Influence of NaOH on the synthesis of Bi2Te3 via a low-temperature aqueous chemical method

NaOH was used to adjust the pH of the solution in the synthesis of nanostructured Bi₂Te₃ alloys via hydrothermal and solvothermal process. However, it is still elusive whether NaOH is necessary and how it affects on the size and morphology of Bi₂Te₃ which contributes a lot to the thermoelectric figure of merit ZT. The present work suggested that bulk quantity of nanostructured Bi₂Te₃ with considerable uniform morphology of nanoflake could be yielded without NaOH when the reaction time ranged from 6 h to 48 h. These nanoflakes have about 10–30 nm thickness and 50–300 nm width. When adding NaOH, the morphology of Bi₂Te₃ becomes various.     

Preparation of Bi2S3 nanorods via a hydrothermal approach

Large-scale bismuth sulfide (Bi₂S₃) nanorods with uniform size have been prepared by hydrothermal method using bismuth chloride (BiCl₃) and sodium sulfide (Na₂S·9H₂O) as raw materials at 180 °C and pH = 1-2 for 12 h. The powder X-ray diffraction (XRD) pattern shows the Bi₂S₃ crystal belongs to the orthorhombic phase with calculated lattice constants a = 1.1187 nm, b = 1.1075 nm and c = 0.3976 nm. Furthermore, the quantification of X-ray photoelectron spectra (XPS) analysis peaks gives an atomic ratio of 1.9:3.0 for Bi:S. Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopic (TEM) studies reveal that the appearance of the as-prepared Bi₂S₃ is rod-like with typical lengths in the range of 2-5 μm and diameters in the range of 10-30 nm. Finally the influences of the reaction conditions are discussed and a possible mechanism for the formation of Bi₂S₃ nanorods is proposed.     

Selective synthesis of Bi2Se3 nanostructures by solvothermal reaction

Bi₂Se₃ nanobelts, nanoflakes and sheets embedded nanotubes were prepared via solvothermal process with different solvents. The reaction conditions influencing the synthesis of Bi₂Se₃ nanostructures such as solvents, and reaction temperatures were studied and optimized. Results indicated that the mixed solvent composed of triethanolamine and ethanol (TEA-EtOH) or triethanolamine and distilled water (TEA-H₂O) can decrease the threshold temperature (TT) of Bi₂Se₃. With the solvents TEA-EtOH and TEA-H₂O, we originally accomplished the shape-controlled synthesis of Bi₂Se₃ nanocrystals by controlling reaction temperature. Based on the viewpoint of crystallography about Bi₂Se₃, the possible growth mechanisms of Bi₂Se₃ nanostructures were discussed.     

Characterization of Bi2S3 with different morphologies synthesized using microwave radiation

Bi₂S₃ with different morphologies (nanoparticles, nanorods and nanotubes) was synthesized using bismuth nitrate pentahydrate (Bi(NO₃)₃·5H₂O) and two kinds of sulfur sources (CH₃CSNH₂ and NH₂CSNH₂) in different solvents (water, ethylene glycol and propylene glycol) via a microwave radiation method at 180 W for 20 min. X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) indicated that all of the products are orthorhombic Bi₂S₃ phase of nanoparticles, nanorods and nanotubes, influenced by the sulfur sources and solvents. Formation mechanisms of the products with different morphologies are also proposed.     

In situ fabrication of Bi2S3 nanocrystal film for photovoltaic devices

A facile wet-chemical method to prepare Bi₂S₃ thin films with flake nanostructures directly on ITO glass substrate is presented in this paper for the first time. The product was characterized by X-ray powder diffractometer (XRD), Raman spectrometer, scanning electron microscope (SEM), and atomic force microscope (AFM). The one-step solvothermal elements treatment on the ITO substrate spare time to form film by spin-coating process and the film could be tightly attached to the ITO electrode. A conjugated polymer, poly 3-hexylthiophene (P3HT), was then spin-coated on the as-prepared Bi₂S₃ film to form an inorganic-organic hybrid thin film. The photovoltaic performance of the resulting solar cell device was also investigated.     

