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Ya-Wen Zhang

Publications and source records attributed to Ya-Wen Zhang.

9 recordsLinked to original sources

From trifluoroacetate complex precursors to monodisperse rare-earth fluoride and oxyfluoride nanocrystals with diverse shapes through controlled fluorination in solution phase.

We report the first systematic synthesis of monodisperse rare-earth (RE=La to Lu, Y) fluoride and oxyfluoride nanocrystals with diverse shapes (trigonal REF3 triangular, truncated-triangular, hexagonal, and polygonal nanoplates; orthorhombic REF3 quadrilateral and zigzag-shaped nanoplates; cubic REOF nanopolyhedra and nanorods) from single-source precursors (SSP) of [RE(CF(3)COO)(3)] through controlled fluorination in oleic acid (OA)/oleylamine (OM)/1-octadecene (ODE). To selectively obtain REF3 or REOF nanocrystals, the fluorination of the RE-O bond to the RE-F bond at the nucleation stage was controlled by finely tuning the ratio of OA/ODE or OA/OM, and the reaction temperature. For phase-pure REF3 or REOF naocrystals, their shape-selective syntheses could be realized by further modifying the reaction conditions. The two-dimensional growth of the REF3 nanoplates and the one-dimensional growth of the REOF nanorods were likely due to the selective adsorption of the capping ligands on specific crystal planes of the nanocrystals. Those well-shaped nanocrystals with diverse geometric symmetries (such as D(3h), D(6h), C(2h), O(h), and D(nh)) displayed a remarkable capability to form self-assembled superlattices. By manipulating the solvent-substrate combination, the plate-shaped REF3 nanocrystals could form highly ordered nanoarrays by means of either the face-to-face formation or the edge-to-edge formation. By using this SSP strategy, we also obtained high-quality LaF3:Eu and LaF3:Eu/LaF3 triangular nanoplates that showed photoluminescent red emissions of Eu3+ ions sensitive to the surface effect.

Crystallization↗

High-quality sodium rare-earth fluoride nanocrystals: controlled synthesis and optical properties.

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.

Journal Article↗

Self-organized monolayer of nanosized ceria colloids stabilized by poly(vinylpyrrolidone).

Four nanometer colloidal ceria nanocrystals in a fluorite cubic structure have been synthesized via an alcohothermal treatment at 180 degrees C for 24 h from Ce(NO(3))(3)*6H(2)O in ethanol, using various alkylamines including triethylamine, butylamine, and hexadecylamine as the bases and poly(vinylpyrrolidone) (PVP) as the stabilizer. They were characterized by multiple measurements of X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), ultraviolet visible (UV-vis) spectroscopy, dynamic light scattering (DLS), and infrared spectroscopy (IR). The introduction of PVP could effectively stabilize the cerium nuclei against self-aggregation and finally lead to the formation of the CeO(2) colloids. As compared with that of their precipitated counterparts, the UV-vis spectra showed a blue-shifted absorption edge for the as-obtained colloidal nanocrystals, revealing that their surfaces were well-passivated by PVP. Four types of self-organized monolayer patterns (i.e., isolated particles, short chainlike (pseudo-1-D aggregated), pearl necklace-like (1-D aggregated), and dendritic (pseudo-2-D aggregated) alignments) appeared for the as-obtained colloidal particles on the copper TEM grids, due to the delicate balance of the attractive and repulsive forces between the PVP-passivated CeO(2) nanocrystals during the irreversible evaporation of the solvent from various colloidal solutions under ambient conditions. The type of alkylamine and the concentration of PVP were confirmed to be the crucial factors determining the oriented-aggregation dimensionality of the CeO(2) colloids. Possible interparticle interaction modes have been suggested to explain such complex self-organization patterns exhibited by the as-obtained CeO(2) nanocrystals.

Journal Article↗

Shape-selective synthesis and oxygen storage behavior of ceria nanopolyhedra, nanorods, and nanocubes.

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.

Cerium↗

Phase evolution, texture behavior, and surface chemistry of hydrothermally derived scandium (hydrous) oxide nanostructures.

