Skip to main content
SpringerLink
Log in

Dependence of the CeO2 morphology in CuO/CeO2 catalysts for the oxidative steam reforming of methanol

  • Published:
Reaction Kinetics, Mechanisms and Catalysis Aims and scope Submit manuscript

Abstract

Copper oxide on ceria supports (CuO/CeO2) were investigated as catalysts for the oxidative steam reforming of methanol (OSRM) reaction at 200–400 °C. Different shapes of CeO2 were obtained, as rod-, mixed- (rod and cube) and cube-shaped with an exposed surface of (110) + (100), (110) + (100) and (100) planes by variation in the hydrothermal synthesis temperature (100–220 °C). The CuO was deposited on CeO2 by deposition–precipitation at a nominal 10% by weight and the obtained CuO/CeO2 catalysts were characterized. The morphological structure of CeO2 influenced the catalytic activities in the OSRM reaction. The CuO/rod-shaped CeO2 (CuO/CeO2-R) gave the highest turnover frequency (TOF) and a CO concentration of less than 1% (v/v). The high catalytic performance of CuO/CeO2-R involved the well-dispersed CuO nanoparticles, level of Cu+ species as the active site, improved reducible oxide, number of relative oxygen vacancies and the stronger interaction between CuO and CeO2.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Murcia-Mascarós S, Navarro RM, Gómez-Sainero L, Costantino U, Nocchetti M, Fierro JLG (2001) Oxidative methanol reforming reactions on CuZnAl catalysts derived from hydrotalcite-like precursors. J Catal 198(2):338–347

    Article  CAS  Google Scholar 

  2. Pérez-Hernández R, Gutiérrez-Martínez A, Gutiérrez-Wing CE (2007) Effect of Cu loading on CeO2 for hydrogen production by oxidative steam reforming of methanol. Int J Hydrog Energy 32(14):2888–2894

    Article  CAS  Google Scholar 

  3. Selva Roselin L, Chiu H-W (2017) Production of hydrogen by oxidative steam reforming of methanol over Cu/SiO2 catalysts. J Saudi Chem Soc 22(6):692–704

    Article  CAS  Google Scholar 

  4. Takezawa N, Iwasa N (1997) Steam reforming and dehydrogenation of methanol: difference in the catalytic functions of copper and group VIII metals. Catal Today 36(1):45–56

    Article  CAS  Google Scholar 

  5. Breen JP, Ross JRH (1999) Methanol reforming for fuel-cell applications: development of zirconia-containing Cu–Zn–Al catalysts. Catal Today 51(3):521–533

    Article  CAS  Google Scholar 

  6. Gu X, Li H, Liu L, Tang C, Gao F, Dong L (2014) Promotional effect of CO pretreatment on CuO/CeO2 catalyst for catalytic reduction of NO by CO. J Rare Earths 32(2):139–145

    Article  CAS  Google Scholar 

  7. Zhou YH, Peterson EW, Zhou J (2015) Effect of nature of ceria supports on the growth and sintering behavior of Au nanoparticles. Catal Today 240:201–205

    Article  CAS  Google Scholar 

  8. Lakhwani S, Rahaman MN (2011) Hydrothermal coarsening of CeO2 particles. J Mater Res 14(4):1455–1461

    Article  Google Scholar 

  9. Li G, Chao K, Peng H, Chen K, Zhang Z (2008) Facile synthesis of CePO4 nanowires attached to CeO2 octahedral micrometer crystals and their enhanced photoluminescence properties. J Phys Chem C 112(42):16452–16456

    Article  CAS  Google Scholar 

  10. Carltonbird M, Eaimsumang S, Pongstabodee S, Boonyuen S, Smith SM, Luengnaruemitchai A (2018) Effect of the exposed ceria morphology on the catalytic activity of gold/ceria catalysts for the preferential oxidation of carbon monoxide. Chem Eng J 344:545–555

    Article  CAS  Google Scholar 

  11. Han J, Kim HJ, Yoon S, Lee H (2011) Shape effect of ceria in Cu/ceria catalysts for preferential CO oxidation. J Mol Catal A 335(1–2):82–88

    Article  CAS  Google Scholar 

  12. Yi N, Si R, Saltsburg H, Flytzani-Stephanopoulos M (2010) Steam reforming of methanol over ceria and gold-ceria nanoshapes. Appl Catal B 95(1–2):87–92

    Article  CAS  Google Scholar 

  13. Mai HX, Sun LD, Zhang YW, Si R, Feng W, Zhang HP, Liu HC, Yan CH (2005) Shape-selective synthesis and oxygen storage behavior of ceria nanopolyhedra, nanorods, and nanocubes. J Phys Chem B 109(51):24380–24385

