Tuning surface grafting density of CeO2 nanocrystals with near- and supercritical solvent characteristics

B. Giroire, C. Slostowski, S. Marre, C. Aymonier, T. Aida, D. Hojo, N. Aoki, S. Takami, T. Adschiri

Research output: Contribution to journalArticlepeer-review

15 Citations (Scopus)

Abstract

In this work, the solvent effect on the synthesis of CeO2 nanocrystals synthesized in near- and supercritical alcohols is discussed. The materials prepared displayed a unique morphology of small nanocrystals (<10 nm) aggregated into larger nanospheres (∼100-200 nm). In such syntheses, alcohol molecules directly interact with the nanocrystal surface through alkoxide and carboxylate bondings. The grafting density was quantified from the weight loss measured using thermogravimetric analysis. A direct correlation between the grafting density and the alcohol chain length can be established. It was demonstrated that the shorter the alcohol chain length (i.e. methanol), the higher the surface coverage is. This trend is independent of the synthesis mode (batch or continuous). Additionally, an influence of the grafting density on the resulting nanocrystal size was established. It is suggested that the surface coverage has a high influence on the early stages of the nucleation and growth. Indeed, when high surface coverages are reached, all surface active sites are blocked, limiting the growth step and therefore leading to smaller particles. This effect was noticed with the materials prepared in the continuous mode where shorter reaction time was performed.

Original languageEnglish
Pages (from-to)1727-1734
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume18
Issue number3
DOIs
Publication statusPublished - 2016

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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