Continuous precipitation of ceria nanoparticles from a continuous flow micromixer

  • Chih Heng T. Tseng
  • Brian K. Paul
  • Chih-Hung Chang
  • Mark H. Engelhard


Cerium oxide nanoparticles were continuously precipitated from a solution of cerium(III) nitrate and ammonium hydroxide using a static microchannel T-mixer. T-mixer synthesis results were compared with synthesis results from batch precipitation. Findings show that the method of mixing is important in the ceria precipitation process. Uniform porous film structures and nanorods were produced when the particle chemistry was synthesized using T-mixing followed by spin coating. Batch mixing, when using higher NH4OH feed concentrations followed by spin coating, was characterized by the heavy agglomeration of nanoparticles. Similar, high aspect ratio nanorods were produced when feed conditions in both batch mixing and T-mixing were identical demonstrating that the momentum effects of continuous microchannel T-mixing did not impact the synthesis process. In addition, it was found that the micromixing approach reduced the exposure of the Ce(OH)3 precipitates to oxygen, yielding hydroxide precipitates in place of CeO2 precipitates. The key advantage of the micro-scale T-mixing approach is higher throughput which is important for the scaling of ceria nanoparticle production.


Continuous flow synthesis Ceria Nanoparticles Microreactor Micromixer 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Tsunekawa S, Kasuya A (2000) Blue shift in ultraviolet absorption spectra of monodisperse CeO nanoparticles. J Appl Phys 87:1318CrossRefGoogle Scholar
  2. 2.
    Trovarelli A, de Leitenburg C, Boaro M, Dolcetti G (1999) The utilization of ceria in industrial catalysis. Catal Today 50:353–367CrossRefGoogle Scholar
  3. 3.
    Spanier JE, Robinson RD, Zhang F, Chan SW, Herman IP (2001) Size-dependent properties of CeO2−y nanoparticles as studied by Raman scattering. Phys Rev B 64:245407CrossRefGoogle Scholar
  4. 4.
    Tsunekawa S, Sahara R, Kawazoe Y, Kasuya A (2000) Origin of the blue shift in ultraviolet absorption spectra of nanocrystalline CeO2−x particles. Mater Trans JIM 41:1104–1107Google Scholar
  5. 5.
    Bekyarova E, Fornasiero P, Kašpar J, Graziani M (1998) CO oxidation on Pd/CeO2–ZrO2 catalysts. Catal Today 45:179–183CrossRefGoogle Scholar
  6. 6.
    Yahiro H, Baba Y, Eguchi K, Arai H (1988) High temperature fuel cell with Ceria-Yttria solid electrolyte. J Electrochem Soc 135:2077–2080CrossRefGoogle Scholar
  7. 7.
    Li M, Zhang R, Zhang H, Feng W, Liu X (2010) Synthesis, structural and magnetic properties of CeO2 nanoparticles. Micro & Nano Letters 5:95CrossRefGoogle Scholar
  8. 8.
    Izu N, Shin W, Murayama N, Kanzaki S (2002) Resistive oxygen gas sensors based on CeO2 fine powder prepared using mist pyrolysis. Sensor Actuator B Chem 87:95–98CrossRefGoogle Scholar
  9. 9.
    Hirta Y, Harada A, Wang X (2005) Wet forming and sintering behavior of nanometer-sized ceria powder. Ceram Int 31:1007–1013CrossRefGoogle Scholar
  10. 10.
    Chu X, Chung W-I, Schmidt LD (1993) Sintering of sol–gel prepared submicrometer particles studied by transmission electron microscopy. J Am Ceram Soc 76:2115–2118CrossRefGoogle Scholar
  11. 11.
    Makishima A, Kubo H, Wada K, Kitami Y, Shimohira T (1986) Yellow coatings produced on glasses and aluminum by the sol–gel process. J Am Ceram Soc 69:C–127–C–129Google Scholar
  12. 12.
    Hakuta Y, Onai S, Terayama H, Adschiri T, Arai K (1998) Production of ultra-fine ceria particles by hydrothermal synthesis under supercritical conditions. J Mater Sci Lett 17:1211–1213CrossRefGoogle Scholar
  13. 13.
    Uekawa N, Ueta M, Wu YJ, Kakegawa K (2004) Characterization of CeO2 fine particles prepared by the homogeneous precipitation method with a mixed solution of ethylene glycol and polyethylene glycol. J Mater Res 19:1087–1092CrossRefGoogle Scholar
  14. 14.
    Dong X, Hong G, Yu D, Yu D (1997) Synthesis and properties of cerium oxide nanometer powders by pyrolysis of amorphous citrate. J Mater Sci Technol 13:113–116Google Scholar
  15. 15.
