Bi2S3 nanomaterials: morphology manipulation and related properties

The Bi(2)S(3) nanomaterials with various morphologies such as nanorods, nanowires, nanowire bundles, urchin-like microspheres and urchin-like microspheres with cavities have been successfully synthesized through a simple hydrothermal method. Experimental results indicate that sulfur sources play crucial roles in determining the morphologies of Bi(2)S(3) products. Moreover, formation mechanisms of different Bi(2)S(3) nanostructures are discussed based on understanding of the growth habit of Bi(2)S(3) crystal. Finally, we also studied the morphologies-dependent electrochemical and optical properties of the as-synthesized Bi(2)S(3) nanomaterials.     

Development of one-dimensional nanostructures through the crystallization of amorphous colloids

In this paper we have demonstrated that the crystallization method of amorphous colloids is convenient and feasible in the large-scale production of one-dimensional (1D) nanostructures. For the crystals with highly anisotropic structures, such as orthorhombic, trigonal, and hexagonal crystals, the crystallization generally tends to occur along the (001) axis. The preparation of orthorhombic bismuth sulfide (Bi2S3) nanorods and trigonal selenium ( t-Se) nanowires by the crystallization route was used as typical examples to illustrate the process and mechanism of crystallization. The as-prepared products were characterized with transmission electron microscopy, field-emission scanning electron microscopy, X-ray diffraction, and selected area electron diffraction. Additionally, the detailed crystal growth processes involved in the crystallization of amorphous Bi2S3 colloid were investigated by studying the morphology and structure of intermediates. It demonstrates that the growth of the nanorods is through two key steps: (1) the formation of multiple activated sites on the surface of spherical Bi2S3 colloid and (2) the subsequent preferential growth along these sites.     

Effect of H2 on the electrical transport properties of single Bi2S3 nanowires

Field effect transistors have been fabricated using Bi2S3 nanowires. Whether the contact is ohmic or non-ohmic, the current of Bi2S3 nanowires was found to increase remarkably in H2 compared to that in a vacuum. Carrier density and mobility within the nanowires and the contact barriers between the nanowires and the electrodes have been extracted using field effect and two-probe current-voltage curves. It was found that H2 enhances electronic mobility and carrier density within the nanowires dramatically. The effect of H2 on the contact barriers was observed to be negligible compared to the other two effects.     

Microwave-assisted synthesis of sulfide M2S3 (m = Bi, Sb) nanorods using an ionic liquid

Single-crystalline Bi(2)S(3) and Sb(2)S(3) nanorods have been successfully synthesized by the microwave-assisted ionic liquid method. The starting reagents were Bi(2)O(3) or Sb(2)O(3), HCl, Na(2)S(2)O(3), and ethylene glycol (EG) or ethanolamine, and the ionic liquid used was 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF(4)]). Our experiments showed that the ionic liquid played an important role in the morphology of M(2)S(3) (M = Bi, Sb). Single-crystalline Bi(2)S(3) nanorods could be prepared in the presence of [BMIM][BF(4)]. However, urchinlike Bi(2)S(3) structures consisting of nanorods were formed without using [BMIM][BF(4)]. Single-crystalline Sb(2)S(3) nanorods were obtained in the presence of [BMIM][BF(4)]. However, single-crystalline Sb(2)S(3) nanosheets could be prepared in the absence of [BMIM][BF(4)]. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and electron diffraction (ED).     

Single-crystal Bi2S3 nanosheets growing via attachment-recrystallization of nanorods

High-quality Bi(2)S(3) discrete single-crystal nanosheets with orthorhombic structure have been synthesized through the thermal decomposition of a single-source precursor, Bi(S(2)CNEt(2))(3), in amine media. The morphology evolution reveals that the Bi(2)S(3) nanosheets are developed through the assembly of nanorods, and an attachment-recrystallization growth mechanism is proposed for the formation of nanosheets with the use of nanorods as building blocks. High-resolution transmission electron microscopy studies reveal that the nanosheets have the largest exposed surface of (100) facets. The effects of experimental variables, such as the reaction temperature, time, precursor concentration, and media, on the morphology of the obtained nanocrystals have been systematically investigated in which the amine has served as the solvent, surfactant, and electron donor.     

