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Interaction of Pd and Rh with ZrCeYLaO2 support during thermal aging and its effect on the CO oxidation activity

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A commercial ceria–zirconia composition modified with yttrium and lanthanum oxides was studied as a support for palladium- and rhodium-containing three-way catalysts. The most attention was paid to an interaction of the supported active metals with the support under high-temperature conditions. It was found that both the metals affect noticeably the porous structure of the support and the loading of metal plays a role in this process. Moreover, oxygen storage capacity of the oxide composition was also influenced by the supported metals. Hydrothermal aging of the metal-loaded samples has decreased the oxygen storage capacity values in more than 2 times. The thermal stability of the monometallic samples was compared with bimetallic Pd–Rh catalysts prepared using a “single-source precursor” approach. The experiments were performed under prompt thermal aging conditions. It was found that monometallic Pd-only samples and bimetallic Pd–Rh samples exhibit excellent stability, while monometallic Rh-only catalysts undergo deactivation being heated up to 800 °C due to diffusion of rhodium into the bulk of the support. All the samples were additionally characterized by a diffuse reflectance UV–vis spectroscopy and a testing reaction of ethane hydrogenolysis. According to the results obtained, the character of the metal-support interaction was found to be strongly affected by the catalyst’s composition. Application of the bimetallic Pd–Rh particles of alloyed type was shown to result in the preferable location of the active components on the support’s surface, thus facilitating high activity and stability of the catalyst.

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  1. 1.

    Heck RM, Farrauto RJ, Gulati ST (2009) Catalytic air pollution control.

  2. 2.

    Taylor KC (1993) Nitric oxide catalysis in automotive exhaust systems. Catal Rev 35(4):457–481.

  3. 3.

    Matsumoto S (1997) Recent advances in automobile exhaust catalyst. Catal Surv Jpn 1(1):111–117.

  4. 4.

    Gandhi HS, Graham GW, McCabe RW (2003) Automotive exhaust catalysis. J Catal 216(1–2):433–442.

  5. 5.

    Matsumoto S (2007) Advances in automobile exhaust catalyst. Stud Surf Sci Catal 172:27–34

  6. 6.

    Bera P, Hegde MS (2010) Recent advances in auto exhaust catalysis. J Indian Inst Sci 90(2):299–325

  7. 7.

    Vedyagin AA, Stoyanovskii VO, Kenzhin RM, Plyusnin PE, Shubin YV, Volodin AM (2019) New trends in automotive exhaust gas purification materials: improvement of the support against stability of the active components. Mater Sci Forum 950:185–189.

  8. 8.

    González-Velasco JR, Botas JA, Ferret R, Pilar González-Marcos M, Marc J-L, Gutiérrez-Ortiz MA (2000) Thermal aging of Pd/Pt/Rh automotive catalysts under a cycled oxidizing–reducing environment. Catal Today 59(3–4):395–402.

  9. 9.

    Rashidzadeh M, Peyrovi MH, Mondegarian R (2000) Alumina-based supports for automotive palladium catalysts. Reac Kinet Catal Lett 69(1):115–122.

  10. 10.

    Shelef M, Graham GW (2006) Why rhodium in automotive three-way catalysts? Catal Rev 36(3):433–457.

  11. 11.

    Zheng Q, Farrauto R, Deeba M (2015) Part II: oxidative thermal aging of Pd/Al2O3 and Pd/CexOy-ZrO2 in automotive three way catalysts: the effects of fuel shutoff and attempted fuel rich regeneration. Catalysts 5(4):1797–1814.

  12. 12.

    Zheng Q, Farrauto R, Deeba M, Valsamakis I (2015) Part I: a comparative thermal aging study on the regenerability of Rh/Al2O3 and Rh/CexOy-ZrO2 as model catalysts for automotive three way catalysts. Catalysts 5(4):1770–1796.

  13. 13.