Uniform Bi2S3 nanowires: Structure, growth, and field-effect transistors

Large-scale single-crystalline Bi₂S₃ nanowires were prepared by a simple one-step hydrothermal reaction between Bi(NO₃)₃ and Na₂S₂O₃, without using any organics in the experiment. These Bi₂S₃ nanowires have uniform size diameters which are about 60 nm. The structure of the nanowires is determined to be of the orthorhombic phase, and the growth direction is along the [001] direction. The growth mechanism of the nanowires was investigated based on high-resolution transmission electron microscopy observations. The field-effect transistors (FETs) have been fabricated using a single Bi₂S₃ nanowire, n-type semiconductor behavior has been observed, and high on/off ratio of about 3 orders of magnitude has been achieved.     

Effects of Bi2O3 and Cr2Ti3O9 Co-doping on dielectric properties in BaTiO3-based ceramics

A microwave ceramic with general composition (1-x-y) BaTiO₃ + x Cr₂Ti₃O₉ + y Bi₂O₃ has been prepared by solid state synthesis at 1300-1400 °C. The phase composition, perovskite structural parameters and dielectric properties have been obtained by X-ray diffraction and dielectric measurements as a function of chemical composition and temperature. At low doping levels the formation of BaTiO₃-based solid solution has been found. The precipitation of BaCrO₃ has been detected at x = y = 2.0 mol%. A model of the incorporation of Cr³⁺ and Bi³⁺ ions into BaTiO₃-based crystal lattice has been proposed. Diffused phase transition in the temperature range 100-140 °C have been revealed by dielectric measurements for different ceramic composition. As high dielectric constant as 7311 and as low dielectric loss as 0.02 have been found for the composition of 0.98BaTiO₃-0.01Cr₂Ti₃O₉-0.01Bi₂O₃.     

Heterostructured Fe3O4/Bi2O2CO3 photocatalyst: Synthesis,characterization and application in recyclable photodegradation of organic dyes under visible light irradiation

Heterostructured Fe₃O₄/Bi₂O₂CO₃ photocatalyst was synthesized by a two-step method. First, Fe₃O₄ nanoparticles with the size of ca. 10 nm were synthesized by chemical method at room temperature and then heterostructured Fe₃O₄/Bi₂O₂CO₃ photocatalyst was synthesized by hydrothermal method at 180 °C for 24 h with the addition of 10 wt% Fe₃O₄ nanoparticles into the precursor suspension of Bi₂O₂CO₃. The pH value of synthesis suspension was adjusted to 4 and 6 with the addition of 2 M NaOH aqueous solution. By controlling the pH of synthesis suspension at 4 and 6, sphere- and flower-like Fe₃O₄/Bi₂O₂CO₃ photocatalysts were obtained, respectively. Both photocatalysts demonstrate superparamagnetic behavior at room temperature. The UV–vis diffuse reflectance spectra of the photocatalysts confirm that all the heterostructured photocatalysts are responsive to visible light. The photocatalytic activity of the heterostructured photocatalysts was evaluated for the degradation of methylene blue (MB) and methyl orange (MO) in aqueous solution over the photocatalysts under visible light irradiation. The heterostructured photocatalysts prepared in this study exhibit highly efficient visible-light-driven photocatalytic activity for the degradation of MB and MO, and they can be easily recovered by applying an external magnetic field.     

Influence of different synthesizing steps on the multiferroic properties of Bi5Fe1Ti3O15 and Bi5Fe0.5Co0.5Ti3O15 ceramics

The compounds Bi₅FeTi₃O₁₅ (BFTO) and Bi₅Fe_0.5Co_0.5Ti₃O₁₅ (BFCT) were prepared by incorporating BiFeO₃ (BFO) and BiFe_0.5Co_0.5O₃ (BFCO) into the host Bi₄Ti₃O₁₂ (abbreviated as BFTO-1 and BFCT-1) and by the conventional solid-state reaction method (abbreviated as BFTO-2 and BFCT-2). X-ray analysis indicates a four-layer Aurivillius phases with an orthorhombic symmetry. At room temperature, the remnant polarization (2P _r) of BFTO-1, BFTO-2, BFCT-1, and BFCT-2 samples are measured to be 11.0, 3.5, 13, and 6.3 μC/cm², respectively, and the corresponding remnant magnetization (2M _r) are about 2.72 × 10⁻³ memu/g, 1.51 × 10⁻³ memu/g, 7.6 and 2.1 memu/g, respectively. Both BFTO-1 and BFCT-1 samples exhibit the dielectric peaks at around 755 and 772 °C in their ε–T curves, respectively.     