微波辐照方式对CdS和Bi2S3纳米粒子结晶度的影响

The effect of traveling microwave irradiation on the crystallinities of CdS nanoparticles and Bi₂S₃ nanorods was studied. Results showed that as compared with stationary microwave irradiation the crystallinities and the crystal growth of sulfide nanoparticles were improved. Traveling microwave irradiation can supply narrower frequency distribution and stronger power density of irradiation， CdS nanoparticles and Bi₂S₃ nanorods obtained are better in crystallinities and larger in size than under stationary microwave irradiation.     

离子液体中微波合成纳米结构的Bi2S3和Bi19Br3S27

在不同咪唑基离子液体中, 利用微波辅助法快速合成了不同形貌的Bi2S3纳米粒子和Bi19Br3S27纳米棒. 利用XRD, TEM和SEM对合成产物进行了结构和形貌的表征. 实验结果表明离子液体在合成过程中对产物的相结构和形貌发挥了重要的作用. 实验中还进一步考察了不同实验条件对产物形貌的影响. 对实验的合成机理进行了初步探讨. 对不同形貌和纳米结构的Bi2S3和Bi19Br3S27进行了UV-Vis光谱分析.     

High-quality ultralong Bi2S3 nanowires: structure, growth, and properties

A simple one-step hydrothermal method for large-scale synthesis of ultralong single-crystalline Bi2S3 nanowires was reported, and the nanowires were comprehensively characterized. The diameters of the nanowires are about 60 nm, and their lengths range from tens of microns to several millimeters. The structure of the nanowires was determined to be of the orthorhombic phase, the growth direction was along [001], and the growth mechanism was investigated based on extensive high-resolution transmission electron microscopy observations. Optical absorption experiments revealed that the Bi2S3 nanowires are narrow-band semiconductors with a band gap E(g) approximately 1.33 eV. Electrical transport measurements on individual nanowires gave a resistivity of about 1.2 ohms cm and an emission current of 3.5 microA at a bias field of 35 V/microm. This current corresponds to a current density of about 10(5) A/cm2, which makes the Bi2S3 nanowire a potential candidate for applications in field-emission electronic devices.     

Negative Feedback Effect of Microwave Irradiation in the Microwave—assisted Hydrothermal Synthesis of Bi2S3 Nanorods

The microwave-assisted hydrothermal synthesis of Bi2S3 nanorods was reported.The result showed that microwave irradiation can help to produce Bi2S3 nanorods in very short time.There is a negative feedback effcet which increases the degree of crystallinity in the reaction.     

Bi2S3-sensitized TiO2 nanorods by bottom-up approach for photoelectrochemical solar cell

Journal of Solid State Electrochemistry - Bismuth sulfide (Bi2S3)-sensitized titanium dioxide (TiO2) nanorods have been successfully synthesized by a simple and cost-effective chemical deposition...     

Visible-light induced photoelectrochemical biosensor for the detection of microRNA based on Bi2S3 nanorods and streptavidin on an ITO electrode

Microchimica Acta - We demonstrate a photo-electrochemical biosensor for the sensitive and specific detection of microRNA using Bi2S3 nanorods as a photoactive material and streptavidin as the unit...     

Biomolecule-assisted synthesis and electrochemical hydrogen storage of Bi2S3 flowerlike patterns with well-aligned nanorods

Bi2S3 flowerlike patterns with well-aligned nanorods were synthesized using a facile solution-phase biomolecule-assisted approach in the presence of L-cysteine (an ordinary and cheap amino acid), which turned out to serve as both the S source and the directing molecule in the formation of bismuth sulfide nanostructures. Emphatically, no nauseous scent (H2S) appeared in our experiments, which could not be avoided in other previous reports. The morphology, structure, and phase composition of the as-prepared Bi2S3 products were characterized using various techniques (scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, selected area electron diffraction, and high-resolution transmission electron microscopy). The formation mechanism for the bismuth sulfide flowerlike assemblies with well-arranged nanorods was also discussed. In addition, other Bi2S3 homogeneous nanostructures (e.g., networklike nanoflakes, nanorod-based bundles, and nanoflakes) were obtained through varying the experimental parameters. Interestingly, we have found that these synthesized bismuth sulfide nanostructures using the biomoleucle-assisted approach could electrochemically charge and discharge with the capacity of 142 (mA h)/g (corresponding to 0.51 wt % hydrogen in single-walled carbon nanotubes) under normal atmosphere at room temperature. A novel two-plateau phenomenon was observed in the synthesized Bi2S3 nanostructures, suggesting that there were two independent steps in the charging process. It has been demonstrated that the bismuth sulfide's morphology and the constant charge-discharge current density had a noticeable influence on their capacity of electrochemical hydrogen storage. These differences in hydrogen storage capacity are likely due to the size and density of space/pores as well as the morphology of different Bi2S3 nanostructures. The novel Bi2S3 nanomaterials may find potential applications in hydrogen storage, high-energy batteries, luminescence, optoelectronic and catalytic fields, as well as in the studies of structure-property relationships. This facile, environmentally benign, and solution-phase biomolecule-assisted method can be potentially extended to the preparation of other metal chalcogenides including FeS, CuS, NiS, PbS, MnS, and CoS nanostructures.     

