Journal of Materials Science

, Volume 55, Issue 1, pp 283–297 | Cite as

Enhanced catalytic performance of cobalt and iron co-doped ceria catalysts for soot combustion

  • Yibo Gao
  • Shichang Teng
  • Zhongpeng WangEmail author
  • Baoqin Wang
  • Wei LiuEmail author
  • Wenxu Liu
  • Liguo Wang
Energy materials


A series of promising Ce–Co–Fe catalysts were successfully synthesized using a cetyl-trimethylammonium-bromide-assisted co-precipitation method and investigated for diesel soot combustion. The surface morphological and structural properties were systematically examined using various techniques: X-ray diffraction, scanning electron microscope, N2 adsorption–desorption, Raman spectroscopy, temperature-programmed reduction and in situ diffuse reflection infrared Fourier transform spectroscopy. The catalyst–soot combustion activities were tested in O2 and NO + O2 using a temperature-programmed technique. Nanometer crystalline solid solutions were formed with high surface areas when the Fe and Co cations were co-doped in the ceria lattice. Transition metals doping played a key role in increasing oxygen vacancies and promoting the redox performance of Ce–Co–Fe catalysts. Co–Fe co-doping accelerated the oxidation of soot under both “tight” and “loose” contact conditions. Among all the ceria-based catalysts, Ce80Co15Fe5 showed superior activity with T10 = 256 °C and high selectivity with \( S_{{{\text{CO}}_{ 2} }} \, = \,100\% \) under tight a contact mode. The observed high catalytic activity following co-doping was proved to have occurred because of various reasons such as improved redox properties, increased oxygen vacancies and high surface area. The presence of NO in O2 also promoted soot oxidation, which follows the NO2-assisted mechanism. Moreover, the in situ DRIFTS performed under an isothermal condition in NO + O2 confirmed the strong adsorption capacity for NOx species on the doped ceria catalyst.



This work was financially supported by the National Natural Science Foundation of China (No. 21777055), Shandong Provincial Natural Science Foundation (ZR2017BB004), Shandong Provincial Key Research and Development Plan (2017GGX202004, 2019GSF109116) and Shandong Provincial Major Science and Technology Innovation Project (2017CXGC1004). Many thanks to Mr. Junwei Ma for his contribution to the DLS analysis in the early preparation of the paper.

Compliance with ethical standards

Conflict of interest

The authors declare no conflict of interest.