    Vedyagin AA, Volodin AM, Kenzhin RM, Stoyanovskii VO, Rogov VA, Medvedev DA, Mishakov IV (2017) Characterization and study on the thermal aging behavior of palladium–alumina catalysts. J Therm Anal Calorim 130(3):1865–1874.

  14. 14.

    Lin S, Yang L, Yang X, Zhou R (2014) Redox behavior of active PdOx species on (Ce, Zr)xO2–Al2O3 mixed oxides and its influence on the three-way catalytic performance. Chem Eng J 247:42–49.

  15. 15.

    Lan L, Chen S, Cao Y, Gong M, Chen Y (2015) New insights into the structure of a CeO2–ZrO2–Al2O3 composite and its influence on the performance of the supported Pd-only three-way catalyst. Catal Sci Technol 5(9):4488–4500.

  16. 16.

    Zhang Z, Fan Y, Xin Y, Li Q, Li R, Anderson JA, Zhang Z (2015) Improvement of air/fuel ratio operating window and hydrothermal stability for Pd-only three-way catalysts through a Pd–Ce2Zr2O8 superstructure interaction. Environ Sci Technol 49(13):7989–7995.

  17. 17.

    Hegde MS, Bera P (2015) Noble metal ion substituted CeO2 catalysts: electronic interaction between noble metal ions and CeO2 lattice. Catal Today 253:40–50.

  18. 18.

    Zhou Z, Ouyang J, Yang H, Tang A (2016) Three-way catalytic performances of Pd loaded halloysite-Ce0.5Zr0.5O2 hybrid materials. Appl Clay Sci 121–122:63–70.

  19. 19.

    Zhou Y, Deng J, Lan L, Wang J, Yuan S, Gong M, Chen Y (2017) Remarkably promoted low-temperature reducibility and thermal stability of CeO2–ZrO2–La2O3–Nd2O3 by a urea-assisted low-temperature (90 °C) hydrothermal procedure. J Mater Sci 52(10):5894–5907.

  20. 20.

    Lan L, Li H, Chen S, Chen Y (2017) Preparation of CeO2–ZrO2–Al2O3 composite with layered structure for improved Pd-only three-way catalyst. J Mater Sci 52(16):9615–9629.

  21. 21.

    Sasmaz E, Wang C, Lance MJ, Lauterbach J (2017) In situ spectroscopic investigation of a Pd local structure over Pd/CeO2 and Pd/MnOx–CeO2 during CO oxidation. J Mater Chem A 5(25):12998–13008.

  22. 22.

    Lan L, Chen S, Li H, Wang J, Li D, Chen Y (2018) Optimized synthesis of highly thermal stable CeO2–ZrO2/Al2O3 composite for improved Pd-only three-way catalyst. Mater Des 147:191–199.

  23. 23.

    Kenzhin RM, Alikin EA, Denisov SP, Vedyagin AA (2019) Study on thermal stability of ceria-supported rhodium catalysts. Mater Sci Forum 950:190–194.

  24. 24.

    Spezzati G, Benavidez AD, DeLaRiva AT, Su YQ, Hofmann JP, Asahina S, Olivier EJ, Neethling JH, Miller JT, Datye AK, Hensen EJM (2019) CO oxidation by Pd supported on CeO2(100) and CeO2(111) facets. Appl Catal B 243:36–46.

  25. 25.

    Markaryan GL, Ikryannikova LN, Muravieva GP, Turakulova AO, Kostyuk BG, Lunina EV, Lunin VV, Zhilinskaya E, Aboukais A (1999) Red–ox properties and phase composition of CeO2–ZrO2 and Y2O3–CeO2–ZrO2 solid solutions. Colloid Surf A 151(3):435–447.

  26. 26.

    Fernández-Garcı́a M, Martı́nez-Arias A, Iglesias-Juez A, Belver C, Hungrı́a AB, Conesa JC, Soria J, (2000) Structural characteristics and redox behavior of CeO2–ZrO2/Al2O3 supports. J Catalysis 194(2):385–392.

  27. 27.