    Article  CAS  PubMed  Google Scholar 

  14. Si R, Flytzani-Stephanopoulos M (2008) Shape and crystal-plane effects of nanoscale ceria on the activity of Au-CeO2 catalysts for the water–gas shift reaction. Angew Chem 120(15):2926–2929

    Article  Google Scholar 

  15. Liu L, Yao Z, Deng Y, Gao F, Liu B, Dong L (2011) Morphology and crystal-plane effects of nanoscale ceria on the activity of CuO/CeO2 for NO reduction by CO. ChemCatChem 3(6):978–989

    Article  CAS  Google Scholar 

  16. Kovacevic M, Mojet BL, Van Ommen JG, Lefferts L (2016) Effects of morphology of cerium oxide catalysts for reverse water gas shift reaction. Catal Lett 146(4):770–777

    Article  CAS  Google Scholar 

  17. Lv J, Shen Y, Peng L, Guo X, Ding W (2010) Exclusively selective oxidation of toluene to benzaldehyde on ceria nanocubes by molecular oxygen. Chem Commun 46(32):5909–5911

    Article  CAS  Google Scholar 

  18. Udani PPC, Gunawardana PVDS, Lee HC, Kim DH (2009) Steam reforming and oxidative steam reforming of methanol over CuO–CeO2 catalysts. Int J Hydrog Energy 34(18):7648–7655

    Article  CAS  Google Scholar 

  19. Gu C, Qi R, Wei Y, Zhang X (2018) Preparation and performances of nanorod-like inverse CeO2–CuO catalysts derived from Ce-1,3,5-Benzene tricarboxylic acid for CO preferential oxidation. Reac Kinet Mech Cat 124(2):651–667

    Article  CAS  Google Scholar 

  20. Araiza DG, Gómez-Cortés A, Díaz G (2017) Partial oxidation of methanol over copper supported on nanoshaped ceria for hydrogen production. Catal Today 282:185–194

    Article  CAS  Google Scholar 

  21. Ren Z, Peng F, Li J, Liang X, Chen B (2017) Morphology-dependent properties of Cu/CeO2 catalysts for the water-gas shift reaction. Catalysts 7(2):48

    Article  CAS  Google Scholar 

  22. Guo X, Zhou R (2016) A new insight into the morphology effect of ceria on CuO/CeO2 catalysts for CO selective oxidation in hydrogen-rich gas. Catal Sci Technol 6(11):3862–3871

    Article  CAS  Google Scholar 

  23. Florea I, Feral-Martin C, Majimel J, Ihiawakrim D, Hirlimann C, Ersen O (2013) Three-dimensional tomographic analyses of CeO2 nanoparticles. Cryst Growth Des 13(3):1110–1121

    Article  CAS  Google Scholar 

  24. Bugayeva N (2011) A Study of the structure of CeO2 nanorods. MRS Proc 876(R8):46

    Google Scholar 

  25. Guo X, Zhou R (2017) Identification of the nano/micro structure of CeO2(rod) and the essential role of interfacial copper-ceria interaction in CuCe(rod) for selective oxidation of CO in H2-rich streams. J Power Sources 361:39–53

    Article  CAS  Google Scholar 

  26. Kurajica S, Minga I, Guliš M, Mandić V, Simčić I (2016) High surface area ceria nanoparticles via hydrothermal synthesis experiment design. J Nanomater 2016:8

    Article  CAS  Google Scholar 

  27. Hirano M, Kato E (1996) The hydrothermal synthesis of ultrafine cenum(w) oxide powders. J Mater Sci Lett 15(14):1249–1250

    Article  CAS  Google Scholar 

  28. Du XJ, Zhang DS, Shi LY, Gao RH, Zhang JP (2012) Morphology dependence of catalytic properties of Ni/CeO2 nanostructures for carbon dioxide reforming of methane. J Phys Chem C 116(18):10009–10016

    Article  CAS  Google Scholar 

  29. Agarwal S, Lefferts L, Mojet Barbara L (2012) Ceria nanocatalysts: shape dependent reactivity and formation of OH. ChemCatChem 5(2):479–489

    Article  CAS  Google Scholar 

  30. Cao L, Lu M, Li G, Zhang S (2018) Hydrogen production from methanol steam reforming catalyzed by Fe modified Cu supported on attapulgite clay. Reac Kinet Mech Cat

  31. Jia A-P, Jiang S-Y, Lu J-Q, Luo M-F (2010) Study of catalytic activity at the CuO − CeO2 interface for CO oxidation. J Phys Chem C 114(49):21605–21610

