Fabrication of heterojunction SnO2/BiVO4 composites having enhanced visible light photocatalystic activity

SnO₂/BiVO₄ heterojunction composite photocatalysts with various mole ratios have been prepared via a simple hydrothermal method. The structure, composition and optical properties of the SnO₂/BiVO₄ composites were determined by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) surface analysis, X-ray photoelectron spectroscopy (XPS) and UV–vis diffuse reflectance spectroscopy (UV–vis DRS). Photocatalytic activities of the composites were evaluated by studying the degradation of methylene blue (MB) solutions under simulated visible light irradiation (500 W halogen tungsten lamp). The 3:7 mol ratio SnO₂/BiVO₄ composite exhibited the highest photocatalytic performance, leading to 72% decompositon of MB within 120 min of irradiation.     

Room temperature NO2 gas sensing properties of DBSA doped PPy–WO3 hybrid nanocomposite sensor

We demonstrate the chemiresistive NO₂ gas sensor based on DBSA doped PPy–WO₃ hybrid nanocomposites operating at room temperature. The sensor was fabricated on glass substrate using simple and cost effective drop casting method. The gas sensing performance of sensor was studied for various toxic/flammable analytes like NO₂, C₂H₅OH, CH₃OH, H₂S and NH₃. The sensor shows higher selectivity towards NO₂ gas with 72% response at 100 ppm. Also the sensor can successfully detect low concentration of NO₂ gas upto 5 ppm with reasonable response of 12%. Structural, morphological and compositional analyses evidenced the successful formation of DBSA doped PPy–WO₃ hybrid nanocomposite with uniform dispersion of DBSA into PPy–WO₃ hybrid nanocomposite and enhance the gas sensing behavior. We demonstrated that DBSA doped PPy–WO₃ hybrid nanocomposite sensor films shows excellent reproducibility, high stability, moderate response and recovery time for NO₂ gas in the concentration range of 5–100 ppm. A gas sensing mechanism based on the formation of random nano p–n junctions distributed over the surface of the sensor film has been proposed. In addition modulation of depletion width takes place in sensor on interaction with the target NO₂ gas has been depicted on the basis of schematic energy band diagram. Impedance spectroscopy was employed to study bulk, grain boundary resistance and capacitance before and after exposure of NO₂ gas. The structural and intermolecular interaction within the hybrid nanocomposites were explored by Raman and X-ray photoelectron spectroscopy (XPS), while field emission scanning electron microscopy (FESEM) was used to characterize surface morphology. The present method can be extended to fabricate other organic dopent-conducting polymer–metal oxide hybrid nanocomposite materials and could find better application in the gas sensing.     

Nitrogen dioxide (NO2) sensing performance of p-polypyrrole/n-tungsten oxide hybrid nanocomposites at room temperature

Polypyrrole (PPy)–tungsten oxide (WO₃) hybrid nanocomposite have been successfully synthesized using different weight percentages of tungsten oxide (10–50%) dispersed in polypyrrole matrix by solid state synthesis method. The sensor based on PPy–WO₃ was fabricated on glass substrate using cost effective spin coating method for detection of NO₂ gas in the low concentration range of 5–100 ppm. The gas sensing performance of hybrid material was studied and compared with those of pure PPy and WO₃. It was found that PPy–WO₃ hybrid nanocomposite sensor can complement the drawbacks of pure PPy and WO₃. The structure, morphology and surface composition properties of PPy–WO₃ hybrid nanocomposites were employed by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The presence of WO₃ in PPy matrix and their interaction was confirmed using XRD, FTIR techniques. The porous surface morphology was observed with addition of WO₃ in PPy matrix which is useful morphology for gas sensing applications. TEM image of PPy–WO₃ hybrid nanocomposites shows the average diameter of 80–90 nm. X-ray photoelectron spectroscopy (XPS) was used to characterize the chemical composition of nanocomposites. It was observed that 50% WO₃ loaded PPy sensor operating at room temperature exhibit maximum response of 61% towards 100 ppm of NO₂ gas and able to detect low concentration of 5 ppm NO₂ gas with reasonable response of 8%. The hybrid sensor shows better sensitivity, selectivity, reproducibility and stability compared to pure PPy and WO₃. The proposed sensing mechanism of hybrid nanocomposite in presence of air and NO₂ atmosphere was discussed with the help of energy band diagram. Furthermore, the interaction of NO₂ gas with PPy–WO₃ hybrid nanocomposites sensor was studied by cole–cole plot using impedance spectroscopy.     