    Suhonen S, Valden M, Hietikko M, Laitinen R, Savimäki A, Härkönen M (2001) Effect of Ce–Zr mixed oxides on the chemical state of Rh in alumina supported automotive exhaust catalysts studied by XPS and XRD. Appl Catal A 218(1–2):151–160.

  28. 28.

    He H, Dai HX, Wong KW, Au CT (2003) RE0.6Zr0.4−xYxO2 (RE = Ce, Pr; x = 0, 0.05) solid solutions: an investigation on defective structure, oxygen mobility, oxygen storage capacity, and redox properties. Appl Catal A 251 (1):61–74

  29. 29.

    Wu X, Yang B, Weng D (2004) Effect of Ce–Zr mixed oxides on the thermal stability of transition aluminas at elevated temperature. J Alloy Compd 376(1–2):241–245.

  30. 30.

    Guo J, Wu D, Zhang L, Gong M, Zhao M, Chen Y (2008) Preparation of nanometric CeO2–ZrO2–Nd2O3 solid solution and its catalytic performances. J Alloy Compd 460(1–2):485–490.

  31. 31.

    Cai L, Wang K-C, Zhao M, Gong M-C, Chen Y-Q (2009) Application of ultrasonic vibrations in the preparation of Ce-Zr-La/Al2O3 and supported Pd three-way-catalyst. Acta Phys-Chim Sin 25(05):859–863.

  32. 32.

    Papavasiliou A, Tsetsekou A, Matsouka V, Konsolakis M, Yentekakis IV (2010) An investigation of the role of Zr and La dopants into Ce1−x−yZrxLayOδ enriched γ-Al2O3 TWC washcoats. Appl Catal A 382(1):73–84.

  33. 33.

    Reddy BM, Thrimurthulu G, Katta L (2010) Design of efficient CexM1−xO2−δ (M = Zr, Hf, Tb and Pr) nanosized model solid solutions for CO oxidation. Catal Lett 141(4):572–581.

  34. 34.

    Wang G, You R, Meng M (2013) An optimized highly active and thermo-stable oxidation catalyst Pd/Ce–Zr–Y/Al2O3 calcined at superhigh temperature and used for C3H8 total oxidation. Fuel 103:799–804.

  35. 35.

    Ouyang J, Zhao Z, Zhang Y, Yang H (2017) Textual properties and catalytic performances of halloysite hybrid CeO2–ZrO2 nanoparticles. J Colloid Interface Sci 505:430–436.

  36. 36.

    Van CZ, Dettling JC (1987) Rhodium-support interactions in automotive exhaust catalysts. In: Catalysis and automotive pollution control, proceedings of the first international symposium (CAPOC I). Studies in Surface Science and Catalysis. pp 369–386.

  37. 37.

    Ciuparu D (2000) Pd–Ce interactions and adsorption properties of palladium: CO and NO TPD studies over Pd–Ce/Al2O3 catalysts. Appl Catal B 26(4):241–255.

  38. 38.

    Boronin AI, Slavinskaya EM, Danilova IG, Gulyaev RV, Amosov YI, Kuznetsov PA, Polukhina IA, Koscheev SV, Zaikovskii VI, Noskov AS (2009) Investigation of palladium interaction with cerium oxide and its state in catalysts for low-temperature CO oxidation. Catal Today 144(3–4):201–211.

  39. 39.

    Luo J-Y, Meng M, Xian H, Tu Y-B, Li X-G, Ding T (2009) The nanomorphology-controlled palladium-support interaction and the catalytic performance of Pd/CeO2 catalysts. Catal Lett 133(3–4):328–333.

  40. 40.

    Cao Y, Ran R, Wu X, Zhao B, Wan J, Weng D (2013) Comparative study of ageing condition effects on Pd/Ce0.5Zr0.5O2 and Pd/Al2O3 catalysts: catalytic activity, palladium nanoparticle structure and Pd-support interaction. Appl Catal A 457:52–61.

  41. 41.

