Optoelectronic Properties of Al/n-Si/ Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript>/Au Photosensor

We have fabricated an Al/n-Si/Bi₄Ti₃O₁₂/Au photodiode by the sol-gel method. The photoelectrical response of the diode was measured under dark and various light intensity conditions. The photocurrent of the diode increases with increase in light intensity. The light sensitivity value of the photosensor was measured and observed to increase from 5.06 × 10^?8 (under dark) to 2.34 × 10^?4 A (under 100 mW/cm²). Furthermore, other parameters for instance, ideality factor and barrier height of the photosensors were calculated. The ideality factor and barrier height of the Al/n-Si/Bi₄Ti₃O₁₂/Au photosensor were found to be 3.01 and 0.86 eV respectively. Also capacitance-voltage (C-V) characteristics were measured. The C-V graph indicates changeable behavior with the varying frequency. The value of capacitance and the interface state density D_it value decrease with increase in frequency. Thus, the obtained results indicate that the Al/n-Si/Bi₄Ti₃O₁₂/Au photosensor can be used as a photosensor in optoelectronic applications.     

Synthesis and Photocatalytic Performance of Bi<Subscript>12</Subscript>O<Subscript>17</Subscript>Cl<Subscript>2</Subscript> Semiconductors Calcined at Different Temperatures

In the current investigation a series of oxygen-rich bismuth oxychloride Bi₁₂O₁₇Cl₂ samples through an ethylene glycol-solvothermal route were constructed at different calcination temperatures and fully characterized by X-ray diffraction patterns, scanning electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy, UV–Vis diffuse reflectance spectra, X-ray energy dispersion spectroscopy, and photoluminescence spectra. It was demonstrated that the calcination temperatures indeed had a crucial effect on the crystallinity, grain size, morphology, optical property, and charge carrier separation of Bi₁₂O₁₇Cl₂ series. These Bi₁₂O₁₇Cl₂ samples showed significantly improved photocatalytic degradation over dye Rhodamine B and colorless antibiotic tetracycline hydrochloride. Particularly, the best candidate, the sample 350 °C—Bi₁₂O₁₇Cl₂ could show apparent reaction rate constants that were nearly 28.2, 1.2 times of N–TiO₂ over Rhodamine B and tetracycline hydrochloride, respectively. The possible reason of enhancing photocatalytic performance by various Bi₁₂O₁₇Cl₂ samples calcined at different temperatures was discussed and major oxidative radicals maybe generated during photocatalytic processes were detected.     

Study on the properties of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-BaO lead-free glass using in the electronic pastes

The Sb₂O₃ doping lead-free glass in Bi₂O₃-B₂O₃-BaO ternary system were prepared in the composition of several different subsystem, and the glass powder was produced through the process of water quenching. Glass transition temperatures (T _g ), glass soften temperatures(T _s ), the volume resistivity (ρ) in the temperature range of 80–200°C, and linear thermal coefficients of expansion in the temperatures range of 25–300°C (α_25–300) were measured for subsystems along with the different ratio of Bi₂O₃, B₂O₃ and BaO. For these subsystems, T _g ranged from 458 to 481°C, and T _s ranged from 490 to 512°C, both decreasing with the increasing of Bi₂O₃/B₂O₃ ratio, and increasing with the increasing of BaO/B₂O₃ ratio. The measured α_25–300 ranged from 65.3 to 76.3 × 10⁻⁷ K⁻¹, with values increasing with increasing Bi₂O₃/B₂O₃ and BaO/B₂O₃ ratio. The volume resistivity remains at a high standards, which may caused by it’s non-alkali composition, and it fluctuated from 10¹³ to 10¹¹ Ω cm with the temperature varied from 80–200°C. The structure of Bi₂O₃-B₂O₃-BaO ternary leadfree glass system was mearsured by FT-IR. The IR studies indicate that these glasses are made up of [BiO₆], [BO₃], and [BO₄] basic structural units, and it appears that Ba²⁺ acts as a glass-modifier in this ternary system, but the Bi³⁺ has entered the glass network when it is in relative high content so as to change the α_25–300, T _s and T _g .     