    Article  CAS  Google Scholar 

  32. Zeng S, Zhang W, Śliwa M, Su H (2013) Comparative study of CeO2/CuO and CuO/CeO2 catalysts on catalytic performance for preferential CO oxidation. Int J Hydrog Energy 38(9):3597–3605

    Article  CAS  Google Scholar 

  33. Gupta D, Garg A (2018) Effect of the preparation method on the catalytic activity of the heterogeneous catalyst CuO/CeO2 for the oxidative degradation of sulfide and phenolic compounds. Reac Kinet Mech Cat 124(1):101–121

    Article  CAS  Google Scholar 

  34. Maciel CG, Silva TdF, Hirooka MI, Belgacem MN, Assaf JM (2012) Effect of nature of ceria support in CuO/CeO2 catalyst for PROX-CO reaction. Fuel 97:245–252

    Article  CAS  Google Scholar 

  35. Zabilskiy M, Djinović P, Tchernychova E, Tkachenko OP, Kustov LM, Pintar A (2015) Nanoshaped CuO/CeO2 materials: effect of the exposed ceria surfaces on catalytic activity in N2O decomposition reaction. ACS Catal 5(9):5357–5365

    Article  CAS  Google Scholar 

  36. Dow W-P, Wang Y-P, Huang T-J (2000) TPR and XRD studies of yttria-doped ceria/γ-alumina-supported copper oxide catalyst. Appl Catal A 190(1):25–34

    Article  CAS  Google Scholar 

  37. Agarwal S, Mojet BL, Lefferts L, Datye AK (2015) Chapter 2—Ceria nanoshapes—structural and catalytic properties. In: Wu Z, Overbury SH (eds) Catalysis by materials with well-defined structures. Elsevier, Amsterdam, pp 31–70

    Chapter  Google Scholar 

  38. Liu Y, Hayakawa T, Suzuki K, Hamakawa S, Tsunoda T, Ishii T, Kumagai M (2002) Highly active copper/ceria catalysts for steam reforming of methanol. Appl Catal A 223(1):137–145

    Article  CAS  Google Scholar 

  39. Schilling C, Hofmann A, Hess C, Ganduglia-Pirovano MV (2017) Raman spectra of polycrystalline CeO2: a density functional theory study. J Phys Chem C 121(38):20834–20849

    Article  CAS  Google Scholar 

  40. Dahrul M, Alatas H, Irzaman (2016) Preparation and optical properties study of CuO thin film as applied solar cell on LAPAN-IPB satellite. Procedia Environ Sci 33:661–667

    Article  CAS  Google Scholar 

  41. Zhang W, Niu X, Chen L, Yuan F, Zhu Y (2016) Soot combustion over nanostructured ceria with different morphologies. Sci Rep 6:29062

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  42. Das D, Llorca J, Dominguez M, Colussi S, Trovarelli A, Gayen A (2015) Methanol steam reforming behavior of copper impregnated over CeO2–ZrO2 derived from a surfactant assisted coprecipitation route. Int J Hydrog Energy 40(33):10463–10479

    Article  CAS  Google Scholar 

  43. Alejo L, Lago R, Peña MA, Fierro JLG (1997) Partial oxidation of methanol to produce hydrogen over Cu-Zn-based catalysts. Appl Catal A 162(1):281–297

    Article  CAS  Google Scholar 

  44. Yang S-C, Su W-N, Lin SD, Rick J, Hwang B-J (2012) Preparation of highly dispersed catalytic Cu from rod-like CuO–CeO2 mixed metal oxides: suitable for applications in high performance methanol steam reforming. Catal Sci Technol 2(4):807–812

    Article  CAS  Google Scholar 

  45. Kozuch S, Martin JML (2012) “Turning over” definitions in catalytic cycles. ACS Catal 2(12):2787–2794

    Article  CAS  Google Scholar 

  46. Lente G (2013) Comment on “‘turning over’ definitions in catalytic cycles”. ACS Catal 3(3):381–382

    Article  CAS  Google Scholar 

  47. Boudart M (1995) Turnover rates in heterogeneous catalysis. Chem Rev 95(3):661–666

    Article  CAS  Google Scholar 

  48. Mullins DR, Albrecht PM, Calaza F (2013) Variations in reactivity on different crystallographic orientations of cerium oxide. Top Catal 56(15):1345–1362

    Article  CAS  Google Scholar 

  49. Mullins DR (2015) The surface chemistry of cerium oxide. Surf Sci Rep 70(1):42–85

    Article  CAS  Google Scholar 

  50. Reitz TL, Ahmed S, Krumpelt M, Kumar R, Kung HH (2000) Characterization of CuO/ZnO under oxidizing conditions for the oxidative methanol reforming reaction. J Mol Catal A 162(1):275–285