Ferroelectric properties of Mn-Doped Bi3.15Nd0.85Ti3O12 thin films prepared under different annealing conditions

Mn-doped Bi_3.15Nd_0.85Ti₃O₁₂ (BNTM) thin films were fabricated on Pt/Ti/SiO₂/Si(100) substrates by a chemical solution deposition technique and annealed at different temperatures from 650 to 800 °C. The structures of the films were analyzed using X-ray diffraction, which showed that the BNTM films exhibit polycrystalline structures and random orientations. The surface morphologies of the samples were investigated using scanning electron microscopy. The average grain size of the films increases with increasing annealing temperature. Electrical properties such as remanent polarization (2P_r) are quite dependent on the annealing temperature of BNTM films. It is found that the film annealed at 750 °C exhibits excellent ferroelectricity with a remanent polarization of 2P_r = 89.3 μC/cm² and a coercive field of E_c = 99.2 kV/cm respectively.     

Synthesis and characterization of Bi2S3 nanorods by solvothermal method in polyol media

Bi₂S₃ nanorods were synthesized via a simple solvothermal process in polyol media through the reaction between Bi(NO₃)₃·5H₂O, urea and CS₂ at 150 °C for 15 h using diethylene glycol as solvent. The nanorods were characterized by XRD, TEM and SAED. The results showed that the products were well-crystallized orthorhombic phase with lattice parameters a = 11.15 Å, b = 11.3 Å and c = 3.984 Å, which are consistent with the value in standard JCPDS card No. 17-0320. DEG served as an excellent solvent and structure director. Besides, compared to water and EG as solvents, the DEG system can provide a mild and homogenous condition, which is favorable to anisotropic growth and increases the yield of high quality Bi₂S₃ nanorods. Based on the experimental results, the growth mechanism was discussed.     

Effect of Bi2O3 and Y2O3 doping methods on electrical properties and PTCR behavior of Ba0.95Ca0.05TiO3 ceramics

Lead-free PTCR ceramics based on Bi₂O₃ and Y₂O₃ doped Ba_0.95Ca_0.05TiO₃ were fabricated by the conventional mixed oxide method, while Bi₂O₃ and Y₂O₃ were doped directly or after pre-calcining, in the molar ratio of Bi₂O₃:Y₂O₃ = 1:1. There were two synthesizing route, i.e. the materials were pre-calcined at 900 °C to obtain BiYO₃ firstly and then doped into the basic materials, and the materials were directly doped into the starting materials, both of which could obtain samples with different electrical properties and PTCR behavior. The samples were characterized by using X-ray diffraction, scanning electron microscope, dielectric constant-temperature and resistivity-temperature measurement instrument. It was revealed that the perovskite lattice, the microstructure and the PTCR behavior of Ba_0.95Ca_0.05TiO₃ varied with different doping contents and methods. A further research was conducted so as to study the electrical properties of ceramics by impedance spectroscopy.     

Synthesis and characterization of Bi2Fe4O9 powders

Bi₂Fe₄O₉ have been successfully prepared using ethylenediaminetetraacetic (EDTA) acid as a chelating agent and ethylene glycol as an esterification agent. Heating of a mixed solution of EDTA, ethylene glycol, and nitrates of iron and bismuth at 140 °C produced a transparent polymeric resin without any precipitation, which after pyrolysis at 250 °C was converted to a powder precursor for Bi₂Fe₄O₉. The precursors were heated at 400–800 °C in air to obtain Bi₂Fe₄O₉ powder and differential scanning calorimetry (DSC), thermogravimetric (TG), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) techniques were used to characterize the precursors and the derived oxide powders. XRD analysis showed that well-crystallized and single-phase Bi₂Fe₄O₉ with orthorhombic symmetry was obtained at 700 °C for 2 h and BiFeO₃ and Fe₂O₃/FeCO₃ were intermediate phases before the formation of Bi₂Fe₄O₉. Bi₂Fe₄O₉ powders show weak ferromagnetism at room temperature.     