Effect of reaction conditions on the catalytic performance of Co<Subscript>9</Subscript>Fe<Subscript>3</Subscript>Bi<Subscript>1</Subscript>Mo<Subscript>12</Subscript>O<Subscript>51</Subscript> in the oxidative dehydrogenation of n-butene to 1,3-butadiene

Oxidative dehydrogenation of n-butene to 1,3-butadiene over Co₉Fe₃Bi₁Mo₁₂O₅₁ catalyst was conducted in a continuous flow fixed-bed reactor. The effect of reaction conditions (steam/n-butene ratio, reaction temperature, and space velocity) on the catalytic performance of Co₉Fe₃Bi₁Mo₁₂O₅₁ was investigated. Steam played an important role in decreasing contact time, suppressing total oxidation of n-butene, and removing coke during the reaction. Yield for 1,3-butadiene showed a volcano-shaped curve with respect to steam/n-butene ratio. The compensation between thermodynamic effect and kinetic effect led to a volcano-shaped curve of 1,3-butadiene yield with respect to reaction temperature. The Co₉Fe₃Bi₁Mo₁₂O₅₁ catalyst showed the best catalytic performance at a certain value of space velocity. The optimum steam/n-butene ratio, reaction temperature, and gas hourly space velocity were found to be 15, 420 °C, and 675 h⁻¹, respectively.     

Synthesis and Thermoelectric Properties of Ceramics Based on Bi<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Co<Subscript>1.7</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Oxide

Layered ceramics based on bismuth–calcium cobaltite with varied cobalt oxide contents is synthesized by the solid-phase method, the ceramics phase composition is determined, and the microstructure, thermal expansion, electroconductivity, and thermal electromotive force are investigated. The formation of just one compound, ternary oxide composed of Bi₂Ca₂Co_1.7O _y , is established within the quasi-binary Bi₂Ca₂O₅–CoO _z system. The effect of the cobalt oxide content on the Bi₂Ca₂Co _x O _y ceramics’ microstructure and physicochemical properties is analyzed. The single-phased ceramic sample Bi₂Ca₂Co_1.7O _y demonstrated the highest power factor value among all the investigated samples—26.0 μW/(m K²) at a temperature of 300 K. This sample showed the lowest value of the thermal linear expansion coefficient of 9.72 × 10^–6 K^–1.     

3D Hierarchical Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> Nanostructures by Polyvinylpyrrolidone (PVP) and Chloride Ion-Assisted Synthesis and Their Photodetecting Properties

A solvothermal method has been employed to synthesize bismuth sulfide (Bi₂S₃) with three-dimensional (3D) hierarchical architectures. The influences of different types of surfactants and Cl^? species on the size and morphology were investigated. A possible formation mechanism was also proposed on the basis of time-dependent experiments. The photoresponse properties show that the conductivity of Bi₂S₃ micro-flowers is significantly enhanced and the photocurrent is approximately two orders of magnitude larger than the dark current. The response and decay times are estimated to be 142 and 151 ms, respectively. It is expected that hierarchical architectures Bi₂S₃ may provide a new pathway to develop advanced nanomaterial for high-speed and high-sensitivity photoelectrical switches and photodetecting devices.     

Synthesis of nanometer sized Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript>s by a hydrothermal method and their conductivities

Nanometer-sized bismuth tungsten oxides, Bi₂WO₆s, were successfully synthesized by hydrothermal treatment at 200 °C for 24 hr, and their morphologies and crystallite sizes were influenced by adjusting the conditions to pH 4, 7, and 9. TEM images revealed that the particles were sheet-shaped and the crystallite sizes ranged from 7–120 nm. The samples absorbed in the visible range at about 380–400 nm. The lowest conductivity, 1.0×10⁶ ohm/square, was observed for Bi₂WO₆ prepared at pH 4 with a 150 nm film thickness. As the annealing temperature for Bi₂WO₆ prepared at pH 7 was increased, the conductivity decreased due of formation of larger particles by coagulation and sintering at high temperatures. Conductivity appears to improve with increasing film thickness up to 1,500 nm.     

Preparation of Bi<Subscript>2</Subscript>MoO<Subscript>6</Subscript> Nanomaterials and Theirs Gas-Sensing Properties

Bi₂MoO₆ nanomaterials are synthesized by a facile solvothermal method. Morphology and structure of the Bi₂MoO₆ nanomaterials are analyzed by SEM, XRD, N₂ adsorption techniques and XPS. Gas-sensing properties of the as-prepared Bi₂MoO₆ sensors are also systematically investigated. The results show the Bi₂MoO₆ nanomaterials consist of nanosheets and demonstrate good crystallinity. The optimal operating temperature of the Bi₂MoO₆ sensors is 240 °C. At this operating temperature, The Bi₂MoO₆ sensor exhibits a fast response-recovery to ethanol, suggesting its excellent potential application as a gas sensor for ethanol gas-sensing applications.     