  1. 1.
    Dai F, Meng M, Zha Y, Li Z, Hu T, Xie Y, Zhang J (2012) Performance of Ce substituted hydrotalcite-derived mixed oxide catalysts Co2.5Mg0.5Al1−x%Cex%O used for soot combustion and simultaneous NOx-soot removal. Fuel Process Technol 104:43–49Google Scholar
  2. 2.
    Cortés-Reyes M, Herrera C, Larrubia M, Alemany L (2016) Intrinsic reactivity analysis of soot removal in LNT-catalysts. Appl Catal B Environ 193:110–120Google Scholar
  3. 3.
    Christensen J, Grunwaldt J, Jensen A (2017) Effect of NO2 and water on the catalytic oxidation of soot. Appl Catal B Environ 205:182–188Google Scholar
  4. 4.
    Cao C, Xing L, Yang Y, Tian Y, Ding T, Zhang J, Hu T, Zheng L, Li X (2017) Diesel soot elimination over potassium-promoted Co3O4 nanowires monolithic catalysts under gravitation contact mode. Appl Catal B Environ 218:32–45Google Scholar
  5. 5.
    Wasalathanthri N, SantaMaria T, Kriz D, Dissanayake S, Kuo C, Biswas S, Suib S (2017) Mesoporous manganese oxides for NO2 assisted catalytic soot oxidation. Appl Catal B Environ 201:543–551Google Scholar
  6. 6.
    Andana T, Piumetti M, Bensaid S, Veyre L, Thieuleux C, Russo N, Fino D, Quadrelli E, Pirone R (2017) Ceria-supported small Pt and Pt3Sn nanoparticles for NOx-assisted soot oxidation. Appl Catal B Environ 209:295–310Google Scholar
  7. 7.
    Piumetti M, Bensaid S, Russo N, Fino D (2015) Nanostructured ceria-based catalysts for soot combustion: investigations on the surface sensitivity. Appl Catal B Environ 165:742–751Google Scholar
  8. 8.
    Shang Z, Sun M, Chang S, Che X, Cao X, Wang L, Guo Y, Zhan W, Guo Y, Lu G (2017) Activity and stability of Co3O4-based catalysts for soot oxidation: the enhanced effect of Bi2O3 on activation and transfer of oxygen. Appl Catal B Environ 209:33–44Google Scholar
  9. 9.
    Wei Y, Liu J, Zhao Z, Chen Y, Xu C, Duan A, Jiang G, He H (2011) Highly active catalysts of gold nanoparticles supported on three-dimensionally ordered macroporous LaFeO3 for soot oxidation. Angew Chem Int Edit 50:2326–2329Google Scholar
  10. 10.
    Zhai G, Wang J, Chen Z, An W, Men Y (2018) Boosting soot combustion efficiency of Co3O4 nanocrystals via tailoring crystal facets. Chem Eng J 337:488–498Google Scholar
  11. 11.
    Cheng L, Men Y, Wang J, Wang H, An W, Wang Y, Duan Z, Liu J (2017) Crystal facet-dependent reactivity of α-Mn2O3 microcrystalline catalyst for soot combustion. Appl Catal B Environ 204:374–384Google Scholar
  12. 12.
    Lee C, Jeon Y, Hata S, Park J, Akiyoshi R, Saito H, Teraoka Y, Shul Y, Einaga H (2016) Three-dimensional arrangements of perovskite-type oxide nano-fiber webs for effective soot oxidation. Appl Catal B Environ 191:157–164Google Scholar
  13. 13.
    Wang J, Cheng L, An W, Xu J, Men Y (2016) Boosting soot combustion efficiencies over CuO–CeO2 catalysts with a 3DOM structure. Catal Sci Technol 6:7342–7350Google Scholar
  14. 14.
    Rashwan W, Fathy N, Elkhouly S (2018) A novel catalyst of ceria-nanorods loaded on carbon xerogel for catalytic wet oxidation of methyl green dye. J Taiwan Inst of Chem E 88:234–242Google Scholar
  15. 15.
    Akah A (2017) Application of rare earths in fluid catalytic cracking: a review. J Rare Earth 35:941–956Google Scholar
  16. 16.
    Ren G, Pei G, Zhang J, Li W (2019) Activity promotion of anti-sintering AuMgGa2O4 using ceria in the water gas shift reaction and catalytic combustion reactions. Chin J Catal 40:600–608Google Scholar
  17. 17.
    Zhai G, Wang J, Chen Z, Yang S, Men Y (2019) Highly enhanced soot oxidation activity over 3DOM Co3O4–CeO2 catalysts by synergistic promoting effect. J Hazard Mater 363:214–226Google Scholar
  18. 18.
    Katta L, Sudarsanam P, Thrimurthulu G, Reddy B (2010) Doped nanosized ceria solid solutions for low temperature soot oxidation: zirconium versus lanthanum promoters. Appl Catal B Environ 101:101–108Google Scholar
  19. 19.
    Trovarelli A (1999) Structural and oxygen storage/release properties of CeO2-based solid solutions. Comment Inorg Chem 20:263–284Google Scholar
  20. 20.