    Masui T, Fujiwara K, Machida K-I, Adachi G-Y, Sakata T, Mori H (1997) Characterization of cerium(IV) oxide ultrafine particles prepared using reversed micelles. Chem Mater 9:2197–2204CrossRefGoogle Scholar
  16. 16.
    Hsu WP, Ronnquist L, Matijevic E (1988) Preparation and properties of monodispersed colloidal particles of lanthanide compounds. 2. Cerium (IV). Langmuir 4:31–37CrossRefGoogle Scholar
  17. 17.
    Chen P-L, Chen IW (1993) Reactive cerium(IV) oxide powders by the homogeneous precipitation method. J Am Ceram Soc 76:1577–1583CrossRefGoogle Scholar
  18. 18.
    Liu K, Zhong M (2010) Synthesis of monodispersed nanosized CeO2 by hydrolysis of the cerium complex precursor. J Rare Earths 28:680–683CrossRefGoogle Scholar
  19. 19.
    Zhou XD, Huebner W, Anderson HU (2002) Room-temperature homogeneous nucleation synthesis and thermal stability of nanometer single crystal CeO2. Appl Phys Lett 80:3814CrossRefGoogle Scholar
  20. 20.
    Hessel V, Löwe H, Schönfeld F (2005) Micromixers—a review on passive and active mixing principles. Chem Eng Sci 60:2479–2501CrossRefGoogle Scholar
  21. 21.
    Nguyen NT, Wu Z (2005) Micromixers—a review. J Micromech Microeng 15:R1CrossRefGoogle Scholar
  22. 22.
    Schwarzer HC, Peukert W (2004) Tailoring particle size through nanoparticle precipitation. Chem Eng Commun 191:580–606CrossRefGoogle Scholar
  23. 23.
    Chang CH, Liu SH, Tennico Y, Rundel JT, Remcho VT, Blackwell E, Tseng CH and Paul BK (2005) Progress towards chip-based high-throughput dendrimer synthesis. In: International Conference on Microreaction Technology. Atlanta, Georgia, pp. 3011–3018Google Scholar
  24. 24.
    Joanicot M, Ajdari A (2005) Droplet control for microfluidics. Science 309:887CrossRefGoogle Scholar
  25. 25.
    Nakamura H, Yamaguchi Y, Miyazaki M, Maeda H, Uehara M, Mulvaney P (2002) Preparation of CdSe nanocrystals in a micro-flow-reactor. Chem Commun 23:2844–2845CrossRefGoogle Scholar
  26. 26.
    Chan EM, Mathies RA, Alivisatos AP (2003) Size-controlled growth of CdSe nanocrystals in microfluidic reactors. Nano Lett 3:199–201CrossRefGoogle Scholar
  27. 27.
    Yen BKH, Stott NE, Jensen KF, Bawendi MG (2003) A continuous-flow microcapillary reactor for the preparation of a size series of CdSe nanocrystals. Adv Mater 15:1858–1862CrossRefGoogle Scholar
  28. 28.
    Krishnadasan S, Tovilla J, Vilar R (2004) On-line analysis of CdSe nanoparticle formation in a continuous flow chip-based microreactor. J Mater Chem 14:2655–2660CrossRefGoogle Scholar
  29. 29.
    Ehrfeld W, Hessel V, Löwe H (2000) Microreactors: new technology for modern chemistry. Wiley, WeinhemGoogle Scholar
  30. 30.
    Tseng C, Paul B (2007) Comparison of batch mixing and micromixing approaches in the synthesis and deposition of ceria nanoparticles. Trans NAMRI 35Google Scholar
  31. 31.
    Chang H, Chen H (2005) Morphological evolution for CeO2 nanoparticles synthesized by precipitation technique. J Cryst Growth 283:457–468CrossRefGoogle Scholar
  32. 32.
    Yamashita M, Kameyama K, Yabe S, Yoshida S, Fujishiro Y, Kawai T, Sato T (2002) Synthesis and microstructure of calcia doped ceria as UV filters. J Mater Sci 37:683–687CrossRefGoogle Scholar
  33. 33.
    Wang ZL, Feng X (2003) Polyhedral shapes of CeO2 nanoparticles. J Phys Chem B 107:13563–13566CrossRefGoogle Scholar
  34. 34.
    Tang C, Bando Y, Liu B, Golberg D (2005) Cerium oxide nanotubes prepared from cerium hydroxide nanotubes. Adv Mater 17:3005–3009CrossRefGoogle Scholar
  35. 35.
    Mai H-X, Sun L-D, Zhang Y-W, Si R, Feng W, Zhang H-P, Liu H-C, Yan C-H (2005) Shape-selective synthesis and oxygen storage behavior of ceria nanopolyhedra, nanorods, and nanocubes. J Phys Chem B 109:24380–24385CrossRefGoogle Scholar

Copyright information

© Springer-Verlag London Limited 2012

Authors and Affiliations

  • Chih Heng T. Tseng
    • 1
  • Brian K. Paul
    • 1
  • Chih-Hung Chang
    • 2
  • Mark H. Engelhard
    • 3
  1. 1.School of Mechanical, Industrial, and Manufacturing EngineeringOregon State UniversityCorvallisUSA
  2. 2.School of Chemical, Biological, and Environmental EngineeringOregon State UniversityCorvallisUSA
  3. 3.Environmental Molecular Sciences LaboratoryPacific Northwest National LaboratoryRichlandUSA

Personalised recommendations