Photoreduction of CO<Subscript>2</Subscript> into CH<Subscript>4</Subscript> using Bi<Subscript>2</Subscript>S<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> double-layered dense films

Nano-sized bismuth sulfide (Bi₂S₃) and titanium dioxide (TiO₂) with the orthorhombic and anatase tetragonal structures, respectively, were synthesized for application as catalysts for the reduction of carbon dioxide (CO₂) to methane (CH₄). Four double-layered dense films were fabricated with different coating sequences—TiO₂ (bottom layer)/Bi₂S₃ (top layer), Bi₂S₃/TiO₂, TiO₂/Bi₂S₃: TiO₂ (1 : 1) mix, and Bi₂S₃: TiO₂ (1 : 1) mix/Bi₂S₃: TiO₂ (1 : 1) mix—and applied to the photoreduction of CO₂ to CH₄; the catalytic activity of the fabricated films was compared to that of the pure TiO₂/TiO₂ and Bi₂S₃/Bi₂S₃ doubled-layered films. The TiO₂/Bi₂S₃ double-layered film exhibited superior photocatalytic behavior, and higher CH₄ production was obtained with the TiO₂/Bi₂S₃ double-layered film than with the other films. A model of the mechanism underlying the enhanced photoactivity of the TiO₂/Bi₂S₃ double-layered film was proposed, and it was attributed in effective charge separation.     

The Structure of Fusion-Cast High-Chrome Oxide Refractories in the Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> - MgO - Al<Subscript>2</Subscript>O<Subscript>3</Subscript> System

The phase composition and structure of fusion-cast refractories composed of 57.0 – 84.2% Cr₂O₃, 4.3 – 36.1% MgO, 2.0 – 9.7% Al₂O₃, and 2.4 – 6.9% SiO₂ have been studied by petrographic and x-ray spectral microprobe analysis methods. Refractories high in MgO with modulus M = (Cr₂O₃ +Al₂O₃)/MgO = 1.64 – 3.1 are shown to consist of spinel phase Mg(Cr, Al)₂O₄ and silicate glass. Refractory materials (80.8 – 84.2% Cr₂O₃, 4.3 – 4.7% MgO, 2.0 – 9.7% Al₂O₃, and 2.7 – 6.9% SiO₂ with M = 18.7 – 20.2) are three-phase systems composed of spinel, escolaite, and glass phase. These materials, owing to their high corrosion resistance, have promising potentiality for practical applications.__________Translated from Novye Ogneupory, No. 12, pp. 69 – 74, December, 2004.     

Synthesis and electrochemical properties of layered LiNi<Subscript>1/2</Subscript>Mn<Subscript>1/2</Subscript>O<Subscript>2</Subscript>prepared by coprecipitation

Spherical LiNi_1/2Mn_1/2O ₂ powders were synthesized from LiOH . H₂O and coprecipitated metal hydroxide, (Ni_1/2Mn_1/2)(OH)₂. The average particle size of the powders was about 10 m and the size distribution was quite narrow due to the homogeneity of the metal hydroxide, (Ni_1/2Mn_1/2)(OH)₂. The tap-density of the LiNi_1/2Mn_1/2O₂ powders was approximately 2.2 g cm_–3, which is comparable to the tap-density of commercial LiCoO₂. The LiNi_1/2Mn_1/2 O₂electrode delivered a discharge capacity of 152, 163, 183, and 189 mA h g^–1 in the voltage ranges of 2.8–4.3, 2.8–4.4, 2.8–4.5, and 2.8–4.6 V, respectively, with good cyclability. Furthermore, Al(OH)₃-coated LiNi_1/2Mn_1/2O₂exhibited excellent cycling behavior and rate capability compared to the pristine electrode.     

Influence of phosphorous addition on Bi<Subscript>3</Subscript>Mo<Subscript>2</Subscript>Fe<Subscript>1</Subscript> oxide catalysts for the oxidative dehydrogenation of 1-butene

Bi₃Mo₂Fe₁P _x oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi₃Mo₂Fe₁ oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi₃Mo₂Fe₁P_0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts.     

