Enhanced ethanol sensing properties of WO3 modified TiO2 nanorods

Pristine and WO₃ decorated TiO₂ nanorods (NRs) were synthesised to investigate n-n-type heterojunction gas sensing properties. TiO₂ NRs were fabricated via hydrothermal method on fluorine-doped tin oxide coated glass (FTO) substrates. Then, tungsten was sputtered on the TiO₂ NRs and thermally oxidised to obtain WO₃ nanoparticles. The heterostructure was characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectroscopy. Fabricated sensor devices were exposed to VOCs such as toluene, xylene, acetone and ethanol, and humidity at different operation temperatures. Experimental results demonstrated that the heterostructure has better sensor response toward ethanol at 200 °C. Enhanced sensing properties are attributed to the heterojunction formation by decorating TiO₂ NRs with WO₃.     

Detection of liquid petroleum gas using mixed nanosized tungsten oxide-based thick-film semiconductor sensor

The thick-film semiconductor sensor for liquid petroleum gas (LPG) detection was fabricated using a mixed WO₃-based sensor. We present the characterization of both their structural properties by means of XRD measurements and the electrical characteristics by using gas-sensing properties. The sensing characteristics such as sensitivity, working range, cross-sensitivity and response time were studied by using nanosized WO₃-based mixed with different metal oxides (SnO₂, TiO₂ and In₂O₃) and doped with noble metals (Au, Pd and Pt). The WO₃-based mixed with 5 wt.% In₂O₃ and 0.5 wt.% Pd showed the higher sensing characteristic at low concentration of LPG sensor at an operating temperature 225 °C.     

Ammonia gas sensor based on a spinel semiconductor,Co<Subscript>0.8</Subscript>Ni<Subscript>0.2</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanomaterial

Thick film of nanocrystalline Co_0.8Ni_0.2Fe₂O₄ was obtained by sol–gel citrate method for gas sensing application. The synthesized powder was characterized by X-ray diffraction (XRD) and transmission electron microscopy. The XRD pattern shows spinel type structure of Co_0.8Ni_0.2Fe₂O₄. XRD of Co_0.8Ni_0.2Fe₂O₄ revels formation of solid solution with average grain size of about 30 nm. From gas sensing properties it observed that nickel doping improves the sensor response and selectivity towards ammonia gas and very low response to LPG, CO, and H₂S at 280 °C. Furthermore, incorporation of Pd improves the sensor response and stability of ammonia gas and reduced the operating temperature upto 210 °C. The sensor is a promising candidate for practical detector of ammonia.     

Highly sensitive acetone gas sensor based on ultra-low content bimetallic PtCu modified WO3·H2O hollow sphere

Acetone is an important industrial raw material as well as biomarker in medical diagnosis. The detection of acetone has great significance for safety and health. However, high selectivity and low concentration (ppb level) detection remain challenges for semiconductor gas sensor. Herein, we present a novel sensitive material with bimetallic PtCu nanocrystal modified on WO₃·H₂O hollow spheres (HS), which shows high sensitivity, excellent selectivity, fast response/recovery speed and low limit of detection (LOD) to acetone detection. Noteworthy, the response (R_a/R_g) of WO₃·H₂O HS sensor increased by 9.5 times after modification with 0.02% bimetallic PtCu nanocrystals. The response of PtCu/WO₃·H₂O HS to 50 ppm acetone is as high as 204.9 with short response/recovery times (3.4 s/7.5 s). Finally, the gas-sensitivity mechanism was discussed based on gas sensitivity test results. This research will offer a new route for high efficient acetone detection.     

WO3纳米片：基于有机-无机杂化前驱物的制备及光催化性能

以商业三氧化钨粉末做为钨源,通过合成WO_x-EDA（EDA=乙二胺）有机-无机杂化纳米带为前驱物,再加盐酸酸化,迅速得到中间产物正交型钨酸单晶纳米片。再在空气气氛下,将中间产物在管式炉中煅烧2h,最终得到单斜型三氧化钨单晶纳米片。一系列对比实验的结果表明,在由杂化纳米带转变成钨酸纳米片时,反应温度、反应时间、酸化浓度等实验参数对产物的结构和形貌有着很大的影响。通过计算,制得的三氧化钨纳米片带隙为2.48eV。对比于商业三氧化钨粉末,三氧化钨纳米片在可见光降解罗丹明B（RhB）中表现出更优越的性能。     

A solid-state pH sensor based on WO3-modified vertically aligned multiwalled carbon nanotubes

In this communication, a novel solid-state pH sensor based on WO₃/MWNTs nanocomposite electrode will be reported. WO₃ nanoparticles were homogeneously coated on vertically aligned MWNTs by magnetron sputtering. Potentiometric pH response of the WO₃/MWNTs electrode in Britton–Robinson buffers revealed a linear working range from pH 2 to12 with a slope of about ?41 mV pH^?1 and a response time less than 90 s. The stability of the electrode remained over a month. Moreover, the WO₃/MWNTs electrode displayed excellent anti-interference property. Compared to conventional pH sensors, the pH sensor based on WO₃/MWNTs nanocomposite electrode also showed excellent reproducibility, high stability and superb selectivity.     

