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• W2839851022 endingPage "5088" @default.
• W2839851022 startingPage "5080" @default.
• W2839851022 abstract "Phase-pure hexagonal lanthanide-doped NaYF4 nanocrystals possess enhanced luminescence properties due to their low phonon energy and chemical stability compared to their cubic phase counterpart. However, the phase-pure hexagonal NaYF4 nanoparticle forms only at high temperature (≥180 °C) and in the presence of certain ligands (e.g., oleic acid), whereas the cubic phase forms at a low reaction temperature. To this end, we report the low temperature (∼48 °C) synthesis of phase-pure hexagonal NaYF4 nanoparticles by converting cubic NaYF4 nanoparticles into the hexagonal phase through surface oxidation of oleic acid (C-18) ligand to azelaic acid (C-9). The mechanism behind the transformation is investigated using density functional theory (DFT) based studies. DFT studies reveal that the phase transformation from cubic → hexagonal phase involves a disorder → order phase transition since all cationic sites are occupied by either Na or Y in the cubic phase, while the hexagonal phase has a more ordered structure with one Y having full occupancy at its cationic site. As carboxyl groups of adsorbents strongly adsorb on Y-terminated surfaces while having no interaction with Na-terminated surfaces of the cubic phase, the surface-ligand interaction promotes surface segregation of Y. This biasing of occupancy toward a more ordered arrangement promotes the formation of a more ordered phase and correspondingly reduces the energy barrier for transformation to the more ordered hexagonal phase. The surface coverage achieved by oleic acid is low due to its bulky long alkyl chains (C-18) imposing steric restriction that is removed on shortening of the alkyl chain length. As a consequence, there is greater surface–ligand interaction leading to further surface segregation of Y and cationic ordering in the cubic phase and making the phase transformation to the hexagonal phase less energy intensive. In addition, oxidation of oleic acid makes nanoparticles hydrophilic, making it suitable for biological applications." @default.
• W2839851022 created "2018-07-19" @default.
• W2839851022 creator A5009977213 @default.
• W2839851022 creator A5076262237 @default.
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• W2839851022 date "2018-07-11" @default.
• W2839851022 modified "2023-10-04" @default.
• W2839851022 title "Catalyzing Cubic-to-Hexagonal Phase Transition in NaYF₄ via Ligand Enhanced Surface Ordering" @default.
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• W2839851022 doi "https://doi.org/10.1021/acs.cgd.8b00535" @default.
• W2839851022 hasPublicationYear "2018" @default.
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