Orthorhombic Bi2S3 Research Articles

Low temperature hydrothermal synthesis of Bi2S3 nanorods using BiOI nanosheets as self-sacrificing templates

The synthesis of one-dimension (1D) Bi2S3 nanorods has been successfully achieved through the transformation of BiOI nanosheets at low hydrothermal temperature. Their crystallization, structure and morphology transformation processes were characterized in detail. Crystallite (Bi(Bi2S3)9I3)0.6667 nanorods were identified as intermediate products in the process, and they were chemically etched and split during the hydrothermal reaction into narrower Bi2S3 nanorods, which tend to bundle together with diameters range from 40 to 100nm and lengths up to ∼800nm. The possible transformation process of tetragonal BiOI nanosheets to orthorhombic Bi2S3 nanorods was investigated to better understand the potential application of this view for constructing novel nanostructures.

A general method for the large-scale synthesis of uniform ultrathin metal sulphide nanocrystals

Ultrathin metal sulphide nanomaterials exhibit many unique properties, and are thus attractive materials for numerous applications. However, the high-yield, large-scale synthesis of well-defined ultrathin metal sulphide nanostructures by a general and facile wet-chemical method is yet to be realized. Here we report a universal soft colloidal templating strategy for the synthesis of high-quality ultrathin metal sulphide nanocrystals, that is 3.2 nm-thick hexagonal CuS nanosheets, 1.8 nm-diameter hexagonal ZnS nanowires, 1.2 nm-diameter orthorhombic Bi(2)S(3) nanowires and 1.8 nm-diameter orthorhombic Sb(2)S(3) nanowires. As a proof of concept, the ultrathin CuS nanosheets are used to fabricate an electrode for a lithium-ion battery, which exhibits a large capacity and good cycling stability, even after 360 cycles. Furthermore, high-yield, gram-scale production of these ultrathin metal sulphide nanomaterials has been achieved (~100%, without size-sorting process). Our method could be broadly applicable for the high-yield production of novel ultrathin nanostructures with great promise for various applications.

Controlling morphologies of Bi2S3 nanostructures synthesized by glycolthermal method

Single crystalline orthorhombic Bi2S3 nanostructures with different morphologies were synthesized by the 180°C and 12h glycolthermal reactions, using ethylene glycol, propylene glycol and polyethylene glycol with different molecular weights as solvents. The as-synthesized products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), and selected area electron diffraction (SAED). In the present research, different solvents played the role in the product morphologies. A formation mechanism of Bi2S3 nanostructures was also proposed.

Preparation and characterization of CdS–Bi2S3 nanocomposite thin film by successive ionic layer adsorption and reaction (SILAR) method

CdS, Bi2S3 and CdS–Bi2S3 nanocomposite thin films were grown by successive ionic layer adsorption and reaction method (SILAR) onto the glass substrates at room temperature. These films were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and electrical measurement systems. A comparative study was made between CdS, Bi2S3 and CdS–Bi2S3 nanocomposite thin films. The XRD patterns reveal that CdS, Bi2S3 and CdS–Bi2S3 nanocomposite thin film have hexagonal, orthorhombic and mixed phase of hexagonal CdS and orthorhombic Bi2S3 crystal structure, respectively. SEM images showed uniform deposition of the material over the entire glass substrate. The energy band gap for CdS, Bi2S3 and CdS–Bi2S3 thin films were revealed from the optical studies and were found to be 2.4, 1.6 and 1.69eV, respectively. The thermoemf measurements of CdS–Bi2S3 nanocomposite thin film revealed n-type electrical conductivity, while the I–V measurement of CdS, Bi2S3 and CdS–Bi2S3 nanocomposite thin film under dark and illumination condition (100mW/cm2) exhibited photoconductivity phenomena suggesting its applicability in photosensors devices.