Nanostructured scandium hydrous oxides were hydrothermally synthesized at 180 degrees C for 18 h, using NaOH, NH(4)OH, and KOH as the bases. They were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption, thermogravimetry and differential thermal analysis (TG-DTA), infrared and Raman spectroscopy, and pyridine adsorption. XRD and TEM measurements showed that the nature and concentration of the bases played key roles in determining the phasic composition, texture behavior (shape and size), and surface chemistry of the hydrothermal products. In addition, the shape evolution of the crystalline products seemed to be closely connected with their crystal structures. As the basicity value was raised from pH 10 to 5 mol L(-1) NaOH (or KOH), alpha-ScOOH nanorods, alpha-ScOOH nanosized hexagonal-like plates, and cubic Sc(OH)3 cubes/cuboids in micrometer size were produced in turn; while within pH 10-12 using NH4OH, gamma-ScOOH nanosized lozenge-like plates were mainly obtained. According to XRD, TEM, and TG-DTA results, all the as-prepared nanostructured ScOOH and micrometric Sc(OH)3 could be converted to cubic Sc2O3 with sustained crystalline shape via calcination at 500 degrees C. Pyridine adsorption revealed the existence of Lewis acid sites on the surfaces of the nanostructured alpha-ScOOH samples and some of their Sc2O3 counterparts calcined at 700 degrees C. The alpha-ScOOH nanorod sample displayed the strongest Lewis acidity among all the samples tested, due to its highest surface area as determined by N2 adsorption. Finally, an olation-oxolation process based on a dissolution/recrystallization mechanism accounts for the formation of various ScOOH polymorphs and Sc(OH)3 with different shapes.

Nanostructures↗

Single-crystalline and monodisperse LaF3 triangular nanoplates from a single-source precursor.

Single-crystalline and monodisperse LaF3 triangular nanoplates (2.0 x 16.0 nm) in trigonal tysonite structure were synthesized by the thermolysis of a single-source precursor (SSP), La(CF3COO)3, in a hot oleic acid/octadecene solution. The combined use of SSP and coordinating and noncoordinating solvents was demonstrated to have played key roles in the formation of such high-quality nanoplates, which could spontaneously organize into two types of superlattices (edge-to-edge and face-to-face) on a large area. This SSP approach has advantages of one-step, mass production, and easy operation, and may represent a rather general route toward metal fluoride nanocrystals.

Journal Article↗

Synthesis, structure, texture, and CO sensing behavior of nanocrystalline tin oxide doped with scandia.

Weakly agglomerated nanocrystalline scandia doped tin oxide powders with high surface area (170-220 m(2)/g) and uniform size (3-4 nm) were synthesized for the first time by a two-step hydrothermal process in the presence of urea, followed by the calcination between 500 and 1200 degrees C. The structure and texture of the binary oxide system were characterized by thermogravimetry and differential thermal analysis, Brunauer-Emmett-Teller-specific surface area analysis, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. A metastable scandium tin oxide solid solution in tetragonal structure was formed for the scandia content lower than 6 mol % as the samples were calcined at 800 degrees C, and the excess Sc atoms were dispersed at the surface of the crystallites above this limit. The solid solution was metastable, so scandium migrated toward the surface region of the crystallites and produced a second phase of Sc(4)Sn(3)O(12) during calcining at high temperatures over 1000-1200 degrees C. In the case of the samples with higher dopant concentration (>15 mol %), the calcination at the temperature between 500 and 800 degrees C caused the precipitation of Sc(2)O(3), and the calcination over 1000-1200 degrees C led to the formation of more Sc(4)Sn(3)O(12). Textural analysis showed that doping an appropriate amount of Sc(2)O(3) into nanosized SnO(2) could effectively inhibit the grain growth and stabilize the surface area against high-temperature calcinations below 1000 degrees C. CO gas-sensing property measurements revealed that the dispersion of Sc at the surfaces of the SnO(2) nanocrystallites could improve the CO sensitivity significantly, and the pellet sample with scandia content of 10 mol % sintered at 800 degrees C showed the best CO gas-sensing property in the operation temperature range of 300-400 degrees C. On the basis of the structural and textural analysis, the correlation between the structure/texture and the sensitivity to CO for the as-calcined (SnO(2))(1-x)(Sc(2)O(3))(x) nanocrystallites has been established and explained.

Journal Article↗