Synthesis of highly selective and sensitive Cu-doped ZnO thin film sensor for detection of H2S gas

Copper (Cu) doped zinc oxide (ZnO) thin films were successfully prepared by a simple sol-gel spin coating technique. The effect of Cu doping on the structural, morphology, compositional, microstructural, optical, electrical and H₂S gas sensing properties of the films were investigated by using XRD, FESEM, EDS, FTIR, XPS, Raman, HRTEM, and UV–vis techniques. XRD analysis shows that the films are nanocrystalline zinc oxide with the hexagonal wurtzite structure and FESEM result shows a porous structured morphology. The gas response of Cu-doped ZnO thin films was measured by the variation in the electrical resistance of the film, in the absence and presence of H₂S gas. The gas response in relation to operating temperature, Cu doping concentration, and the H₂S gas concentration has been systematically investigated. The maximum H₂S gas response was achieved for 3 at% Cu-doped ZnO thin film for 50 ppm gas concentration, at 250 °C operating temperature.     

SnO2 gas sensor fabricated by low frequency alternating field electrophoretic deposition

SnO₂ thick film gas sensor has been prepared by applying low frequency (0.1 Hz) AC electric fields to a stable suspension of SnO₂ nanoparticles in acetylacetone. Parallel gold electrodes were used as the deposition substrate. Effect of CO, O₂ and H₂ gas exposure as well as ethanol vapor on conductivity of the SnO₂ film at 300 °C is investigated. Results show that the sensor is sensitive and its response is repeatable. This work shows that ACEPD can be used as an easy and cheap technique for fabrication of electronic devices such as ceramic-based gas sensors.     

Detection of H2S,SO2, and NO2 using electrostatic sprayed tungsten oxide films

This paper presents the electrostatic spray deposition of tungsten oxide (WO₃) films for the detection of different pollutant gases. The influence of several types of precursors on the structure and morphology of the films was studied by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. This preliminary study allowed to select the proper precursor for the preparation of pure and porous WO₃ films which offer high gas response (R_air/R_gas=1200) to low concentrations of H₂S (10 ppm) at low operating temperature (200 °C). The gas response to NO₂ and SO₂ is low at this temperature suggesting no possible interference with these two gases during the H₂S detection. Furthermore, the films are able to detect very low concentrations of NO₂ (less than 1 ppm) at 150 °C.     

WO3/TiO2 nanocomposites: Salt–ultrasonic assisted hydrothermal synthesis and enhanced photocatalytic activity

A series of WO₃/TiO₂ composite photocatalysts were fabricated via a facile salt–ultrasonic assisted hydrothermal process. The obtained samples were characterized by X-ray diffraction, scanning eletron microscopy, energy dispersive X-ray spectroscopy and UV–vis diffused reflectance spectroscopy. It was confirmed that anatase TiO₂ and monoclinic WO₃ coexisted in the composites. The photocatalytic activity of as-prepared WO₃/TiO₂ composites for degradation of Rhodamin B (RhB) under visible light irradiation was investigated. The results showed that WO₃/TiO₂ composites have a higher photocatalytic activity than those of pure TiO₂ and pure WO₃. First-principle calculations based on density functional theory were performed to explore the electronic structure and illustrate the photocatalytic mechanism of WO₃/TiO₂. The calculated energy gap was 2.53 eV, which was close to the experimental observation (2.58 eV). Due to the combination of WO₃/TiO₂, the photoinduced electrons and holes transfer between the WO₃ and TiO₂ in opposite directions, thus providing sufficient charge separation, which contributed to the photocatalytic activity enhancement.     

Photocatalytic and bactericidal activities of hydrothermally and sonochemically prepared Fe2O3–SnO2 nanoparticles

Fe₂O₃–SnO₂ nanocomposites (NCs) were prepared by hydrothermal and sonochemical methods. Transmission electron micrographs confirmed that the composites comprise nanoparticles. Energy-dispersive X-ray analyses revealed compositions of 25 at.% Sn and 22 at.% Fe for hydrothermally prepared NC (HNC) and 4 at.% Sn and 56 at.% Fe for sonochemically prepared NC (SNC). X-Ray diffractograms revealed rutile SnO₂, γ-Fe₂O₃, and FeO(OH) as components of HNC, and rutile SnO₂, γ-Fe₂O₃, β-Fe₂O₃ and FeO(OH) of SNC. Both NCs absorb visible light and display red emission. The solid-state impedance spectrum for HNC is a half-semicircular arc and SNC exhibits a quasi-linear relationship between Z′′ and Z′. Both NCs are ferromagnetic. The saturation magnetization of HNC is much less than that of the SNC, which in turn is far less than that of the γ-Fe₂O₃ precursor. Both NCs display visible light photocatalysis and HNC is a better photocatalyst than SNC. Furthermore, both NCs exhibit bactericidal activity.     