EDTA辅助水热法合成硫化铋晶体

以Bi(NO3)3·5H2O和Na2S2O3·5H2O为原料,用乙二胺四乙酸(EDTA)辅助水热法合成了纳米或微米级的Bi2S3晶体(1),其结构、形貌和光谱性能经XRD,FE-SEM和UV-Vis表征。结果表明:溶液的pH对1的形貌有显著的影响,随着pH的增大,1由纳米棒组成的微米球逐渐转变为微米级片状结构;1出现蓝移。     

Bismuth telluride (Bi2Te3) nanowires: synthesis by cyclic electrodeposition/stripping, thinning by electrooxidation, and electrical power generation

Nanowires composed of the thermoelectric material Bi2Te3 were synthesized on highly oriented pyrolytic graphite (HOPG) electrodes using the electrochemical step edge decoration (ESED) method. Nanowire synthesis was initiated by applying a voltage pulse of -0.75 V versus SCE for 5 ms to an HOPG electrode in an aqueous solution containing both Bi3+ and TeO22-, thereby producing nuclei at the step edges. Bi2Te3 was electrodeposited onto these nuclei using a cyclic electrodeposition-stripping scheme that involved the electrodeposition of bismuth-rich Bi2Te3 on a negative-going voltammetric scan (to -0.05 V) and the subsequent anodic stripping of excess bismuth from these nanowires during a positive-going scan (to +0.35 V). When this cycle was repeated 10-50 times, Bi2Te3 nanowires in the 100-300-nm-diameter range were obtained. These nanowires were narrowly dispersed in diameter (RSDdia = 10-20%), were more than 100 microm in length, and were organized into parallel arrays containing hundreds of wires. Smaller nanowires, with diameters down to 30 nm, were obtained by electrooxidizing 150-nm-diameter Bi2Te3 nanowires at +0.37 V under conditions of kinetic control. This oxidation process unexpectedly improved the uniformity of Bi2Te3 nanowires, and X-ray photoelectron spectroscopy (XPS) shows that these nanowires retain a Bi2Te3 core but also have a thin surface layer composed of Bi and Te oxides. The ability of Bi2Te3 nanowires to generate electrical power was assessed by transferring ensembles of these nanowires onto cyanoacrylate-coated glass surfaces and evaporating 4-point nickel contacts. A dimensionless figure of merit, ZT, ranging from 0 to 0.85 was measured for fresh samples that were less than 1 day old. XPS reveals that Bi2Te3 nanowires are oxidized within a week to Bi2O3 and TeO2. These oxides may interfere with the application by evaporation of electrical contacts to these nanowires.     

Controlled synthesis of olive-shaped Bi2S3/BiVO4 microspheres through a limited chemical conversion route and enhanced visible-light-responding photocatalytic activity

Well-defined olive-shaped Bi(2)S(3)/BiVO(4) microspheres were synthesized through a limited chemical conversion route (LCCR), where olive-shaped BiVO(4) microspheres and thioacetamide (TAA) were used as precursors and sulfur source, respectively. The as-synthesized products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high-resolution transmission microscope (HRTEM), X-ray photoelectron spectra (XPS), UV-visible diffuse-reflectance spectroscopy (UV-vis DRS), and photoluminescence (PL) spectra in detail. Compared with pure BiVO(4) microspheres and Bi(2)S(3) nanorods, the Bi(2)S(3)/BiVO(4) products showed obviously enhanced photocatalytic activity for the degradation of rhodamine B (Rh B) in aqueous solution under visible-light irradiation (λ > 400 nm). In addition, the Bi(2)S(3)/BiVO(4) composite microspheres showed good visible-light-driven photocatalytic activity for the degradation of refractory oxytetracycline (OTC) as well. On the basis of UV-vis DRS, the calculated energy band positions, and PL spectra, the mechanism of enhanced photocatalytic activity of Bi(2)S(3)/BiVO(4) was proposed. The present study provides a new strategy to design composite materials with enhanced photocatalytic performance.     