Single-Source Route to Bi2S3 Nanorods and their Electrochemical Sensing Properties

A simple and environmentally benign process for the synthesis of Bi2S3 nanorods and their electrochemical sensing properties are desirable to be developed in electrochemical sensor application. Orthorhombic Bi2S3 nanorods have been synthesized via a singlesource approach using bismuth diethyldithiocarbamate as the precursor under hydrothermal conditions. The products were characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, IR, UV-vis spectra and electrochemical sensing analysis. The decomposition of the complex bismuth diethyldithiocarbamate produces Bi2S3 nanorods with the average diameter of about 80 nm and length of less than 5 μm. The electrochemical responses of Bi2S3 nanorod modified glassy carbon electrode to cysteine and ascorbic acid are greatly enhanced suggesting that hydrogen ions participate in the electrochemical oxidation process. The electrochemical results demonstrated that the Bi2S3 nanorods are expected to have great potential as the electrochemical sensing cell for detecting cysteine and ascorbic acid. Keywords: Bi2S3 nanaorods, hydrothermal decomposition, electrochemical sensing properties, single-source route, scanning electron microscopy, transmission electron microscopy, photoluminescence spectrum, X-ray

Synthesis and characterization of thiosemicarbazone derivatives of methylbismuth(III) dichloride: generation of one dimensional micro-rods of bismuthinite from [MeBiCl2·n{(C6H4OH)CHNNHCSNH2}] by a solvothermal process

Reactions of methylbismuth(III) dichloride with thiosemicarbazones (TSC) in 1:1 and 1:2 molar ratios in anhydrous methanol yield [MeBiCl2.n{RR’CNNHCSNH2}] [where, R=R’=CH3 and n=1 (1) or n=2 (2); R=C6H4OH, R’=H and n=1 (3) or n=2 (4); R=C5H4N, R’=CH3 and n=1 (5) or n=2 (6)]. These monomeric adducts have been characterized by elemental analyses, Fourier transform infrared, nuclear magnetic resonance [1H, 13C{1H}] and fast atom bombardment mass spectrometry. The ligand appears to bind bismuth through sulfur and azomethine nitrogen atoms rendering penta- and hepta- coordination geometries, in (1, 3 and 5) and (2, 4 and 6), respectively, in the solution state. Low temperature (143–145°C) solvothermal transformation of (3) or (4) in refluxing xylene yields nano-structured flowers of amorphous bismuthinite (Bi2S3). Prolonged (~10 h) sintering at 150°C of the powder obtained from (4) yielded one-dimensional micro/nanorods of orthorhombic Bi2S3. All the materials were characterized by X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray analyses.

Morphology Controlled Synthesis of Spherical Bi<SUB>2</SUB>S<SUB>3</SUB> Flowers

The spherical Bi2S3 flowers have been fabricated by a facile environmentally friendly hydrothermal method. It was found that the flowers are composed of pure orthorhombic phase Bi2S3, the nanorods (nanowires) composed of the flowers grow radically from a center toward all directions to form a spherical structure, and the nanowires are single-crystalline and grow along the [001] direction. The reaction time, reaction temperature and thiourea play key roles for the formation of the flowers. The morphology of the Bi2S3 flowers (e.g., honeycombs, porous nanorods, nanorods, and nanowires) can be controlled simply by controlling the reaction time without varying experimental parameters or addition of other surfactant. The formation mechanism of Bi2S3 flowers is self-assembly and the intrinsic splitting character of the Bi2S3 structure. The spherical Bi2S3 flowers could be found potential applications in optical, catalysts and sensor devices.

