Metal nanocrystals with highly branched morphologies

Metal nanocrystals with highly branched morphologies are an exciting new class of nanomaterials owing to their unique structures, physicochemical properties, and great potential as catalysts, sensing materials, and building blocks for nanoscale devices. Various strategies have recently been developed for the solution-phase synthesis of metal nanocrystals with branched morphologies, such as multipods and nanodendrites. In this Minireview, the procedures and mechanisms underlying the formation of branched metal nanocrystals are presented in parallel with recent advances in synthetic approaches based on kinetically controlled overgrowth, aggregation-based growth, heterogeneous seeded growth, selective etching, and template-directed methods, as well as their properties for catalytic or electrocatalytic applications.     

Controllable synthesis of nickel hydroxide and porous nickel oxide nanostructures with different morphologies

Alpha-Ni(OH)(2) nanobelts, nanowires, short nanowires, and beta-Ni(OH)(2) nanoplates have been successfully prepared in high yields and purities by a convenient hydrothermal method under mild conditions from very simple systems composed only of NaOH, NiSO(4), and water. It has been found that the ratio of NaOH to NiSO(4) not only affects the morphology of the Ni(OH)(2) nanostructures, but also determines whether the product is of the alpha- or beta-crystal phase. A notable finding is that porous NiO nanobelts were produced after exposure of the Ni(OH)(2) products to an electron beam for several minutes during transmission electron microscopy (TEM) observations. Another unusual feature is that rectangular nanoplates with many gaps were obtained. Furthermore, porous NiO nanobelts, nanowires, and nanoplates could also be obtained by annealing the as-prepared Ni(OH)(2) products. A sequence of dissolution, recrystallization, and oriented attachment-assisted self-assembly of nanowires into nanobelts is proposed as a plausible mechanistic interpretation for the formation of the observed structures. The method presented here possesses several advantages, including high yields, high purities, low cost, and environmental benignity. It might feasibly be scaled-up for industrial mass production.     

Chemical synthesis, structural characterization, optical properties, and photocatalytic activity of ultrathin ZnSe nanorods

Ultrathin ZnSe nanorods in the cubic phase have been synthesized by the reaction of selenium and zinc oleate for 30 min at 240 °C. These nanorods showed an average diameter of 2.4 nm, which is much smaller than the Bohr size of bulk ZnSe. Thus, they exhibited a remarkable quantum size effect in terms of their optical properties. The formation of the ultrathin nanorods could be attributed to the oriented attachment mechanism, which was supported by the structure of the nanorods and the control experiments. The ultrathin nanorods were transferred into an aqueous solution by ligand exchange. The performance of these nanorods as a catalyst was examined, using the photodegradation of methyl orange as a model reaction. It was found that the ultrathin nanorods possessed better photocatalytic activities than conventional ones.     

Synthesis of Ag2O nanocrystals with systematic shape evolution from cubic to hexapod structures and their surface properties

We report the development of a facile method for the synthesis of Ag(2)O crystals with systematic shape evolution from cubic to edge- and corner-truncated cubic, rhombicuboctahedral, edge- and corner-truncated octahedral, octahedral, and hexapod structures by mixing AgNO(3), NH(4)NO(3), and NaOH at molar ratios of 1:2:11.8. A sufficient volume of NaOH solution was first added to a mixture of AgNO(3) and NH(4)NO(3) solution to promote the formation of Ag(NH(3))(2)(+) complex ions and the growth of Ag(2)O nanocrystals with good morphological control. The crystals are mostly submicrometer-sized. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy characterization has been performed to determine the crystalline surface facets. A band gap value of approximately 1.45 eV has been found for the octahedral Ag(2)O crystals. By changing the molar ratios of AgNO(3)/NH(4)NO(3)/NaOH to 1:2:41.8, corner-depressed rhombicuboctahedra and elongated hexapods were obtained as a result of enhanced crystal growth along the [100] directions. Smaller nanocubes with average sizes of approximately 200 and 300 nm and octapods can also be prepared by adjusting the reagent molar ratios and their added volumes. Both the octahedra and hexapods with largely silver atom-terminated {111} surface facets responded repulsively and moved to the surface of the solution when dispersing in a solution of positively charged methylene blue, but can be suspended in a negatively charged methyl orange solution. The cubes and octapods, bounded by the {100} faces, were insensitive to the molecular charges in solution. The dramatic facet-dependent surface properties of Ag(2)O crystals have been demonstrated.     

