In Situ Heating TEM Study of Onion-like WS2 and MoS2 Nanostructures Obtained via MOCVD

We report on the in situ heating transmission electron microscopy (TEM) study of WS2 and MoS2 nanoparticles obtained from metal–organic chemical vapor deposition (MOCVD). The general behavior of MoS2 and WS2 is similar: Round, amorphous particles in the pristine sample transform to hollow, onion-like particles upon annealing. A second type of particle with straight layers exhibits only minor changes. A significant difference between both compounds could be demonstrated in their crystallization behavior. The results of the in situ heating experiments are compared to those obtained from an ex situ annealing process under Ar.

Bismuth-Catalyzed Growth of SnS2 Nanotubes and Their Stability

Perovskite solar cells employing organic charge-transport layers

Thin-film photovoltaics play an important role in the quest for clean renewable energy. Recently, methylammonium lead halide perovskites were identified as promising absorbers for solar cells(1). In the three years since, the performance of perovskite-based solar cells has improved rapidly to reach efficiencies as high as 15%(1-10). To date, all high-efficiency perovskite solar cells reported make use of a (mesoscopic) metal oxide, such as Al2O3, TiO2, or ZrO2, which requires a high-temperature sintering process. Here, we show that methylammonium lead iodide perovskite layers, when sandwiched between two thin organic charge-transporting layers, also lead to solar cells with high power-conve…

Synthetic Approaches to Functionalized Chalcogenide Nanotubes

Reversible Selbstorganisation von Metallchalkogenid-Metalloxid- Nanostrukturen basierend auf dem Pearson-Konzept

&Titel gek rzt. OK?& Die Nanotechnologie hat ein Entwicklungsstadium erreicht, in dem nicht mehr einzelne Nanopartikel, sondern komplexere Systeme im Fokus des Interesses stehen. Solche Strukturen bestehen aus zwei oder mehr unterschiedlichen Materialien, wie Metall-HalbleiterHybride, die die Eigenschaften beider Materialien effektiv vereinen. Der Aufbau von Nanopartikeln aus mehreren Komponenten mit unterschiedlichen optischen, elektronischen, magnetischen oder chemischen Eigenschaften kann zu neuartigen Funktionalit ten f hren, die unabh ngig von den einzelnen Komponenten masgeschneidert werden k nnen, um spezifischen Anforderungen zu gen gen. M gliche Anwendungen liegen in Gebieten wie d…

Reversible self-assembly of metal chalcogenide/metal oxide nanostructures based on Pearson hardness.

Nanotechnology has reached a stage of development where not individual nanoparticles but rather systems of greater complexity are the focus of concern. These complex structures incorporate two or more types of materials, an example of which is the formation of metal–semiconductor hybrids, which effectively combine the properties of both materials. The assembly of multicomponent nanoparticles from constituents with different optical, electrical, magnetic, and chemical properties can lead to novel functionalities that are independent of the individual components and may be tailored to fit a specific application. These applications include such far-reaching challenges as solar energy conversio…

ChemInform Abstract: Synthesis and Functionalization of Chalcogenide Nanotubes

New synthetic approaches to MS 2 (M = Sn, Nb, Mo, W) chalcogenide nanostructures are highlighted. Most chalcogenide particles can be functionalized directly with inorganic nanoparticles such as Au, ZnO or MnO. Depending on the Pearson hardness of the metal involved, the functionalization may be reversible or irreversible. A covalent functionalization strategy is based on a steric shielding of the coordination sphere of transition metal atoms in such a way that only coordination sites are available for bonding to the chalcogenide surface. This allows the immobilization of fluorophors, redox active groups or proteins onto chalcogenide nanoparticle.

Synthesis, characterization, and hierarchical organization of tungsten oxide nanorods: spreading driven by Marangoni flow.

Tungsten oxide nanorods were synthesized by a soft chemistry approach using tungsten alkoxide and trioctyl amine and oleic acid as the surfactants. The optical properties of the nanorods were studied. The nanorods were found to be soluble in a wide range of solvents like chloroform, cyclohexane, and so on. Upon solvent evaporation, the nanorods formed hierarchically organized solid state structures. Depending on the solvent used, the nanorods organized in different mesostructures. Moreover, the organization of the nanorods from mixtures of polar and nonpolar solvents was studied. Here, the Marangoni effect resulting from differences in the surface tensions of the two solvents was found to p…

Synthesis and functionalization of chalcogenide nanotubes

New synthetic approaches to MS 2 (M = Sn, Nb, Mo, W) chalcogenide nanostructures are highlighted. Most chalcogenide particles can be functionalized directly with inorganic nanoparticles such as Au, ZnO or MnO. Depending on the Pearson hardness of the metal involved, the functionalization may be reversible or irreversible. A covalent functionalization strategy is based on a steric shielding of the coordination sphere of transition metal atoms in such a way that only coordination sites are available for bonding to the chalcogenide surface. This allows the immobilization of fluorophors, redox active groups or proteins onto chalcogenide nanoparticle.