Effect of fluorine doping on the structural,optical and electrical properties of spray deposited cadmium stannate thin films

Cadmium stannate (Cd₂SnO₄) thin films were coated on Corning 1737 glass substrates at 540 °C by spray pyrolysis technique, from the aqueous solution of cadmium acetate and tin (II) chloride precursors. Fluorine doped Cd₂SnO₄ (F: Cd₂SnO₄) thin films were prepared by adding ammonium fluoride in the range of 0–5 wt% of the total weight of cadmium acetate and tin (II) chloride in the spray solution. Thickness of the prepared films is about 300 nm. X-ray diffraction analysis of the Cd₂SnO₄ and 3 wt% F: Cd₂SnO₄ films shows the signature for the growth along (222) direction. Scanning electron micrographs showed that fluorine doping effectively modifies the surface morphology of Cd₂SnO₄ films. Average optical transmittance in the visible region (500–850 nm) for Cd₂SnO₄ is ~79% and it is increased to ~83% for 1 wt% doping concentration of the NH₄F in the solution. Fluorescence spectra of F: Cd₂SnO₄ (1 wt% and 3 wt%) exhibit peak at 601 nm. F: Cd₂SnO₄ film (1 wt%) shows mobility of ~42 cm²/V s, carrier concentration of ~9.5×10¹⁹ cm^?3 and resistivity of ~1.5×10^?3 Ω cm.     

Structural properties of size-controlled SnO2 nanopowders produced by sol–gel method

SnO₂ nanoparticles were synthesized by sol–gel method with different sol concentrations and the effect of sol concentration on the structural properties of SnO₂ was investigated. The aim of this work is synthesizing of SnO₂ nanoparticles from SnCl₂·2H₂O (tin (II) chloride dihydrate) precursor to obtain high quality powders for using as Li-ion anode material. For this purpose, during the SnO₂ precursor solution preparation, chloride ions were removed from the solution and then the sol–gel synthesis was applied. Produced SnO₂ nanopowders were characterized by x-ray diffraction (XRD), field emission gun scanning electron microscopy (FEG-SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and energy dispersive x-ray spectroscopy (EDS) analyses. TG-DTA and FT-IR analysis were performed on the synthesized sol. Grain size, crystal index and lattice strains of SnO₂ particles were calculated. The results showed that the grain size of particles has increased by the increasing of sol concentration, and the crystallinity has been improved. The smallest crystallite size (6.03 nm) was obtained from the SnO₂ sample of 6 mmole concentration sol and maximum size (9.65 nm) from 14 mmole sol according to W–H analysis.     

Nitrogen oxide gas-sensing characteristics of hierarchical Bi2WO6 microspheres prepared by a hydrothermal method

Hierarchical Bi₂WO₆ microspheres are synthesized by a hydrothermal method. Morphology and structure of Bi₂WO₆ are analyzed by SEM, XRD, XPS, and Raman spectra. Gas-sensing properties of the as-prepared Bi₂WO₆ sensor are also systematically investigated. The results show the hierarchical Bi₂WO₆ microspheres are assembled by nanosheets and demonstrate good crystallinity. The optimal operating temperature of the Bi₂WO₆ sensors is 300 °C. At this operating temperature, the Bi₂WO₆ sensor exhibits a fast response–recovery to nitrogen oxide, suggesting its excellent potential application as a gas sensor for nitrogen oxide gas-sensing applications.     

