We report a general synthesis of high-quality cubic (alpha-phase) and hexagonal (beta-phase) NaREF4 (RE: Pr to Lu, Y) nanocrystals (nanopolyhedra, nanorods, nanoplates, and nanospheres) and NaYF(4):Yb,Er/Tm nanocrystals (nanopolyhedra and nanoplates) via the co-thermolysis of Na(CF3COO) and RE(CF3COO)3 in oleic acid/oleylamine/1-octadecene. By tuning the ratio of Na/RE, solvent composition, reaction temperature and time, we can manipulate phase, shape, and size of the nanocrystals. On the basis of its alpha --> beta phase transition behavior, along the rare-earth series, NaREF4 can be divided into three groups (I: Pr and Nd; II: Sm to Tb; III: Dy to Lu, Y). The whole controlled-synthesis mechanism can be explained from the point of view of free energy. Photoluminescent measurements indicate that the value of I610/I590 and the overall emission intensity of the NaEuF4 nanocrystals are highly correlative with the symmetries of the Eu3+ ions in both the lattice and the surface.
Single-crystalline and uniform nanopolyhedra, nanorods, and nanocubes of cubic CeO2 were selectively prepared by a hydrothermal method at temperatures in the range of 100-180 degrees C under different NaOH concentrations, using Ce(NO3)3 as the cerium source. According to high-resolution transmission electron microscopy, they have different exposed crystal planes: {111} and {100} for polyhedra, {110} and {100} for rods, and {100} for cubes. During the synthesis, the formation of hexagonal Ce(OH)3 intermediate species and their transformation into CeO2 at elevated temperature, together with the base concentration, have been demonstrated as the key factors responsible for the shape evolution. Oxygen storage capacity (OSC) measurements at 400 degrees C revealed that the oxygen storage takes place both at the surface and in the bulk for the as-obtained CeO2 nanorods and nanocubes, but is restricted at the surface for the nanopolyhedra just like the bulk one, because the {100}/{110}-dominated surface structures are more reactive for CO oxidation than the {111}-dominated one. This result suggests that high OSC materials might be designed and obtained by shape-selective synthetic strategy.
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