Dielectric Properties of Sol–Gel‐Derived Bi12SiO20 Thin Films

In this paper the dielectric properties of crack‐free, Bi₁₂SiO₂₀ thin films were investigated. The films were prepared on Pt/TiO₂/SiO₂/Si and corundum substrates using the sol–gel method. The formation of a pure Bi₁₂SiO₂₀ phase was observed at a temperature of 700°C. The Bi₁₂SiO₂₀ thin films, heat treated at 700°C for 1 h, had a dense microstructure with an average roughness (R_a) of 50 nm. The dielectric properties of the film were characterized by using both low‐ and microwave‐frequency measurement techniques. The low‐frequency measurements were conducted with a parallel capacitor configuration. The dielectric constant and dielectric losses were 44 and 7.5 × 10^?3, respectively. The thin‐film dielectric properties at the microwave frequency were measured using the split‐post, dielectric resonator method (15 GHz) and the planar capacitor configuration (1–5 GHz). The dielectric constant and the dielectric losses measured at 15 GHz were 40 and 17 × 10^?3, respectively, while the dielectric constant and the dielectric losses measured with the planar capacitor configuration were 39 and 65 × 10^?3, respectively.     

Study of electrochemical properties and the charge/discharge mechanism for Li<Subscript>4</Subscript>Mn<Subscript>5</Subscript>O<Subscript>12</Subscript>/MnO<Subscript>2</Subscript>-AC hybrid supercapacitor

Spinel Li₄Mn₅O₁₂ was prepared by a sol–gel method. The manganese oxide and activated carbon composite (MnO₂-AC) were prepared by a method in which KMnO₄ was reduced by activated carbon (AC). The products were characterized by XRD and FTIR. The hybrid supercapacitor was fabricated with Li₄Mn₅O₁₂ and MnO₂-AC, which were used as materials of the two electrodes. The pseudocapacitance performance of the Li₄Mn₅O₁₂/MnO₂-AC hybrid supercapacitor was studied in various aqueous electrolytes. Electrochemical properties of the Li₄Mn₅O₁₂/MnO₂-AC hybrid supercapacitor were studied by using cyclic voltammetry, electrochemical impedance measurement, and galvanostatic charge/discharge tests. The results show that the hybrid supercapacitor has electrochemical capacitance performance. The charge/discharge test showed that the specific capacitance of 51.3 F g⁻¹ was obtained within potential range of 0–1.3 V at a charge/discharge current density of 100 mA g⁻¹ in 1 mol L⁻¹ Li₂SO₄ solution. The charge/discharge mechanism of Li₄Mn₅O₁₂ and MnO₂-AC was discussed.     

Thermophysical properties of composite materials in the Si<Subscript>3</Subscript>N<Subscript>4</Subscript> - BN system

The results of a study of the thermophysical properties (thermal diffusivity, heat capacity, heat conductivity, and coefficient of linear thermal expansion) of Si₃N₄ - BN hot-pressed composite (with BN concentration varying from 10 to 60 wt.%) in the temperature range of 20 – 900°C are reported.__________Translated from Novye Ogneupory, No. 10, pp. 47 – 49, October, 2004.     

Phase cooperation of V<Subscript>2</Subscript>O<Subscript>5</Subscript> and Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> in the selective oxidation of H<Subscript>2</Subscript>S containing ammonia and water

The selective oxidation of hydrogen sulfide containing excess water and ammonia was studied over vanadium oxide-based catalysts. The investigation was focused on the role of V₂O₅, and phase cooperation between V₂O₅ and Bi₂O₃ in this reaction. The conversion of H₂S continued to decrease since V₂O₅ was gradually reduced by treatment with H₂S. The activity of V₂O₅ was recovered by contact with oxygen. A strong synergistic phenomenon in catalytic activity was observed for the mechanically mixed catalysts of V₂O₅ and Bi₂O₃. Temperature-programmed reduction (TPR) and oxidation (TPO) and two bed reaction tests were performed to explain this synergistic effect by the reoxidation ability of Bi₂O₃. This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University.     