WO3/SnO2复合薄膜的制备及光电性能

采用水热法和电化学沉积法,成功制备了包覆有SnO₂纳米颗粒的WO₃纳米棒阵列薄膜,退火处理后形成WO₃/SnO₂异质结复合薄膜。通过改变SnO₂的沉积时间得到了复合薄膜的最佳制备条件。采用XRD,FESEM对WO₃/SnO₂复合薄膜的物相和形貌进行了分析,通过电化学工作站对WO₃/SnO₂复合薄膜的光电性能进行了研究,结果表明,电沉积时间为120 s时,WO₃/SnO₂复合薄膜具有最小的阻抗,且在0.6 V的偏压下光电流密度为0.46 mA/cm²,相比于单一WO₃纳米棒薄膜,表现出更好的光电化学性能。     

A study on phase transformation of SnOx thin films prepared by reactive magnetron sputtering

In the paper, SnO_x thin films were deposited by reactive magnetron sputtering from a tin target in O₂ containing working gas. The evolution from Sn-containing SnO to tetravalent SnO₂ films was investigated. The films could be classified into three groups according to their optical band gaps, which are E_g<2.5 eV, E_g=3.0–3.3 eV and E_g>3.7 eV. The electric measurements show that high conductivity can be obtained much easier in SnO₂ than in SnO films. A high electron mobility of 15.7 cm² V⁻¹ s⁻¹, a carrier concentration of 1.43×10²⁰ cm⁻³ and a resistivity of 2.8×10⁻³ Ω cm have been achieved in amorphous SnO₂ films. Films with the optical band gap of 3.0–3.3 eV remain amorphous though the substrate temperature is as high as 300 °C, which implies that °btaining high mobility in p-type SnO is more challenging in contrast to n-type SnO₂ films.     

Cr2WO6 nanoparticles prepared by hydrothermal assisted method with selective adsorption properties for methylene blue in water

Cr₂WO₆ nanocrystallites were prepared using a facile hydrothermal assisted process. The microstructures and preferential adsorption performance for methylene blue (MB) of the prepared nanoparticles were investigated using a solid state reaction resulted in Cr₂WO₆ crystallites as a baseline. Their structural information were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectrometer, transmission electron microscopy, N₂–sorption BET surface area, thermogravimetric and differential scanning calorimeters. Results show that the Cr₂WO₆ nanocrystallines with ~50 nm in size are achieved by calcination at 650 °C for only 2 h using a hydrothermal product as precursor, while the micrometer sized Cr₂WO₆ crystallites synthesized by the solid state reaction at higher temperature (950 °C) for at least 20 h. For the as-prepared Cr₂WO₆ nanocrystallines, the adsorption performance were tested using methyl orange (MO), Rhodamine B (RhB) and methylene blue (MB). The adsorption ability was found to be in the order of MB>>RhB>MO owing to electrostatic interactions between the adsorbent and the dye. Results of this study provide a kind of promising alternative adsorbent for color removal from industrial wastewaters.     

Effect of different ethanol/water solvent ratios on the morphology of SnO2 nanocrystals and their electrochemical properties

We report on the effect of different ethanol/water solvent ratios on the morphology of SnO₂ nanocrystals prepared by the conventional hydrothermal method and their electrochemical properties. The nanocrystals were structurally and morphologically characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), surface area measurements, and transmission electron microscopy. The XRD patterns indicate that the sphere-like SnO₂ microcrystals have a rutile-type tetragonal structure and FESEM images show that the microspheres have a diameter of 2–5 μm. We found that the ethanol/water volume ratio plays an important role in formation of the final product. Electrochemical tests revealed that the SnO₂ microspheres had a high initial capacity of 1546 mAh g^?1 at a current density of 100 mA g^?1 and retained a reversible capacity of 439 mAh g^?1 after 30 discharge cycles.     

Fabrication of WO3 nanostructures by anodization method for visible-light driven water splitting and photodegradation of methyl orange

Visible light-responsive WO₃ nanostructures were synthesized by anodization in a NH₄F/Na₂SO₄ electrolyte solution. Applied potential and anodization time play an important role in the formation of self-organized WO₃ nanostructures, further developed upon anodization. The average pore diameter of ～80 nm with thickness of～300 nm of WO₃ nanoporous layer was successfully synthesized at 50 V for 15 min. The uniform and regular WO₃ nanoporous layer exhibited better photocurrent density of～0.18 mA/cm² at 0.7 V vs. SCE and better photodegradation of MO solution of ～50% after 5 h of visible-light illumination. The larger active surface area of WO₃ nanoporous layer played a significant role to generate more electron-hole pairs, which triggered the PEC water splitting reaction and photodegradation reaction much more effectively.     