Syntheses, Growth Mechanism, and Optical Properties of [001] Growing Bi2S3 Nanorods

Uniform Bi2S3 nanorods growing along [001] have been synthesized from the precursor of Bi[S2CN(C8H17)2]3 by two different approaches: solventless and solvothermal methods. The structure, morphology, and formation process of the nanorods have been investigated by SEM, TEM, HRTEM, XRD, and EDX analyses. The growth direction is intrinsically governed by the crystal structure motif and the high surface energy of the (001) plane of orthorhombic Bi2S3 according to the CASTEP calculations. Besides, some important factors that influence the growth of Bi2S3 nanorods, such as the length of alkyl group in the precursor and the reaction temperature are investigated. The optical band gap of the as-synthesized Bi2S3 nanorods is measured to be 1.50 eV indicating a slightly blue shift owing to the quantum size effect.

Low‐temperature urea‐assisted hydrothermal synthesis of Bi2S3 nanostructures with different morphologies

AbstractDifferent morphologies of single‐crystalline orthorhombic phase bismuth sulfide (Bi2S3) nanostructures, including sub‐microtubes, nanoflowers and nanorods were synthesized by a urea‐assisted hydrothermal method at a low temperature below 120 °C for 12 h. The as‐synthesized powders were characterized by X‐ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM) and UV‐vis spectrophotometry. The experimental results showed that the sulfur sources had a great effect on the morphology and size of the resulting powders. The formation mechanism of the Bi2S3 nanostructures with different morphologies was discussed. All Bi2S3 nanostructures showed an appearance of blue shift relative to the bulk orthorhombic Bi2S3, which might be ascribed to the quantum size effect of the final products. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Topotactic Transformation of Single‐Crystalline Precursor Discs into Disc‐Like Bi2S3 Nanorod Networks

AbstractHierarchical, two‐dimensional (2D), disc‐like networks consisting of crossed single‐crystalline Bi2S3 nanorods have been synthesized via a novel 2D‐template‐engaged topotactic transformation process, which involves the formation of intermediate BiOCl single‐crystalline discs and their subsequent chemical transformation into disc‐like Bi2S3 nanofabrics. The transformation process from (001)‐oriented BiOCl discs to disc‐like Bi2S3 nanorod networks has been followed by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron diffraction (ED) and X‐ray diffraction (XRD), which revealed that the close matching between the lattice constants of the c‐axis for orthorhombic Bi2S3 and the a‐ or b‐axis for tetragonal BiOCl could be responsible for the preferential growth of [001]‐oriented Bi2S3 nanorods on the top faces of (001)‐oriented BiOCl discs along the two perpendicular [100] and [010] directions of BiOCl. The diameter of the Bi2S3 nanorods involved in the networks can be adjusted by changing the bismuth ion concentration in the reaction solution; moreover, an increase of the HCl concentration would prevent the formation of precursor BiOCl discs, leading to the formation of Bi2S3 nanostructures with varied morphologies. Charge–discharge curves and cyclic voltammograms of the obtained Bi2S3 nanostructures were measured to investigate their electrochemical hydrogen storage behaviors. It was found that the disc‐like Bi2S3 nanorod networks could electrochemically charge and discharge with a capacity of 162 mA h g−1 at room temperature, indicating their potential applications in hydrogen storage, high‐energy batteries, and catalytic fields.

Solventless Synthesis of Bi2S3 Nanowires and their Application to Solar Cells

Orthorhombic Bi2S3 (bismuthinite) nanorods and nanowires were synthesized by the solventless thermolysis of bismuth alkylthiolate precursors. Reactions producing high aspect ratio nanowires were carried out in air at 225°C with the presence of a capping ligand species, octanoate. Nanorods with a lower aspect ratio were produced by the same approach with the addition of elemental sulfur at a lower temperature (~160°C). Current density –Voltage characterization of the devices under illumination with 500 W Xenon lamp showed the photovoltaic performance. Both the nanorods and the nanowires hybrid with the polymer show the improved photovoltaic performance than polymer only. As far as we know, we are the first to apply Bi2S3 nanorods and nanowires to solar cells with the structure of ITO/PEDOT:PSS/MDMO-PPV:Bi2S3/Al.