    Zheng T, He J, Zhao Y, Xia W, He J (2014) Precious metal-support interaction in automotive exhaust catalysts. J Rare Earth 32(2):97–107.

  42. 42.

    Lin S, Yang L, Yang X, Zhou R (2014) Redox properties and metal-support interaction of Pd/Ce0.67Zr0.33O2–Al2O3 catalyst for CO, HC and NOx elimination. Appl Surf Sci 305:642–649.

  43. 43.

    Vedyagin AA, Volodin AM, Kenzhin RM, Stoyanovskii VO, Shubin YV, Plyusnin PE, Mishakov IV (2017) Effect of metal-metal and metal-support interaction on activity and stability of Pd–Rh/alumina in CO oxidation. Catal Today 293–294:73–81.

  44. 44.

    Stoyanovskii VO, Vedyagin AA, Aleshina GI, Volodin AM, Noskov AS (2009) Characterization of Rh/Al2O3 catalysts after calcination at high temperatures under oxidizing conditions by luminescence spectroscopy and catalytic hydrogenolysis. Appl Catal B 90(1–2):141–146.

  45. 45.

    Stoyanovskii VO, Vedyagin AA, Volodin AM, Kenzhin RM, Shubin YV, Plyusnin PE, Mishakov IV (2017) Peculiarity of Rh bulk diffusion in La-doped alumina and its impact on CO oxidation over Rh/Al2O3. Catal Commun 97:18–22.

  46. 46.

    Stoyanovskii VO, Vedyagin AA, Volodin AM, Kenzhin RM, Bespalko YN, Plyusnin PE, Shubin YV (2018) Optical spectroscopy of Rh3+ ions in the lanthanum-aluminum oxide systems. J Lumin 204:609–617.

  47. 47.

    Alikin EA, Vedyagin AA (2016) High Temperature interaction of rhodium with oxygen storage component in three-way catalysts. Top Catal 59(10–12):1033–1038.

  48. 48.

    Vedyagin AA, Gavrilov MS, Volodin AM, Stoyanovskii VO, Slavinskaya EM, Mishakov IV, Shubin YV (2013) Catalytic purification of exhaust gases over Pd–Rh alloy catalysts. Top Catal 56(11):1008–1014.

  49. 49.

    Vedyagin AA, Volodin AM, Stoyanovskii VO, Kenzhin RM, Slavinskaya EM, Mishakov IV, Plyusnin PE, Shubin YV (2014) Stabilization of active sites in alloyed Pd–Rh catalysts on γ-Al2O3 support. Catal Today 238:80–86.

  50. 50.

    Vedyagin AA, Plyusnin PE, Rybinskaya AA, Shubin YV, Mishakov IV, Korenev SV (2018) Synthesis and study of Pd–Rh alloy nanoparticles and alumina-supported low-content Pd–Rh catalysts for CO oxidation. Mater Res Bull 102:196–202.

  51. 51.

    Vedyagin AA, Stoyanovskii VO, Kenzhin RM, Slavinskaya EM, Plyusnin PE, Shubin YV (2019) Purification of gasoline exhaust gases using bimetallic Pd–Rh/δ-Al2O3 catalysts. Reac Kinet Mech Cat 127(1):137–148.

  52. 52.

    Vedyagin AA, Stoyanovskii VO, Plyusnin PE, Shubin YV, Slavinskaya EM, Mishakov IV (2018) Effect of metal ratio in alumina-supported Pd–Rh nanoalloys on its performance in three way catalysis. J Alloy Compd 749:155–162.

  53. 53.

    Vedyagin AA, Shubin YV, Kenzhin RM, Plyusnin PE, Stoyanovskii VO, Volodin AM (2018) Prospect of using nanoalloys of partly miscible rhodium and palladium in three-way catalysis. Top Catal 62(1–4):305–314.

  54. 54.