Synthesis and thermodynamic stability of multiferroic BiFeO3

Ceramic BiFeO₃ samples were prepared by the sol gel combustion method using urea as fuel. The obtain powders were thermal treated at different temperatures (300-840  °C) and times (1-64  h) to investigate the best synthesis conditions of the material. The resulting materials were analysed by TGA, FTIR, SEM/EDS and XRD. Rietveld analysis was applied to the diffraction data. The temperature and time of the heat treatment are critical for a high BiFeO₃ phase content. Thermal treatment of 1  h at 600  °C yielded 99% molar of the BiFeO₃ phase with a mean particle size of 120  nm. Upper or lower calcinations temperatures yielded higher content of the secondary phases Bi₂Fe₄O₉ and Bi₂₅FeO₃₉. Further heat treatment in air or in argon, up to 64  h, induces a decomposition of the BiFeO₃ phase according to the reaction 49 BiFeO₃ BiFeO₃ → 12 Bi₂Fe₄O₉ + Bi₂₅FeO₃₉ pointing out that BiFeO₃ is not thermodynamically stable at 600  °C. The BiFeO₃ decomposition follows Avrami-Erofeev law with a slope of 1 indicating a one-dimensional kinetics.     

Hierarchical BiOI and hollow Bi2WO6 microspheres: Topochemical conversion and photocatalytic activities

We present here a facile one-pot surfactant-free solvothermal route to synthesize hierarchical BiOI microspheres assembled from nanosheets at 120 °C for 16 h. The as-synthesized BiOI microspheres could be topochemically converted into hollow hierarchical Bi₂WO₆ ones built by nanoplates for the first time under hydrothermal condition because of the analogies of crystal structures. The transformation process of hierarchical BiOI microspheres to hollow Bi₂WO₆ ones was surveyed through XRD analyses and FE-SEM observations of the intermediates at different reaction stages. Rhodamine B (RhB) was selected as pollutant model and visible-light-driven photocatalytic activities of hierarchical BiOI and Bi₂WO₆ microspheres under the same measurement conditions were comparatively studied. As a result, the photocatalytic activities of BiOI obviously outshone Bi₂WO₆. The present study not only develops a new method for fabricating hierarchical architectures but also provides some useful information on relative visible-light-responding photocatalytic activity of hierarchical BiOI and Bi₂WO₆ microspheres.     

Anisotropic grain growth of Bi4Ti3O12 in molten salt fluxes

Bismuth titanate (Bi₄Ti₃O₁₂) platelets were obtained by the molten salt synthesis method in NaCl-KCl and Na₂SO₄-K₂SO₄ fluxes, using an amorphous Bi₄Ti₃O₁₂ precursor and a mechanically mixed Bi₂O₃-TiO₂ mixture as the starting materials. It was found that the synthesizing temperature, salt species and starting materials could significantly affect the crystallization habit and morphology of Bi₄Ti₃O₁₂ platelets. Under the same processing conditions (i.e. in Na₂SO₄-K₂SO₄ flux at 1000 °C), the Bi₄Ti₃O₁₂ platelets synthesized from the Bi₂O₃-TiO₂ mixture generally showed a smaller particle size than those synthesized using the amorphous Bi₄Ti₃O₁₂ precursor. The Bi₄Ti₃O₁₂ platelets prepared in the chloride flux were faceted along either (0 0 1) or (1 1 2) planes, while those prepared in the sulfate flux were solely (0 0 1) faceted. The former system also had smaller particle size than the latter. Furthermore, the salt content and the addition of plate-like Bi₄Ti₃O₁₂ seeds in the amorphous Bi₄Ti₃O₁₂ precursor showed a strong influence on the particle size of the synthesized Bi₄Ti₃O₁₂ platelets. The particle size of Bi₄Ti₃O₁₂ platelets prepared in the sulfate flux decreased as the mole ratio of the sulfate salts to Bi₄Ti₃O₁₂ was increased from 7.9 to 23.7. And the addition of 10 wt.% plate-like Bi₄Ti₃O₁₂ seeds into the amorphous Bi₄Ti₃O₁₂ precursor led to a significant increase in the particle size of the resulting Bi₄Ti₃O₁₂ platelets.     