Structural,morphological, electrical and optical studies of Cr doped SnO2 thin films deposited by the spray pyrolysis technique

Tin oxide (SnO₂) and chromium (Cr) doped tin oxide (Cr:SnO₂) thin films were deposited on the preheated glass substrates at 673 K by spray pyrolysis. Concentration of Cr was varied in the solution by adding chromium (III) chloride hexahydrate from 0 to 3 at%. The effect of Cr doping on the structural, electrical and optical properties of tin oxide films is reported. X-ray diffraction pattern confirms the tetragonal crystal structure for undoped and Cr doped tin oxide films. Scanning electron microscopic photographs show the modification of surface morphology of tin oxide film due to varying concentration of Cr. X-ray photoelectron spectra of Cr:SnO₂ (3 at%) thin film revealed the presence of carbon, tin, oxygen, and chromium. Carrier concentration and mobility of the SnO₂ films decrease with increasing concentration of Cr and 0.5 at% Cr doped tin oxide film acquires a mobility of 70 cm²/V s. Average optical transmittance in the 550–850 nm range varies from 38% to 47% with varying Cr concentration in the solution.     

Structural,electrical and optical properties of sintered SnO2 pellets

Tin dioxide (SnO₂) powder was prepared by the co-precipitation method using SnCl₂ solution as a precursor. The powder was then pelletized and sintered. Structural characterization of the samples with XRD confirmed that all the pellets were of SnO₂ having polycrystalline nature with the crystallite size of the order of 90 nm. SEM-EDAX was used to confirm the morphology and composition of the samples. The measurements of electrical properties were carried out in the frequency range of 100 Hz to 100 kHz at various fixed temperatures from 40 °C to 160 °C. The a.c. conductivity and the dielectric constant were found to be dependent on both frequency and temperature. The frequency and temperature dependent conduction properties of SnO₂ are found to be in accordance with correlated barrier hoping model. Infrared and visible spectroscopic studies show that a strong vibration band characteristic of the SnO₂ stretching mode was present at around 620 cm^?1 and the samples exhibited optical transmittance in the visible range.     

Effect of oxygen vacancy in tungsten oxide on the photocatalytic activity for decomposition of organic materials in the gas phase

The relationship between the oxygen vacancy of tungsten oxide and its ability to decompose organic materials under visible-light irradiation was investigated experimentally. In the field of rechargeable batteries, the highest charge-discharge rate is obtained when tungsten oxide is used as a negative electrode with an O/W ratio of 2.72. This result suggested that the number of oxygen vacancies in tungsten oxide affects the photocatalytic decomposition behavior of organic materials. Therefore, with the aim of increasing the photocatalytic activity of tungsten oxide to decompose organic materials, we attempted to clarify the role of the oxygen vacancy. WO_3 − x nanoparticles, including WO_2.83 and WO_2.72 nanoparticles, were fabricated by changing the annealing temperature in a 10% H₂, 90% N₂ atmosphere to generate different densities of oxygen vacancies. Tungsten oxide with O/W ratios of 2.83 and 2.72 exhibited no photocatalytic activity for the photodecomposition of organic materials. The maximum decomposition rate was obtained for stoichiometric WO₃ (O/W = 3). The reason for the decrease or disappearance of the photodecomposition ability should originate in the increase in the number of electrons generated by the oxygen vacancies. These excess electrons promote the recombination reaction between electrons and holes in WO_3 − x, and hence reduce the lifetime of electron-hole pairs.     

Study of sensitivity and selectivity of α-Fe2O3 thin films for different toxic gases and alcohols

This paper presents a detailed study on the sensitivity and selectivity of α-Fe₂O₃ thin films produced by deposition of Fe and post-deposition annealed at two temperatures of 600 °C and 800 °C with flow of oxygen for application as a sensor for toxic gases including CO, H₂S, NH₃ and NO₂ and alcohols such as C₃H₇OH, CH₃OH, and C₂H₅OH. The crystallographic structure of the samples was studied by X-ray diffraction (XRD) method while an atomic force microscope (AFM) was employed for surface morphology investigation. The electrical response of the films was measured while they were exposed to various toxic gases and alcohols in the temperature range of 50–300 °C. The sample annealed at higher temperature showed higher response for different gases and alcohols tested in this work which can be due to the higher resistance of this sample. Results also indicated that the α-Fe₂O₃ thin films show higher selectivity to NO₂ gas relative to the other gases and alcohols while the best sensitivity is obtained at 200 °C. The α-Fe₂O₃ thin film post-deposition annealed at 800 °C also showed a good stability and reproducibility and a detection limit of 10 ppm for NO₂ gas at the operating temperature of 200 °C.