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Chun-Hua Yan

Publications and source records attributed to Chun-Hua Yan.

At least 19 recordsLinked to original sources
PubMed2007

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↗
PubMed2006

Size-controllable one-dimensional SnO2 nanocrystals: synthesis, growth mechanism, and gas sensing property.

Single crystalline one-dimensional (1-D) SnO(2) nanocrystals with controllable sizes, including the diameter and the aspect ratio, were synthesized by modulating the precursor concentration, reaction time and temperature via a solution method. By regulating the growth in a kinetic regime, a higher temperature range (220-240 degrees C) was beneficial to the growth of SnO(2) nanowires, while reactions below 220 degrees C only resulted in nanorods or even nanoparticles. The aggregates of SnO(2) nanocrystals in the forms of hollow spheres and dendrites were observed as the intermediates for the nanowires. Based on the TEM and SEM observations, the growth mechanism is discussed from the viewpoints of the nature of the reverse micelles and the crystal habit of rutile SnO(2). CO gas sensing measurements were also carried out for SnO(2) nanocrystals with different assembly styles. The results indicate that the sensitivity had close correlation to the specific surface area of the nanocrystals.

Carbon Monoxide↗
PubMed2006

Coordination polymers with end-on azido and pyridine carboxylate N-oxide bridges displaying long-range magnetic ordering with low dimensional character.

A series of 2D and one 3D transition-metal-azido coordination polymers with pyridine carboxylate N-oxide, isonicotinate N-oxide (INO), and nicotinate N-oxide (NNO) as the coligands were synthesized by a hydrothermal method and structurally and magnetically characterized. These complexes have the formulas [M(L)(N3)(H2O)]n (L = INO and M = Mn, 1.Mn; Co, 2.Co; Ni, 3.Ni and L = NNO and M = Mn, 4.Mn; Co, 5.Co; Ni, 6.Ni) and [Cu(L)(N3)(H2O)(0.5)]n (L = INO, 7.Cu; NNO, 8.Cu). All complexes consist of end-on azido and syn-syn carboxylato mixed-bridged M-N(3)/COO chains that are further linked by the pyridine N-oxide group of the INO or NNO to give rise to 2D layered structures for 1.Mn, 2.Co, 3.Ni, 4.Mn, 5.Co, 6.Ni, and 8.Cu and a 3D framework for 7.Cu. The high-temperature magnetic susceptibilities are dominated by low-dimensional behavior while long-range ordering sets in at low temperatures. The Mn complexes are antiferromagnets, and the others are metamagnets. In addition, 5.Co exhibits slow magnetic relaxation behavior at low temperatures. The metamagnetism in each case is due to strong intrachain ferromagnetic interactions and weak interchain antiferromagnetic ones.

Journal Article↗
PubMed2006

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↗
PubMed2006

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↗
PubMed2005

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↗
PubMed2005

From low-dimensional manganese(II) azido motifs to higher-dimensional materials: structure and magnetic properties.

Four new inorganic-organic hybrid coordination polymers in which 1D or 2D manganese(II) azido inorganic motifs are interlinked into higher-dimensional networks have been synthesized by use of a series of bis(pyridyl)-type organic bridging ligands (linkers) with different side groups and/or different coordination orientations. The dimensionality and the topology of the manganese(II) azido motif and the whole structure are sensitive to the organic linkers used. Compounds 1 and 3 are 3D coordination polymers with pillared-layer architectures: in 1, 2D Mn(II) layers with alternate double end-on (EO) and single end-to-end (EE) azido bridges are pillared by zigzag organic linkers, and 3 is built from single EE azido-bridged Mn(II) layers and linear organic linkers. The 3D nets of 1, 3, and related compounds have been related to the specific length and coordination orientation of the organic pillars and the undulate shape of the manganese(II) azido layers. Consistent with their structures, both 1 and 3 exhibit weak ferromagnetism due to spin canting. Compound 1 is a weak ferromagnet with T(c) = 16 K, and 3 is a metamagnet with T(c) = 23 K. On the other hand, compounds 2 and 4 are 2D coordination networks in which 1D manganese(II) azido chains are interlinked by organic linkers: 2 is the first 2D network built from Mn(II) chains with alternate double EE and double EO azido bridges, which mediate antiferro- and ferromagnetic interactions, respectively; 4 is the first 2D network built from Mn(II) chains with only single EE azido bridges, which mediate antiferromagnetic interactions. The magnetic susceptibility of 4 exhibits a rapid rise at very low temperature, which may be attributed to paramagnetic impurities or spin canting.

Journal Article↗
PubMed2005

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↗
PubMed2005

Hierarchical assembly of SnO2 nanorod arrays on alpha-Fe2O3 nanotubes: a case of interfacial lattice compatibility.

SnO2 nanorod arrays were hierarchically assembled onto the surface of alpha-Fe2O3 nanotubes via a facile solution method. Determined by the hexagonal geometrical nature of the alpha-Fe2O3 nanotubes, the heterostructures were of 6-fold symmetry. HRTEM characterizations demonstrated that the lattice mismatch at the interface was an important factor in determining the growth direction of the secondary nanorod arrays.

Journal Article↗
PubMed2005

Attachment-driven morphology evolvement of rectangular ZnO nanowires.