Synthesis of Na0.5Bi0.5TiO3 anisotropic particles with grain orientation by conversion of Na0.5Bi4.5Ti4O15 crystals

A novel method for synthesizing Na_0.5Bi_0.5TiO₃ (BNT) anisotropic particles with grain orientation is reported. Anisotropically shaped particles of BNT were prepared by conversion of Na_0.5Bi_4.5Ti₄O₁₅ (NBT15) single crystals. Platelet NBT15 was produced by molten-salt synthesis. They were converted to BNT by second molten-salt synthesis at 800–1200 °C. NBT15 single-crystal platelets were transformed into platelet particles of polycrystalline BNT. The reaction is topotaxial, those recrystallized BNT were oriented with (h 0 0) plane parallel to the platelet. The use of converted BNT particles as seed was confirmed by performing templated grain growth (TGG) of BNT with 5% grain-oriented, anisotropic particles of BNT.     

Sol-gel synthesis of lead-free (K0.5Bi0.5)0.4Ba0.6TiO3 nanorods

A kind of lead-free ferroelectric nanorods, (K_0.5Bi_0.5)_0.4Ba_0.6TiO₃, has been prepared by the sol-gel process. The phase formation, structure and morphological analyses of (K_0.5Bi_0.5)_0.4Ba_0.6TiO₃ were investigated by XRD, FTIR, Raman and TEM. The results revealed that single-crystalline (K_0.5Bi_0.5)_0.4Ba_0.6TiO₃ nanorods with width around 80 to 120 nm, and length around 200-300 nm were obtained by calcining dried gels at 800 °C for 2 h. Raman analysis of (K_0.5Bi_0.5)_0.4Ba_0.6TiO₃ nanorods indicated that A₁(TO₂) and E(TO) mode incorporated into one broad peak at around 285 cm^− 1, which can be attributed to the cation disorder (Bi, K, Ba) on the 12-fold coordinated A site of ABO₃ structure.     

A very simple and low cost route to Bi2S3 nanorods bundles and dandelion-like nanostructures

Bi₂S₃ nanorods bundles as well as three-dimensional dandelion-like nanostructures were synthesized in high yield at lower temperature (room temperature or ambient temperature of 15 °C) in a very simple system composed only of Bi(NO₃)₃, thioacetamide (TAA), hydrochloride acid and distilled water. It is the first report to obtain such nanostructures at such a low temperature and by such a simple method, and the reaction does not demand any additional energy such as heating or agitation. A splitting crystal growth and self-assemble mechanism should be responsible for the formation of these structures. This kind of novel Bi₂S₃ nanostructures may find potential applications in hydrogen storage, high-energy batteries, as well as luminescence and catalysis fields.     

Influence of doping Nb5+ and Mn2+ on the PTCR effects of Ba0.92Ca0.05(Bi0.5Na0.5)0.03TiO3 ceramics

As a positive temperature coefficient of resistivity (PTCR) material, Ba_0.92Ca_0.05(Bi_0.5Na_0.5)_0.03TiO₃ ceramics with donor doping of Nb⁵⁺ and acceptor doping of Mn²⁺ were prepared by a conventional mixed oxide method. The influence of contents of Nb⁵⁺ and Mn²⁺ on the microstructure and PTCR characteristics of Ba_0.92Ca_0.05(Bi_0.5Na_0.5)_0.03TiO₃ ceramics sintered at 1,360°C for 2 h was investigated. The result showed that the Curie temperature (T _c) was shifted to a lower temperature with increasing of the content of Nb⁵⁺ and the resistance jump (ρ_max/ρ_min) was enhanced with doping of Mn²⁺. The grain size of ceramic sample decreased with increasing of contents of donor Nb⁵⁺ and acceptor Mn²⁺. The Ba_0.92Ca_0.05(Bi_0.5Na_0.5)_0.03TiO₃ ceramic with 0.4 mol%Nb⁵⁺ and 0.04 mol%Mn²⁺ exhibited a low ρ_RT of 5.0 × 102 Ω cm, a typical PTCR effect of ρ_max/ρ_min > 10³, and a T _c of 158°C.