Preparation of Uniform Bi2S3 Nanorods Using Xanthate Complexes of Bismuth (III)

Orthorhombic Bi2S3 nanorods were synthesized via hydrothermal treatment from a novel kind of single-source precursors, the adducts of Bi(S2COR)3 [R = sec-butyl] with neutral ligands (pyridine [C5H5N] or 1,10-phenanthroline [C12H8N2]). The decomposition of the complex [Bi(S2COC4H9)3(C5H5N)2] (1) produces Bi2S3 nanorods with diameters in the range of 20−35 nm and lengths of hundreds of nanometers. The nanodispersed Bi2S3 in dichloromethane maintains a long-term stability and shows a blue shift on the optical band edge with a band gap Eg ≈ 1.67 eV. High-resolution transmission electron microscopy studies reveal that the Bi2S3 nanorods are oriented in a [001] growth direction.

Solventless Synthesis of Bi2S3 (Bismuthinite) Nanorods, Nanowires, and Nanofabric.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Solventless Synthesis of Bi2S3 (Bismuthinite) Nanorods, Nanowires, and Nanofabric

Orthorhombic Bi2S3 (bismuthinite) nanorods and nanowires are synthesized by the solventless thermolysis of bismuth alkylthiolate precursors. Reactions carried out in air at ∼225 °C in the presence of a capping ligand species, octanoate, produce high aspect ratio (>100) nanowires. Lower aspect ratio nanowires (∼7) are produced by the same approach with the addition of elemental sulfur at lower reaction temperature (∼160 °C). Both the nanowires and nanorods are oriented with their long axes in the [002] crystallographic direction. Higher reaction temperatures (∼250 °C) produce crossed nanowire networks, or fabrics, with highly oriented growth as a result of heterogeneous nanowire nucleation and epitaxial elongation off the surface of existing wires.

Deposition of Bismuth Chalcogenide Thin Films Using Novel Single‐Source Precursors by Metal‐Organic Chemical Vapor Deposition.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Deposition of Bismuth Chalcogenide Thin Films Using Novel Single-Source Precursors by Metal-Organic Chemical Vapor Deposition

The metal-organic compounds, Bi[(EPR2)2N]3 (E = S, Se; R = Ph, iPr), have been synthesized and used as single-source precursors for the deposition of bismuth chalcogenide thin films via low-pressure and aerosol-assisted metal-organic chemical vapor deposition. Crystalline thin films of rhombohedral Bi2Se3 (using Bi[(SePiPr2)2N]3), hexagonal BiSe (using Bi[(SePPh2)2N]3), and orthorhombic Bi2S3 (using Bi[(SPR2)2N]3) have been deposited on glass substrates. Films have been characterized by X-ray powder diffraction, scanning electron microscopy, and energy-dispersive analysis of X-rays.

Stabilisterung von Cu-Fe-Bi-Pb-Sn-Sulfiden

Three stabilization phenomena, 1: special e.g. hydrothermal conditions, 2: stabilization by replacements of ions, as e.g. Cu and Fe and 3: heterogeneous nucleation as, e.g., by epitaxy are tested for phases in the system Cu2S-CuS2-Bi2S3-FeS-FeS2. Hydrothermal solution and precipitation conditions can metastabilize or stabilize phases, which are not existent under dry conditions as Cu4Bi5S10 or CuS2-FeS2 mixed crystals, but are stable at high pressures. Stabilization by Cu-Fe substitution leads to the assumption that stabilization basically depends on the ionic radii similarity, but necessarily electronic interactions have to be involved. Stabilization by heterogeneous nucleation is tested for Pb-Bi sulfosalts, e.g. for the epitaxial growth of Bi2S3 on NaCl. In contrast to the “normal” orthorhombic Bi2S3, the epitaxial Bi2S3 shows a pseudotetragonal subcell correlated to NaCl. Satellite reflections indicate a modulation probably caused by a modulation of the metal vacancies.