    Kumar P, Tanwar M, Russo N, Pirone R, Fino D (2012) Synthesis and catalytic properties of CeO2 and Co/CeO2 nanofibres for diesel soot combustion. Catal Today 184:279–287Google Scholar
  21. 21.
    Hernández W, Centeno M, Romero-Sarria F, Odriozola J (2009) Synthesis and characterization of Ce1−xEuxO2−x/2 mixed oxides and their catalytic activities for CO oxidation. J Phys Chem C 113:5629–5635Google Scholar
  22. 22.
    Zhao Q, Chen B, Bai Z, Yu L, Crocker M, Shi C (2019) Hybrid catalysts with enhanced C3H6 resistance for NH3-SCR of NOx. Appl Catal B Environ 242:161–170Google Scholar
  23. 23.
    Xu J, Lu G, Guo Y, Guo Y, Gong X (2017) A highly effective catalyst of Co–CeO2 for the oxidation of diesel soot: the excellent NO oxidation activity and NOx storage capacity. Appl Catal A-Gen 535:1–8Google Scholar
  24. 24.
    Shen Q, Lu G, Du C, Guo Y, Wang Y, Guo Y, Gong X (2013) Role and reduction of NOx in the catalytic combustion of soot over iron–ceria mixed oxide catalyst. Chem Eng J 218:164–172Google Scholar
  25. 25.
    Bao H, Chen X, Fang J, Jiang Z, Huang W (2008) Structure-activity relation of Fe2O3–CeO2 composite catalysts in CO Oxidation. Catal Lett 125:160–167Google Scholar
  26. 26.
    Jeong D, Potdar H, Roh H (2012) Comparative study on nano-sized 1 wt% Pt/Ce0.8Zr0.2O2 and 1 wt% Pt/Ce0.2Zr0.8O2 catalysts for a single stage water gas shift reaction. Catal Lett 142:439–444Google Scholar
  27. 27.
    Kim K, Han J (2017) Mechanistic study for enhanced CO oxidation activity on (Mn, Fe) co-doped CeO2(111). Catal Today 293–294:82–88Google Scholar
  28. 28.
    Hu P, Chen Y, Sun R, Chen Y, Yin Y, Wang Z (2017) Synthesis, characterization and frictional wear behavior of ceria hybrid architectures with 111 exposure planes. Appl Surf Sci 401:100–105Google Scholar
  29. 29.
    Pérez-Alonso F, López Granados M, Ojeda M, Terreros P, Rojas S, Herranz T, Fierro J, Gracia M, Gancedo J (2005) Chemical structures of coprecipitated Fe–Ce mixed oxides. Chem Mater 17:2329–2339Google Scholar
  30. 30.
    Laguna O, Romero Sarria F, Centeno M, Odriozola J (2010) Gold supported on metal-doped ceria catalysts (M = Zr, Zn and Fe) for the preferential oxidation of CO (PROX). J Catal 276:360–370Google Scholar
  31. 31.
    Sudarsanam P, Mallesham B, Durgasri D, Reddy B (2014) Physicochemical characterization and catalytic CO oxidation performance of nanocrystalline Ce–Fe mixed oxides. RSC Adv 4:11322–11330Google Scholar
  32. 32.
    Alcalde-Santiago V, Davó-Quiñonero A, Lozano-CastellóD Bueno-López A (2018) On the soot combustion mechanism using 3DOM ceria catalysts. Appl Catal B Environ 234:187–197Google Scholar
  33. 33.
    Dai Q, Huang H, Zhu Y, Deng W, Bai S, Wang X, Lu G (2012) Catalysis oxidation of 1,2-dichloroethane and ethyl acetate over ceria nanocrystals with well-defined crystal planes. Appl Catal B Environ 117–118:360–368Google Scholar
  34. 34.
    Liu S, Wu X, Weng D, Ran R (2015) Ceria-based catalysts for soot oxidation: a review. J Rare Earth 33:567–590Google Scholar
  35. 35.
    Jampaiah D, Venkataswamy P, Tur K, Ippolito S, Bhargava S, Reddy B (2015) Effect of MnOx loading on structural, surface, and catalytic properties of CeO2–MnOx mixed oxides prepared by sol–gel method. Z Anorg Allg Chemie 641:1141–1149Google Scholar
  36. 36.
    Gu D, Schüth F (2014) Synthesis of non-siliceous mesoporous oxides. Chem Soc Rev 43:313–344Google Scholar
  37. 37.
    Kaplin I, Lokteva E, Golubina E, Maslakov K, Strokova N, Chernyak S, Lunin V (2017) Sawdust as an effective biotemplate for the synthesis of Ce0.8Zr0.2O2 and CuO–Ce0.8Zr0.2O2 catalysts for total CO oxidation. RSC Adv 7:51359–51372Google Scholar
  38. 38.
    Kaplin I, Lokteva E, Golubina E, Shishova V, Maslakov K, Fionov A, Isaikina O, Lunin V (2019) Efficiency of manganese modified CTAB-templated ceria–zirconia catalysts in total CO oxidation. Appl Surf Sci 485:432–440Google Scholar
  39. 39.
    Zhu H, Xu J, Yichuan Y, Wang Z, Gao Y, Liu W, Yin H (2017) Catalytic oxidation of soot on mesoporous ceria-based mixed oxides with cetyltrimethyl ammonium bromide (CTAB)-assisted synthesis. J Colloid Interf Sci 508:1–13Google Scholar
