of NO and NO 2 storage in ceria: the role of defects and Ce-O surface sites. Appl. Catal., B. 237, 1066–1081 (2018)

    Article  Google Scholar 

  45. Azambre, B., Zenboury, L., Koch, A., Weber, J.V.: Adsorption and desorption of NOx on commercial ceria-zirconia (CexZr1−xO2) mixed oxides: a combined TGA, TPD-MS, and DRIFTS study. J. Phys. Chem. C. 113(30), 13287–13299 (2009)

    Article  Google Scholar 

  46. Atribak, I., Azambre, B., Lopez, A.B., Garcia-Garcia, A.: Effect of NOx adsorption/desorption over ceria-zirconia catalysts on the catalytic combustion of model soot. Appl. Catal., B. 92(1-2), 126–137 (2009)

    Article  Google Scholar 

  47. Azambre, B., Atribak, I., Bueno-López, A., García-García, A.: Probing the surface of ceria−zirconia catalysts using NOx adsorption/desorption: a first step toward the investigation of crystallite heterogeneity. J. Phys. Chem. C. 114(31), 13300–13312 (2010)

    Article  Google Scholar 

  48. Rico-Pérez, V., Bueno-López, A., Kim, D.J., Ji, Y., Crocker, M.: Pt/Ce x Pr 1−x O 2 ( x = 1 or 0.9) NO x storage–reduction (NSR) catalysts. Appl. Catal., B. 163, 313–322 (2015)

    Article  Google Scholar 

  49. Hadjiivanov, K.I.: Identification of neutral and charged NxOySurface species by IR spectroscopy. Catal. Rev. Sci. Eng. 42(1-2), 71–144 (2000)

    Article  Google Scholar 

  50. Philipp, S., Drochner, A., Kunert, J., Vogel, H., Theis, J., Lox, E.S.: Investigation of NO adsorption and NO/O2Co-adsorption on NOx-storage-components by DRIFT-spectroscopy. Top. Catal. 30/31, 235–238 (2004)

    Article  Google Scholar 

  51. Chakarova, K., Ivanova, E., Hadjiivanov, K., Klissurski, D., Knozinger, H.: Co-ordination chemistry of palladium cations in Pd-H-ZSM-5 as revealed by FTIR spectra of adsorbed and CO-adsorbed probe molecules (CO and NO). PCCP. 6(13), 3702–3709 (2004)

    Article  Google Scholar 

  52. Lonyi, F., Solt, H.E., Valyon, J., Decolatti, H., Gutierrez, L.B., Miro, E.: An operando DRIFTS study of the active sites and the active intermediates of the NO-SCR reaction by methane over In,H- and In,Pd,H-zeolite catalysts. Appl. Catal., B. 100(1-2), 133–142 (2010)

    Article  Google Scholar 

  53. Shimizu, K.-i., Okada, F., Nakamura, Y., Satsuma, A., Hattori, T.: Mechanism of NO reduction by CH4 in the presence of O2 over Pd–H–mordenite. J. Catal. 195(1), 151–160 (2000)

    Article  Google Scholar 

  54. Karjalainen, H., Lassi, U., Rahkamaa-Tolonen, K., Kröger, V., Keiski, R.L.: Thermodynamic equilibrium calculations of sulfur poisoning in Ce–O–S and La–O–S systems. Catal. Today. 100(3-4), 291–295 (2005)

    Article  Google Scholar 

  55. Kolli, T., Kanerva, T., Lappalainen, P., Huuhtanen, M., Vippola, M., Kinnunen, T., Kallinen, K., Lepistö, T., Lahtinen, J., Keiski, R.L.: The effect of SO2 and H2O on the activity of Pd/CeO2 and Pd/Zr–CeO2 diesel oxidation catalysts. Top. Catal. 52(13-20), 2025–2028 (2009)

    Article  Google Scholar 

  56. Boaro, M., de Leitenburg, C., Dolcetti, G., Trovarelli, A., Graziani, M.: Oxygen storage behavior of ceria–zirconia-based catalysts in the presence of SO2. Top. Catal. 16(17), 299–306 (2001)

    Article  Google Scholar 

  57. Luo, T., Gorte, R.J.: Characterization of SO2-poisoned ceria-zirconia mixed oxides. Appl. Catal., B. 53(2), 77–85 (2004)

    Article  Google Scholar 

Download references

Funding

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (MSIP) (NRF2016R1A5A1009592).

Author information

Author notes

  1. Yongwoo Kim and Sungha Hwang contributed equally to this work.

Authors and Affiliations

  1. School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul, 08826, Republic of Korea

    Yongwoo Kim, Sungha Hwang, Jaeha Lee, YoungSeok Ryou & Do Heui Kim

  2. Hyundai-Kia Motors R&D Center, Hwaseong, 445-706, Republic of Korea

    Hyokyoung Lee & Chang Hwan Kim

Authors
  1. Yongwoo Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sungha Hwang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jaeha Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. YoungSeok Ryou
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Hyokyoung Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Chang Hwan Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Do Heui Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Do Heui Kim.

Ethics declarations

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

Kim, Y., Hwang, S., Lee, J. et al. Comparison of NOx Adsorption/Desorption Behaviors over Pd/CeO2 and Pd/SSZ-13 as Passive NOx Adsorbers for Cold Start Application. Emiss. Control Sci. Technol. 5, 172–182 (2019). https://doi.org/10.1007/s40825-019-00119-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40825-019-00119-0

Keywords

  • Passive NOx adsorber (PNA)
  • Pd/CeO2
  • Pd/SSZ-13
  • Cold start
  • Low temperature NO adsorption
  • NO adsorption site