Crystal overgrowth on gold nanorods: tuning the shape, facet, aspect ratio, and composition of the nanorods

Electrochemically prepared Au nanorods were used as seeds for the overgrowth of thin shells of gold, silver, and palladium by using a mild reducing agent, ascorbic acid, in the presence of surfactants at ambient condition. The unique crystal facets of the starting nanorods results in anisotropic crystal overgrowth. The overgrowth rates along different crystallographical directions can be further regulated by adding foreign ions or by using different metal reduction methods. This overgrowth study provides insights on how different metal ions could be reduced preferentially on different Au nanorod surfaces, so that the composition, aspect ratio, shape, and facet of the resulting nanostructures can be rationally tuned. These surfactant-stabilized bimetallic Au(core)M(shell) (M=Au, Ag, Pd) nanorod colloids might serve as better substrates in surface-enhanced Raman spectroscopy as well as exhibiting enhanced catalytic properties.     

Selective synthesis of Fe7Se8 polyhedra with exposed high-index facets and Fe7Se8 nanorods by a solvothermal process in a binary solution and their collective intrinsic properties

Fe(7)Se(8) polyhedra with high-index facets and Fe(7)Se(8) nanorods can be selectively synthesized by a solvothermal reaction in a mixed solvent of diethylenetriamine (DETA) and deionized water (DIW). It is found that the morphologies of Fe(7)Se(8) nanocrystals can be effectively controlled by adjusting the volume ratio of DETA and DIW. The unusual polyhedral crystals are bounded by two {001} and twelve {012} facets. The intrinsic properties of Fe(7)Se(8) nanocrystals have been investigated. Magnetic measurements indicate that the obtained polyhedra and nanorods show a weak ferromagnetic ordering at room temperature. In particular, a new photoluminescence emission at 403 nm from the Fe(7)Se(8) nanocrystals has been observed. The described solvothermal reaction in a mixed solvent may be extended to the synthesis of other transition-metal chalcogenide crystals with controlled shape, facets, and structure, which may bring new functionalities.     

One-pot aqueous solution syntheses of iron oxide nanostructures with controlled crystal phases through a microbial-mineralization-inspired approach

Iron-oxidizing bacteria produce trivalent iron oxides with the controlled crystal phases outside of their cells. Herein we have synthesized iron oxides with controlled oxidation states and crystal phases through a microbial-mineralization-inspired approach in an aqueous solution at low temperature. Trivalent iron oxides, such as lepidocrocite, ferrihydrite, goethite, and hematite, are selectively obtained from an aqueous solution containing divalent iron ions below 90 °C. The presence of a chelating agent facilitates the control of the oxidation states through the ligand-controlled approach because the precipitation of the divalent iron species is inhibited by the complexation between divalent iron ion and a chelating agent. The control of the crystal phases is achieved by the tuning of the synthetic conditions, such as the initial pH, the concentration of a chelating agent, and the reaction temperature. Furthermore, the resultant iron oxides have hierarchically organized structures consisting of nanoscale objects. The microbial-mineralization-inspired approach by using a chelating agent has potentials for the further morphological control of iron oxides and the further application to aqueous-solution syntheses of other metal oxides.     