利用牛血清蛋白合成CdS纳米棒和网状纳米线

采用简单易控、对环境友好的矿化方法, 利用牛血清蛋白(BSA)做模板, 通过Cd2+与硫代乙酰胺(TAA)反应制备了形貌均一的CdS纳米棒和网状纳米线. 分别采用透射电子显微镜(TEM)、X射线能谱(EDS)、X射线衍射(XRD)、荧光(PL)发射谱和导电原子力显微镜(C-AFM)等方法对不同实验温度下制备的CdS样品的结构形貌、成分组成和光学性质及微区电子传输行为进行了表征. 结果表明: 在实验反应温度为20 ℃时, 得到的产物为单分散性好的CdS 纳米棒, 长度为250 nm, 直径为30 nm; 在50 ℃时, 得到网状CdS纳米线, 其长度为2-3 μm; CdS纳米棒和网状纳米线均为立方相闪锌矿结构. 荧光性质的测试表明, CdS纳米棒和网状纳米线具有优良的荧光性能, 电流-电压(I-V)特性的表征表明CdS纳米线具有很好的电导特性.     

Monodisperse lanthanide oxysulfide nanocrystals

Monodisperse lanthanide oxysulfide nanoplates and short nanorods were synthesized by the thermal decomposition of molecular precursors in the presence of oxygen. The nanoplates have uniform thicknesses and further self-organize to nanowires up to micron scale. The Eu2O2S and Eu3+-doped Gd2O2S nanocrystals both show unusual fluorescence properties obviously differing from the bulk powder phosphors, which are related to the surface-modification effects.     

Polymorph-tuned synthesis of α- and β-Bi2O3 nanowires and determination of their growth direction from polarized Raman single nanowire microscopy

We report polymorph-tuned synthesis of α- and β-Bi(2)O(3) nanowires and their single nanowire micro-Raman study. The single crystalline Bi(2)O(3) nanowires in different phases (α and β) were selectively synthesized by adjusting the heating temperature of Bi precursor in a vapor transport process. No catalyst was employed. Furthermore, at an identical precursor evaporation temperature, α- and β- phase Bi(2)O(3) nanowires were simultaneously synthesized along the temperature gradient at a substrate. The growth direction of α-Bi(2)O(3) nanowires was revealed by polarized Raman single nanowire spectra. For thin β-Bi(2)O(3) nanowires with a very small diameter, the polarized Raman single nanowire spectrum was strongly influenced by the shape effect.     

Facile controlled synthesis of MnO2 nanostructures of novel shapes and their application in batteries

In this paper, MnO2 nanomaterials of different crystallographic types and crystal morphologies have been selectively synthesized via a facile hydrothermal route and electrochemically investigated as the cathode active materials of primary and rechargeable batteries. Beta-MnO2 nano/microstructures, including one-dimensional (1-D) nanowires, nanorods, and nanoneedles, as well as 2-D hexagramlike and dendritelike hierarchical forms, were obtained by simple hydrothermal decomposition of an Mn(NO3)2 solution under controlled reaction conditions. Alpha- and gamma-MnO2 nanowires and nanorods were also prepared on the basis of previous literature. The as-synthesized samples were characterized by instrumental analyses such as XRD, SEM, TEM, and HRTEM. Furthermore, the obtained 1-D alpha- and gamma-MnO2 nanostructures were found to exhibit favorable discharge performance in both primary alkaline Zn-MnO2 cells and rechargeable Li-MnO2 cells, showing their potential applications in high-energy batteries.     

Microsphere organization of nanorods directed by PEG linear polymer

We demonstrate the sphere organization of ZnO, Bi2S3, MnO2, and La(OH)3 nanorods directed by PEG linear polymer. Our study shows that zinc, bismuth, manganese, or lanthanum species added to PEG solutions, in which PEG molecules are well dissolved in a coil state, convert the polymer coils to aggregate structures, which further aggregate into micrometer-sized M(n+)-PEG globules. The concentration of metallic species is higher in the globules than in bulk solutions. The surfaces of the globules act as soft templates for the initial nucleation and thereafter the growth of the nanorods. Finally, echinus-type assemblies of single-crystalline nanorods form by the metallic species hydrolyzing or reacting with deposition agents. This approach opens the possibility of using polymers as soft templates to control the organization of nano building units into designed structures.