The rectangular cross-sectional ZnO nanowires were synthesized in a solution method. An attachment-driven growth mechanism was proposed for the morphology evolvement of ZnO nanocrystals from nanoparticles to nanoplates and eventually to nanowires. Due to the pileup attachment of the nanoplates to recrystallize into nanowires, unique one-dimensional (1D) ZnO nanowires with the rectangular cross section were obtained, which is different from those nanowires in the previous reports. It is the first time the evidence that "oriented attachment" can occur not only for nanoparticles but also for nanoplates was obtained, suggesting that "oriented attachment" is an intrinsic behavior for nanosized materials. According to the growth model proposed based on the direct TEM observations, ZnO nanocrystals can be easily controlled as nanoparticles, nanoplates, or nanowires by tuning the synthetic parameters.

Journal Article↗
PubMed2005

Field-induced magnetic transitions in metal phosphonates with ladderlike chain structures: (NH3C6H4NH3)M2(hedpH)2.H2O [M = Fe, Co, Mn, Zn; hedp = C(CH3)(OH)(PO3)2].

This paper reports the syntheses and characterization of four isomorphous compounds (NH(3)C(6)H(4)NH(3))M(2)(hedpH)(2).H(2)O [M = Fe (1), Co (2), Mn (3), Zn (4); hedp = C(CH(3))(OH)(PO(3))(2)]. Each contains two crystallographically different kinds of {M(2)(hedpH)(2)}(n) double chains, where the {M(2)(mu-O)(2)} dimer units are connected by O-P-O bridges. The double chains are connected through extensive hydrogen bonds, hence generating a three-dimensional supramolecular network. The temperature-dependent magnetic susceptibility measurements show dominant antiferromagnetic interactions in compounds 1-3, mediated through the mu-O and/or O-P-O bridges between the metal(II) centers. The magnetization measurements reveal that compounds 1-3 experience field-induced magnetic transitions at low temperatures.

Journal Article↗
PubMed2005

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↗
PubMed2005

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↗
PubMed2005

Selective synthesis of monazite- and zircon-type LaVO(4) nanocrystals.

Pure monoclinic (m-) and tetragonal phased (t-) LaVO(4) nanocrystals could be obtained by a hydrothermal method in a controllable way with additives. It is found that chelating ligands, such as ethylenediaminetetraacetic acid [EDTA or H(4)L, where L(4-) = (CH(2)COO)(2)N(CH(2))(2)N(CH(2)COO)(2)(4-)], favor the formation of t-LaVO(4) and can induce the polymorph transformation from stable m-LaVO(4) to metastable t-LaVO(4). Further studies demonstrated the important roles of chelating ligands in this transformation process. Careful investigation over the phase transition from t- to m-LaVO(4) was also conducted with high-temperature X-ray diffraction (HTXRD) studies. The phase transition occurred at 850 degrees C, which is about 250 degrees C higher than for the bulk. The enhanced thermal stability of the nanosized metastable t-LaVO(4) may come from the small size effect. Our capability of obtaining and stabilizing t-LaVO(4) not only benefits the wider applications based on LaVO(4) due to the improved luminescent and catalytic performance but also provides a new idea in the studies of polymorph control and selective synthesis of inorganic materials.

Journal Article↗
PubMed2005

Coordination polymers based on inorganic lanthanide(II) sulfate skeletons and an organic isonicotinate N-oxide connector: segregation into three structural types by the lanthanide contraction effect.

Fourteen three-dimensional coordination polymers of general formula [Ln(lNO)(H2O)(SO4)]n, where Ln = La, 1.La; Ce, 2.Ce; Pr, 3.Pr; Nd, 4.Nd; Sm, 5.Sm; Eu, 6.Eu; Gd, 7.Gd; Tb, 8.Tb; Dy, 9.Dy; Ho, 10.Ho; Er. 11.Er; Tm, 12.Tm; Yb, 13.Yb; and Lu, 14.Lu; INO = isonicotinate-N-oxide, have been synthesized by hydrothermal reactions of Ln3+, MnCO3, MnSO4 x H2O, and isonicotinic acid N-oxide (HINO) at 155 degrees C and characterized by single-crystal X-ray diffraction, IR, thermal analysis, luminescence spectroscopy, and the magnetic measurement. The structures are formed by connection of layer, chain, or dimer of Ln-SO4 by the organic connector, INO. They belong to three structural types that are governed exclusively by the size of the ions: type I for the large ions, La, Ce, and Pr; type II for the medium ions, Nd, Sm, Eu, Gd, and Tb; and type III for the small ions, Dy, Ho, Er, Tm, Yb, and Lu. Type I consists of two-dimensional undulate Ln-sulfate layers pillared by INO to form a three-dimensional network. Type II has a 2-fold interpenetration of "3D herringbone" networks, in which the catenation is sustained by extensive pi-pi interactions and O-H...O and C-H...O hydrogen bonds. Type III comprises one-dimensional chains that are connected by INO bridges, resulting in an alpha-Po network. The progressive structural change is due to the metal coordination number decreasing from nine for the large ions via eight to seven for the small ions, demonstrating clearly the effect of lanthanide contraction. The sulfate ion acts as a micro4- or micro3-bridge, connecting two, three, or four metals, and is both mono- and bidentate. The INO ligand acts as a micro3- or micro2-bridge with carboxylate group in syn-syn bridging or bidentate chelating mode. The materials show considerably high thermal stability. The magnetic properties of 4.Nd, 6.Eu, 7.Gd, and 13.Yb and the luminescence properties of 6.Eu and 8.Tb are also investigated.

Journal Article↗