    Vedyagin AA, Kenzhin RM, Tashlanov MY, Stoyanovskii VO, Plyusnin PE, Shubin YV, Mishakov IV, Kalinkin AV, Smirnov MY, Bukhtiyarov VI (2019) Synthesis and study of bimetallic Pd–Rh system supported on zirconia-doped alumina as a component of three-way catalysts. Emiss Control Sci Technol. 5(4):363–377.

  55. 55.

    Porsin AV, Alikin EA, Bukhtiyarov VI (2016) A low-temperature method for measuring oxygen storage capacity of ceria-containing oxides. Catal Sci Technol 6(15):5891–5898.

  56. 56.

    Vedyagin AA, Volodin AM, Stoyanovskii VO, Mishakov IV, Medvedev DA, Noskov AS (2011) Characterization of active sites of Pd/Al2O3 model catalysts with low Pd content by luminescence, EPR and ethane hydrogenolysis. Appl Catal B 103(3–4):397–403.

  57. 57.

    Stoyanovskii VO, Vedyagin AA, Volodin AM, Kenzhin RM, Slavinskaya EM, Plyusnin PE, Shubin YV (2018) Optical spectroscopy methods in the estimation of the thermal stability of bimetallic Pd–Rh/Al2O3 three-way catalysts. Top Catal 62(1–4):296–304.

  58. 58.

    Alikin EA, Denisov SP, Vedyagin AA (2019) Partial regeneration of model TWC after high-temperature aging on engine bench. Top Catal 62(1–4):324–330.

  59. 59.

    Birgersson H, Boutonnet M, Jaras S, Eriksson L (2004) Deactivation and regeneration of spent three-way automotive exhaust gas catalysts (TWC). Top Catal 30–1(1–4):433–437.

  60. 60.

    Kang SB, Han SJ, Nam SB, Nam I-S, Cho BK, Kim CH, Oh SH (2013) Effect of aging atmosphere on thermal sintering of modern commercial TWCs. Top Catal 56(1–8):298–305.

  61. 61.

    Vedyagin AA, Volodin AM, Kenzhin RM, Stoyanovskii VO, Rogov VA, Kriventsov VV, Mishakov IV (2018) The role of chemisorbed water in formation and stabilization of active sites on Pd/Alumina oxidation catalysts. Catal Today 307:102–110.

  62. 62.

    Vedyagin A, Volodin A, Kenzhin R, Chesnokov V, Mishakov I (2016) CO oxidation over Pd/ZrO2 catalysts: role of support′s donor sites. Molecules 21(10):1289.

  63. 63.

    Yates D, Sinfelt JH (1967) The catalytic activity of rhodium in relation to its state of dispersion. J Catal 8(4):348–358.

  64. 64.

    Sinfelt J (1972) Kinetics of ethane hydrogenolysis. J Catal 27(3):468–471.

  65. 65.

    Sinfelt JH (1973) Specificity in catalytic hydrogenolysis by metals. In: DD Eley, H Pines, PB Weisz (eds.). Advances in catalysis. Reinhold, New York, pp 91–119.

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The study was financially supported by the Ministry of Education and Science of the Russian Federation within the framework of subsidizing agreement of October 23, 2017 (No. 14.581.21.0028, unique agreement identifier RFMEFI58117X0028) of the Federal Target Program “Research and development in priority directions of the progress of the scientific and technological complex of Russia for the years 2014–2020. The authors are grateful to A. Gladky for the assistance in TPR experiments. Characterization of the samples was performed using the equipment of the Center of Collective Use “National Center of Catalysts Research”.

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Correspondence to Aleksey A. Vedyagin.

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Vedyagin, A.A., Alikin, E.A., Kenzhin, R.M. et al. Interaction of Pd and Rh with ZrCeYLaO2 support during thermal aging and its effect on the CO oxidation activity. Reac Kinet Mech Cat 129, 117–133 (2020).

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  • Palladium
  • Rhodium
  • Ceria–zirconia support
  • Metal-support interaction
  • Thermal stability
  • Bimetallic Pd–Rh alloys