Thermoelectric Properties of <Emphasis Type="Italic">x</Emphasis>PbTe/Yb<Subscript>0.2</Subscript>Co<Subscript>4</Subscript>Sb<Subscript>12</Subscript> Hot-Pressed Samples

The xPbTe/Yb_0.2Co₄Sb₁₂ compounds were prepared by the ball-milling and hot-pressed process. Electrical conductivity of the composite samples are reduced with a increase in PbTe content; and, their temperature dependence coefficients show the positive values. The maximum electrical conductivity of composite materials is ~80000 Sm⁻¹ at 800 K. The Seebeck coefficient (absolute value) of the composite material is obviously improved with an increase in the dispersed phase (PbTe) content; the Seebeck coefficient (absolute value) of the 10PbTe sample is ~260 μVK⁻¹ at 700 K, which increases by 13.6% relative to that of the Yb_0.2Co₄Sb₁₂ sample. The thermal conductivity of the composite samples is improved due to introduction of PbTe, and the thermal conductivity of the 10PbTe sample is ~3 Wm⁻¹ K⁻¹ at 550 K. The maximum value of ZT is 0.78 at 700 K for the 2.5PbTe sample.     

Crystal structure of Pb<Subscript>6</Subscript>O[(Si<Subscript>6</Subscript>Al<Subscript>2</Subscript>)O<Subscript>20</Subscript>]

The crystal structure of Pb₆O[(Si₆Al₂)O₂₀)] is investigated using X-ray diffraction. The compound has tetragonal symmetry, space group I4/mmm, a = 11.7162(10) Å, c = 8.0435(12) Å, and V = 1104.13(2) ų. The structure is refined to R ₁ = 0.036 for 562 unique reflections with [F ₀] ≥ 4σF. The structure contains two symmetrically independent positions of the Pb²⁺ cations coordinated by five O atoms (Pb²⁺-O^2? = 2.34–2.68 Å). The TO₄ tetrahedra (T = Si, Al) form tubular [(Si₆Al₂)O₂₀] chains extended along the c axis. The O₄ oxygen atom is not bonded to the Si and Al atoms and is octahedrally coordinated by six Pb atoms with the formation of an oxo-centered OPb₆ octahedron. The assumption is made that, in some of lead silicate and aluminosilicate glasses, a number of oxygen atoms are located outside the tetrahedral structure and represent segregation centers of the Pb²⁺ cations due to the formation of oxo-centered complexes.     

Preparation and Characterization of LiNi<Subscript>0.8</Subscript>Co<Subscript>0.2</Subscript>O<Subscript>2</Subscript> Synthesized by an Emulsion Drying Method

A layered LiNi_0.8Co_0.2O₂ solid solution, which is a promising cathode material for secondary lithium batteries, was successfully synthesized by an emulsion drying method. Because electrochemical properties significantly depend on the conditions of the synthesis, the calcination temperature was carefully determined on the basis of X-ray diffraction and TG studies. The prepared cathodes were characterized by means of SEM, BET, X-ray diffraction, Rietveld refinement, cyclic voltammetry and a charge-discharge experiment. From the Rietveld analysis, it was found that powder calcined at 800 °C for 12 h exhibits a well ordered and lower cation mixed layered structure than the others. The cyclic voltammetry experiment shows that phase transformation can be suppressed considerably by increasing the calcination temperature to 800 °C. The highest discharge capacity of 188.4 mA h g⁻¹ was obtained from the sample prepared at 800 °C. Furthermore, a high capacity retention ratio of 88.1% was found for the initial value after 50 cycles at a constant current density of 40 mA g⁻¹ between 2.7 V_Li/Li⁺ and 4.3 V_Li/Li⁺. In the rate capability test, the cathode delivered a higher discharge capacity of 153.1 mA h g⁻¹ at a 4 C (800 mA g⁻¹) rate.     

Thermal behavior of layered perovskite-like compounds in the Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript>-BiFeO<Subscript>3</Subscript> system

The thermal properties of compounds of the general formula Bi _{m + 1} Fe _{m ? 3} Ti₃O_{3m + 3}, which are layered perovskite-like phases of the Aurivillius type, are investigated as a function of their composition. It is demonstrated that the temperature of decomposition of the Bi _{m + 1} Fe _{m ? 3} Ti₃O_{3m + 3} compounds decreases with an increase in the thickness of perovskite-like layers alternating in the structure and that the composition dependence of the temperature of the structural transition observed in these compounds exhibits a more complex behavior. The linear thermal expansion coefficients of all the compounds under investigation are found to be virtually independent of the composition.