Titelbild: Reversible Selbstorganisation von Metallchalkogenid-Metalloxid- Nanostrukturen basierend auf dem Pearson-Konzept (Angew. Chem. 41/2010)

Low melting Metal Catalysed Growth of Tin Disulfide Nanotubes

AbstractWe report here the synthesis of tin disulfide nanotubes by a vapour liquid solid growth using bismuth, a low melting metal, as a catalyst. The reaction was carried out in a single step process by heating SnS2 and bismuth in a horizontal tube furnace at 800oC. TEM analysis allowed proposing a plausible mechanism for the formation of SnS2 nanotubes. Pure material could be obtained by optimizing the reaction based on a product analysis using powder X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) combined with energy dispersive X-ray spectroscopy (EDX).

Asymmetric tungsten oxide nanobrushes via oriented attachment and Ostwald ripening

Tungsten oxide nanobrushes were synthesized using a solvothermal approach that lead to self-branching in the presence of citric acid and hexadecylamine as surfactants. Our synthetic approach yielded branched nanorods of tungsten oxide in a single synthetic step. Based on our results, we propose a phenomenological pathway for the formation, branching, and assembly of these tungsten oxide brushes. The formation of tungsten oxide brushes proceeds by thermal decomposition of ammonium tungstate in the presence of citric acid and hexadecylamine. The pale blue powder obtained after solvothermal reaction was analyzed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolu…

Enzyme-Mediated Deposition of a TiO2Coating onto Biofunctionalized WS2 Chalcogenide Nanotubes

A chemically specific and facile method for the biofunctionalization of WS2 nanotubes (NT-WS2) is reported. The covalent modification strategy is based on the affinity of the nitrilotriacetic acid (NTA) side chain, which serves as a ligand for the surface binding to NT-WS2 and simultaneously as an anchor group for the binding of His-tagged proteins to the polymer backbone. The polymer functionalized WS2 nanotubes can be solubilized either in water or organic solvents; they are stable for at least one week. The probes were characterized by FT-IR and UV-vis spectroscopy. The immobilization of silicatein, a hydrolytic protein encountered in marine sponges, was visualized by scanning force micr…

Snapshots of the Formation of Inorganic MoS2 Onion-Type Fullerenes: A “Shrinking Giant Bubble” Pathway

ChemInform Abstract: Large Scale MOCVD Synthesis of Hollow ReS2Nanoparticles with Nested Fullerene-Like Structure.

Bismut-katalysiertes Wachstum von SnS2-Nanoröhren und deren Stabilität

Synthesis of Hierarchically Grown ZnO@NT-WS2 Nanocomposites

A chemically specific and facile method for growth of ZnO nanorods on WS2 nanotubes (NT-WS2) is reported. The modification strategy is based on the chalcophilic affinity of Zn, which serves as an anchor to immobilize ZnO colloids onto the WS2 nanotubes. The surface bound ZnO colloids have been used as a seed to grow ZnO nanorods on WS2 nanotubes. The immobilization of ZnO colloids was monitored by UV−vis spectroscopy and photoluminescence spectroscopy whereas the growth of ZnO nanorods was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

Cover Picture: Reversible Self-Assembly of Metal Chalcogenide/Metal Oxide Nanostructures Based on Pearson Hardness (Angew. Chem. Int. Ed. 41/2010)

Soluble IF-ReS2 nanoparticles by surface functionalization with terpyridine ligands.

A major drawback in the application of layered chalcogenide nanoparticles/tubes is their inertness to chemical and biological modification and functionalization. Their potential use in composite materials might be greatly enhanced by improving the chalcogenide/matrix interface bonding. A novel modification strategy for layered chalcogenide nanoparticles based on the chalcophilic affinity of metals and the chelating terpyridine is reported. The terpyridine anchor group can be conjugated to fluorescent tags or hydrophilic/hydrophobic groups that confer solubility in various solvents to the otherwise insoluble chalcogenide nanoparticles. The functionalized particles are characterized using TEM…

Mechanische Spannung und Valenzabsättigung in Konkurrenz: Nano-Münzrollen aus Stapeln nanoskaliger Schichten

Graphene-type sheets of Nb(1-x)W(x)S2: synthesis and in situ functionalization.