  40. 40.
    Wang Z, Chen T, Chen W, Chang K, Ma L, Huang G, Chen D, Lee J (2013) CTAB-assisted synthesis of single-layer MoS2–graphene composites as anode materials of Li-ion batteries. J Mater Chem A 1:2202–2210Google Scholar
  41. 41.
    Renuka N, Praveen A, Aniz C (2013) Ceria rhombic microplates: synthesis, characterization and catalytic activity. Micropor Mesopor Mat 169:35–41Google Scholar
  42. 42.
    Dunne P, Carnerup A, Węgrzyn A, Witkowski S, Walton R (2012) Hierarchically structured ceria–silica: synthesis and thermal properties. J Phys Chem C 116:13435–13445Google Scholar
  43. 43.
    Sing K, Haul R, Everett D, Moscou L, Pierotti R, RouQuelol J (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure Appl Chem 57(4):603–619Google Scholar
  44. 44.
    Hossain S, Azeeva E, Zhang K, Zell E, Bernard D, Balaz S, Wang R (2018) A comparative study of CO oxidation over Cu–O–Ce solid solutions and CuO/CeO2 nanorods catalysts. Appl Surf Sci 455:132–143Google Scholar
  45. 45.
    Li S, Yan S, Xia Y, Cui B, Pu Y, Ye Y, Wang D, Liu Y, Chen B (2019) Oxidative reactivity enhancement for soot combustion catalysts by co-doping silver and manganese in ceria. Appl Catal A-Gen 570:299–307Google Scholar
  46. 46.
    Li Y, Wei Z, Gao F, Kovarik L, Baylon R, Peden C, Wang Y (2015) Effect of oxygen defects on the catalytic performance of VOx/CeO2 catalysts for oxidative dehydrogenation of methanol. ACS Catal 5:3006–3012Google Scholar
  47. 47.
    Lorite I, Romero J, Fernández J (2012) Effects of the agglomeration state on the Raman properties of Co3O4 nanoparticles. J Raman Spectrosc 43:1443–1448Google Scholar
  48. 48.
    Saw E, Oemar U, Ang M, Kus H, Kawi S (2016) High-temperature water gas shift reaction on Ni–Cu/CeO2 catalysts: effect of ceria nanocrystal size on carboxylate formation. Catal Sci Technol 6:5336–5349Google Scholar
  49. 49.
    Zhang Z, Han D, Wei S, Zhang Y (2010) Determination of active site densities and mechanisms for soot combustion with O2 on Fe-doped CeO2 mixed oxides. J Catal 276:16–23Google Scholar
  50. 50.
    Wang A, Guo Y, Gao F, Peden C (2017) Ambient-temperature NO oxidation over amorphous CrOx–ZrO2 mixed oxide catalysts: significant promoting effect of ZrO2. Appl Catal B Environ 202:706–714Google Scholar
  51. 51.
    Yang J, Zhang J, Liu X, Duan X, Wen Y, Chen R, Shan B (2018) Origin of the superior activity of surface doped SmMn2O5 mullites for NO oxidation: a first-principles based microkinetic study. J Catal 359:122–129Google Scholar
  52. 52.
    Ji F, Men Y, Wang J, Sun Y, Wang Z, Zhao B, Tao X, Xu G (2019) Promoting diesel soot combustion efficiency by tailoring the shapes and crystal facets of nanoscale Mn3O4. Appl Catal B Environ 242:227–237Google Scholar
  53. 53.
    Krishna K, Bueno-López A, Makkee M, Moulijn J (2007) Potential rare earth modified CeO2 catalysts for soot oxidation. Appl Catal B Environ 75:189–200Google Scholar
  54. 54.
    Guo X, Meng M, Dai F, Li Q, Zhang Z, Jiang Z, Zhang S, Huang Y (2013) NOx-assisted soot combustion over dually substituted perovskite catalysts La1−xKxCo1−yPdyO3−δ. Appl Catal B Environ 142–143:278–289Google Scholar
  55. 55.
    Liu S, Wu X, Weng D, Li M, Lee H (2012) Combined promoting effects of platinum and MnOx–CeO2 supported on alumina on NOx-assisted soot oxidation: thermal stability and sulfur resistance. Chem Eng J 203:25–35Google Scholar
  56. 56.
    Hwang J, Rao RR, Giordano L, Katayama Y, Yu Y, Shao-Horn Y (2017) Perovskites in catalysis and electrocatalysis. Science 358(6364):751–756Google Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Water Conservancy and EnvironmentUniversity of Jinan, Key Laboratory of Water Resources and Environmental Engineering in Universities of ShandongJinanPeople’s Republic of China
  2. 2.Environmental Monitoring Center, West Coast New Area BranchQingdao Municipal Bureau of Ecology and EnvironmentQingdaoPeople’s Republic of China

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