BiOCl nanostructures with different morphologies: Tunable synthesis and visible-light-driven photocatalytic properties

BiOCl nanostructures including microspheres,microflowers,microplates,and nanoplates,have been synthesized by a simple solvothermal method using bismuth nitrate and sodium chloride as raw materials without adding any additives.Structure and morphology of the products were characterized by powder X-ray diffraction,scanning electron microscopy,and transmission electron microscopy.The results indicated that the as-prepared microspheres and microflowers were composed of nanosheets.Although with different shape and lateral size,the nanoplates and microplales were all single-crystalline plates with exposed {001) facets.It was found that the volume ratio of polyethylene glycol 400 and H₂O in the solvent played a key role in the morphology of the products,and the possible growth mechanism was also discussed.The photocatalytic measurements indicated that the BiOCl samples exhibit good photocatalytic properties towards Rhodamine B.     

Sb2S3 with various nanostructures: controllable synthesis, formation mechanism, and electrochemical performance toward lithium storage

The size- and shape-controlled synthesis of Sb(2)S(3) nanostructures has been successfully realized by a facile hydrothermal route. A range of dimensional nanostructures, such as one-dimensional nanorods, two-dimensional nanowire bundles, three dimensional sheaf-like superstructures, dumbbell-shaped superstructures, and urchin-like microspheres, could be obtained through introducing different organic complex reagents or ionic liquids to the reaction system. The formation mechanisms of various Sb(2)S(3) nanostructures have been rationally proposed based on the crystal structure and the nature of the complex reagents and the ionic liquid. The effects of experimental parameters on the final product are also discussed in detail. In addition, electrochemical measurements demonstrate that the as-synthesized Sb(2)S(3) nanostructures have higher initial Li intercalation capacity and excellent cyclic performances, which indicates that the as-synthesized Sb(2)S(3) nanostructures could have potential applications in commercial batteries.     

Aqueous-solution growth of GaP and InP nanowires: a general route to phosphide, oxide, sulfide, and tungstate nanowires

A general synthetic route has been developed for the growth of metal phosphide, oxide, sulfide, and tungstate nanowires in aqueous solution. In detail, cetyltrimethylammonium cations (CTA(+)) can be combined with anionic inorganic species along a co-condensation mechanism to form lamellar inorganic-surfactant intercalated mesostructures, which serve as both microreactors and reactants for the growth of nanowires. For example, GaP, InP, gamma-MnO(2), ZnO, SnS(2), ZnS, CdWO(4), and ZnWO(4) nanowires have been grown by this route. To the best of our knowledge, this is the first time that the synthesis of GaP and InP nanowires in aqueous solution has been achieved. This strategy is expected to extend to grow nanowires of other materials in solution or by vapor transport routes, since the nanowire growth of any inorganic materials can be realized by selecting an appropriate reaction and its corresponding lamellar inorganic-surfactant precursors.     

Controlled synthesis of ZnO with adjustable morphologies from nanosheets to microspheres

The synthesis of ZnO with different morphologies (hexagonal prisms, nanosheets, microspheres and quasi-flowers) was realized through a solvothermal method. During the synthetic procedure, the decomposition of hexamethylenetetramine at the temperature ≥100 °C provided (OH)⁻¹ ions at the rate of good distribution, and sodium dodecyl sulfate was used as templates. By adjusting the basicity in the synthetic system, ZnO nanosheets, or microspheres with nanosheet assemblies were obtained. Adjusting the concentration of surfactant, ZnO hexagonal crystals were formed; by adjusting the synthetic temperature, ZnO quasi-flowers with some nanosheet assemblies were produced. Based on experimental observation and analysis, the forming mechanism was discussed.     

Facile shape and size-controlled growth of uniform magnetite and hematite nanocrystals with tunable properties

Monodispersed magnetite Fe3O4 and hematite α-Fe2O3 nanocrystals have been grown in co-solvents of alcohol and water. Either the shape or the size of the nanocrystals could be easily controlled. Both the phases and nanostructures have been characterized by powder X-ray diffraction patterns and electron microscopy. The magnetic and catalytic properties of these products were investigated and compared with each other. The obtained results clearly demonstrate that these iron oxide nanocrystals are soft ferromag...     