    Article  CAS  Google Scholar 

  51. Agrell J, Birgersson H, Boutonnet M, Melián-Cabrera I, Navarro RM, Fierro JLG (2003) Production of hydrogen from methanol over Cu/ZnO catalysts promoted by ZrO2 and Al2O3. J Catal 219(2):389–403

    Article  CAS  Google Scholar 

  52. Turco M, Bagnasco G, Costantino U, Marmottini F, Montanari T, Ramis G, Busca G (2004) Production of hydrogen from oxidative steam reforming of methanol: I. Preparation and characterization of Cu/ZnO/Al2O3 catalysts from a hydrotalcite-like LDH precursor. J Catal 228(1):43–55

    CAS  Google Scholar 

  53. Lykaki M, Pachatouridou E, Carabineiro SAC, Iliopoulou E, Andriopoulou C, Kallithrakas-Kontos N, Boghosian S, Konsolakis M (2018) Ceria nanoparticles shape effects on the structural defects and surface chemistry: implications in CO oxidation by Cu/CeO2 catalysts. Appl Catal B 230:18–28

    Article  CAS  Google Scholar 

  54. Liu W, Flytzanistephanopoulos M (1995) Total oxidation of carbon monoxide and methane over transition metal fluorite oxide composite catalysts: I. Catalyst composition and activity. J Catal 153(2):304–316

    Article  CAS  Google Scholar 

  55. Aboukaïs A, Aouad S, El-Ayadi H, Skaf M, Labaki M, Cousin R, Abi-Aad E (2012) Physicochemical characterization of Au/CeO2 solid. Part 1: The deposition–precipitation preparation method. Mater Chem Phys 137(1):34–41

    Article  CAS  Google Scholar 

  56. Wang Z, Deng Y, Shen G, Akram S, Han N, Chen Y, Wang Q (2016) Catalytic degradation of benzene over nanocatalysts containing cerium and manganese. ChemistryOpen 5(5):495–504

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  57. Wang X, Rodriguez JA, Hanson JC, Gamarra D, Martínez-Arias A, Fernández-García M (2005) Unusual physical and chemical properties of Cu in Ce1-xCuxO2 oxides. J Phys Chem B 109(42):19595–19603

    Article  CAS  PubMed  Google Scholar 

  58. Huang XS, Sun H, Wang LC, Liu YM, Fan KN, Cao Y (2009) Morphology effects of nanoscale ceria on the activity of Au/CeO2 catalysts for low-temperature CO oxidation. Appl Catal B 90(1–2):224–232

    Article  CAS  Google Scholar 

  59. Wu Z, Li M, Howe J, Meyer HM, Overbury SH (2010) Probing defect sites on CeO2 nanocrystals with well-defined surface planes by raman spectroscopy and O2 adsorption. Langmuir 26(21):16595–16606

    Article  CAS  PubMed  Google Scholar 

  60. Nolan M, Grigoleit S, Sayle DC, Parker SC, Watson GW (2005) Density functional theory studies of the structure and electronic structure of pure and defective low index surfaces of ceria. Surf Sci 576(1):217–229

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors acknowledge the contributions and financial support of the following organizations: Chulalongkorn University (CU-GES-60-04-63-03); Thammasat University Research Fund under the Research University Network (RUN) Initiative (No. 8/2560), and Grant for International Research Integration: Chula-Research Scholar, Ratchadaphiseksomphot Endowment Fund, Thailand. The authors thank the Thailand Research Fund (TRF) and National Science and Technology Development Agency (PHD/0237/2558) for the PhD scholarship funding of Ms. Srisin Eaimsumang.

Author information

Authors and Affiliations

  1. The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok, 10330, Thailand

    Srisin Eaimsumang, Sivinee Petchakan & Apanee Luengnaruemitchai

  2. Center of Excellence on Petrochemical and Materials Technology, Chulalongkorn University Research Building, Soi Chula 12, Phayathai Rd., Bangkok, 10330, Thailand

    Apanee Luengnaruemitchai

  3. Center of Excellence in Catalysis for Bioenergy and Renewable Chemicals (CBRC), Chulalongkorn University, Bangkok, 10330, Thailand

    Apanee Luengnaruemitchai

Authors
  1. Srisin Eaimsumang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sivinee Petchakan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Apanee Luengnaruemitchai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Apanee Luengnaruemitchai.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 2212 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Eaimsumang, S., Petchakan, S. & Luengnaruemitchai, A. Dependence of the CeO2 morphology in CuO/CeO2 catalysts for the oxidative steam reforming of methanol. Reac Kinet Mech Cat 127, 669–690 (2019). https://doi.org/10.1007/s11144-019-01570-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11144-019-01570-4

Keywords

Search

Navigation