Enlightened by the discovery of graphenes, a variety of inorganic analogues have been synthesized and characterized in recent years. Solvated Nb1−xWxS2 analogues of graphene-type sheets were prepared by lithiation and exfoliation of multistacked Nb1−xWxS2 coin roll nanowires (CRNWs), followed by in situ functionalization with gold nanoparticles to synthesize gold-loaded Nb1−xWxS2/Au nanocomposites. The Nb1−xWxS2 nanosheets and the corresponding Nb1−xWxS2/Au nanocomposites were characterized by high resolution electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX), scanning transmission electron microscopy (STEM), dynamic light scattering (DLS) and scanning force microscopy …

From Single Molecules to Nanoscopically Structured Materials: Self-Assembly of Metal Chalcogenide/Metal Oxide Nanostructures Based on the Degree of Pearson Hardness

A chemically specific and facile method for the immobilization of metal oxide nanoparticles onto the surface of IF-MoS2 nested fullerenes is reported. The modification strategy is based on the chalcophilic affinity of transition metals such as Fe2+/Fe3+, Fe3+, or Zn2+ as described by the Pearson HSAB concept. The binding capabilities of the 3d metals are dictated by their Pearson hardness. Pearson hard cations such as Fe3+ (Fe2O3) do not bind to the chalcogenide surfaces; borderline metals such as Fe2+ (Fe3O4) or Zn2+ (ZnO) bind reversibly. Pearson-soft metals like Au bind irreversibly. The immobilization of metal oxide nanoparticle colloids was monitored by transmission electron microscopy…

Synthesis of Fullerene- and Nanotube-Like SnS2 Nanoparticles and Sn/S/Carbon Nanocomposites

SnS2 nested fullerene-type (IF) nanoparticles, nanotubes, and SnS2/C hybrid nanostructures were obtained by vapor transport starting from elemental tin and CS2. The reaction was carried out in a single-step process by heating elemental tin metal powder in a horizontal tube furnace at 800−1000 °C. TEM analysis allowed proposing a plausible mechanism for the formation of fullerene-like particles of SnS2 as well as tubes and scrolls from nanosheets of SnS2. Pure material could be obtained by optimizing the reaction based on a product analysis using powder X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) combined with energy-dispersive X-ray spectroscopy (EDX…

IF-ReS2 with Covalently Linked Porphyrin Antennae

The preparation of inorganic and organic hybrid materials, of metals or semiconductor systems which are functionalized with functional molecules to fabricate devices — nanotechnology — is currently an area of intense activity in both fundamental science and applied science on an international scale. Principally, nanotechnology aims at manipulating atoms, molecules, and nanosize particles in a precise and controlled manner in order to build materials with a fundamentally new organization and novel properties. The embryonic stage of nanotechnology is atomic assembly, whereas the mature form of nanotechnology will be molecular assembly to make nano-building blocks for the design of nanocomposi…

Large Scale MOCVD Synthesis of Hollow ReS2 Nanoparticles with Nested Fullerene-Like Structure

The synthesis of ReS2 onionlike nanoparticles by means of a high-temperature MOCVD process starting from Re2(CO)10 and elemental sulfur is reported. The reaction is carried out in a two-step proces...

Mismatch strain versus dangling bonds: formation of "coin-roll nanowires" by stacking nanosheets.

Diffusion-Driven Formation of MoS2 Nanotube Bundles Containing MoS2 Nanopods

MoS2 nanotube bundles, along with embedded nested fullerenes, were formed in a gas-phase reaction of molybdenum carbonyl and H2S gas with the assistance of I2. The amorphous Mo-S-I precursor particles obtained by quenching a modified metal organic chemical vapor deposition (MOCVD) reaction in a large temperature gradient were annealed at elevated temperature in an inert atmosphere. Under the influence of the iodine, the amorphous precursor formed a surface film with an enhanced mobility of the molybdenum and sulfur components. Point defects within the MoS2 layers, combined with the enhanced surface diffusion, lead to a scrolling of the inherently unstable MoS2 lamellae. The role of the reac…