Linked crystallites in the conducting topmost layer of polymer bilayer films controlled by temperature: from micro- to nanocrystallites.

Temperature has great impact on the structure and size of the linked crystallites of the conducting topmost layer formed at the surface of a polycarbonate film via the reaction BEDT-TTF+IBr [BEDT-TTF=bis(ethylenedithio)tetrathiafulvalene]. We show that fine temperature control permits formation of a semiconducting topmost layer of alpha'-(BEDT-TTF)(2)(I(x)Br(1-x))(3) crystallites with either micro- or nanometre size, a result that opens a route to miniaturized conducting plastic materials.     

Ternary Chlorides of the Trivalent Early Lanthanides. Phase diagrams,crystal structures and thermodynamic properties

A comprehensive review on phase diagrams, crystal structures and thermodynamics of ternary chlorides formed in systems ACl/LnCl₃ (A=Cs, Rb, K, Na; Ln=La−Gd) is presented. The review summarizes the author’s own studies, published since 1985, and original papers of other scientists. With the larger alkali metal ions compounds such as A₃LnCl₆, A₂LnCl₅ and ALn₂Cl₇were obtained. With sodium additional compounds NaLnCl₄ and Na₃Ln₅Cl₁₈ were obtained. The crystal structures are discussed with the concept of ionic radii, which determine the coordination numbers of Ln³⁺ and A⁺ cations against Cl⁻ anions. The formation enthalpies of the compounds from ACl and LnCl₃ were determined by solution calorimetry. Gibbs’ free energies and entropies for these reactions were obtained by e.m.f. measurements vs. temperature. The stability of a ternary chloride in a systemACl−LnCl₃ is given by the ‘free enthalpy of synproportionation’, that is, the formation of a compound from its neighbour compounds in the system. This ΔG ⁰ _syn must be negative. A surprising result is, that the highest-melting compounds in the systems, A₃LnCl₆, are formed from ACl+A₂LnCl₅ by a loss in lattice energy. They exist as high-temperature compounds due to sufficiently high gain in entropy at temperatures whereTΔS>ΔH. This revised version was published online in August 2006 with corrections to the Cover Date.     

Single‐Crystalline and Near‐Monodispersed NaMF3 (M=Mn,Co, Ni,Mg) and LiMAlF6 (M=Ca,Sr) Nanocrystals from Cothermolysis of Multiple Trifluoroacetates in Solution

We report the synthesis of single‐crystalline and near‐monodispersed NaMF₃ (M=Mn, Co, Ni, Mg), LiMAlF₆ (M=Ca, Sr), and NaMgF₃:Yb,Er nanocrystals (quasisquare nanoplates, nanorods, and nanopolygons) by the cothermolysis of multiple trifluoroacetates in hot combined organic solvents (oleic acid, oleylamine, and 1‐octadecene). The nanocrystals were characterized by XRD, TEM, superconductive quantum interference device (SQUID), and upconversion luminescence spectroscopy. By regulating the polarity of the dispersant, the NaMF₃ (M=Mn, Co, Ni) nanoplates were partially aligned to form nanoarrays on copper TEM grids. The sizes of the NaMF₃ nanocrystals were easily tuned by the use of proper synthetic conditions such as reaction temperature and time and solvent composition. On the basis of a series of experiments in which the reaction conditions were varied, together with GC–MS and FTIR analysis, the reaction pathways for the formation of these nanocrystals from trifluoroacetate precursors were proposed. The magnetic measurements showed that the differently sized NaMnF₃ square plates displayed interesting weak ferromagnetic behavior on the nanometer scale. The strong red upconversion luminescence emitted from the NaMgF₃:Yb,Er nanorods under 980‐nm near‐IR laser excitation suggests that NaMgF₃ may be a good candidate host material for red upconversion luminescence.     

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.