Detection of nitrogen dioxide using mixed tungsten oxide-based thick film semiconductor sensor

The thick film semiconductor sensor for NO₂ gas detection was fabricated by screen-printing method using a mixed WO₃-based as sensing material. The sensing characteristics, such as response time, response linearity, sensitivity, working range, cross sensitivity, and long-term stability were further studied by using a WO₃-based mixed with different metal oxides (SnO₂, TiO₂ and In₂O₃) and doped with noble metals (Au, Pd and Pt) as sensing materials was observed. The highest sensitivity for low concentrations (<16 mg l⁻¹) was observed using WO₃-based mixed with In₂O₃ or TiO₂. The NO₂ gas sensor showing the fastest response and recovery time (both within 2 min), good linearity (Y=0.606X+0.788 R²=0.991) for gas concentrations from 3 to 310 mg l⁻¹, low resistance (3 MΩ), high sensitivity, undesirable cross sensitivity effect and good long-term stability (at least 120 days) using WO₃-SnO₂-Au as sensing material.     

WO_3纳米片:基于无机-有机杂化前驱物的制备及光催化性能

以商业三氧化钨粉末做为钨源,通过合成WOx-EDA(EDA=乙二胺)无机-有机杂化纳米带为前驱物,再加盐酸酸化,迅速得到中间产物正交型钨酸单晶纳米片。再在空气气氛下,将中间产物在管式炉中煅烧2 h,最终得到单斜型三氧化钨单晶纳米片。一系列对比实验的结果表明,在由杂化纳米带转变成钨酸纳米片时,反应温度、反应时间、酸化浓度等实验参数对产物的结构和形貌有着很大的影响。通过计算,制得的三氧化钨纳米片带隙为2.48 eV。对比于商业三氧化钨粉末,三氧化钨纳米片在可见光降解罗丹明B(RhB)中表现出更优越的性能。     

Microstructure control of WO3 film by adding nano-particles of SnO2 for NO2 detection in ppb level

To fabricate more excellent NO₂ sensor with high sensor response and good linearity between the sensor response and NO₂ concentration, the microstructure of WO₃ lamellae was controlled by adding nano-particles of SnO₂. It was found that the sintering of WO₃ lamellae was inhibited by adding nano-particles of SnO₂. The device using WO₃ lamellae added a small amount of SnO₂ nano-particles had the highest sensor response, exhibiting a high sensor response (S = 60-540) even to dilute NO₂ (100–1000 ppb) in air at 200°C.     

Detection of acetone in the human breath as diabetes biomarker based on PPy/WO3 nanocomposite sensor by FFT continuous cyclic voltammetry method

This research represents a novel detection method of acetone level in the exhaled breath samples (RH=88 %) based on polypyrrole/tungsten oxide (PPy/WO₃) nanocomposite sensor. The PPy/WO₃ sensor was fabricated by the deposition of nanocomposite on/between interdigitated electrodes (IDEs) through electrospray coating and was then characterized by FE-SEM imaging. In this detection method, the coulometric signal of the sensor was calculated using Fast Fourier Continuous Cyclic Voltammetry (FFTCCV), where cyclic voltammetry (CV) was applied to the sensor in the defined potential rang and then charge changes of the sensor was obtained by integration of the current in all scanned potential ranges. FFTCCV method enhances the sensitivity of the sensor when exposed to the gas mixtures containing acetone. In addition to its fast coulometric response time (≤5 s) in the two linear ranges of 0.7–2.8 ppm and 2.8–28.2 ppm (R²=0.99), FFTCCV method provides the low detection limit of 70 ppb, and high sensitivity toward acetone at the optimum values of the parameters. The fabricated sensor showed great selectivity toward acetone when exposed to humid air and some exhaled gas like carbon dioxide, ammonia, methanol, ethanol and alkyl amines. The results were very satisfying as the sensor was capable to detect different acetone levels in human exhaled breath as non-invasive diagnosis of diabetes with a good correlation (R²≃0.9) to the routine blood sugar test taken by different commercial glucometers results.     

Controllable synthesis of highly crystallized mesoporous TiO_2/WO_3 heterojunctions for acetone gas sensing

Mesoporous semiconducting metal oxides(SMOs) heterojunctions are appealing sensors for gas detecting.However,due to the different hydrolysis and condensation mechanism of every metal precursor and the contradiction between high crystallinity and high surface area,the synthesis of mesoporous SMOs heterojunctions with highly o rdered mesostructures,highly crystallized frameworks,and high surface area remains a huge challenge.In this work,we develop a novel "acid-base pair"adjusted solvent evaporation induced self-assembly(EISA) strategy to prepare highly crystallized ordered mesoporous TiO_2/WO_3(OM-TiO_2/WO_3) heterojunctions.The WCl_6 and titanium isopropoxide(TIPO) are used as the precursors,respectively,which function as the "acid-base pair",enabling the coassembly with the structure directing agent(PEO-b-PS) into highly ordered meso structures.In addition,PEO-b-PS can be converted to rigid carbon which can protect the meso structures from collapse during the crystallization process.The resultant OM-TiO_2/WO_3 heterojunctions possess primitive cubic mesostructures,large pore size(～21.1 nm),highly crystalline frameworks and surface area(～98 m~2/g).As a sensor for acetone,the obtained OM-TiO_2/WO_3 show excellent re sponse/recovery perfo rmance(3 s/5 s),good linear dependence,repeatability,selectivity,and long-term stability(35 days).     

A nanosized Y(2)O(3)-based catalytic chemiluminescent sensor for trimethylamine

The development of a catalytic chemiluminescent trimethylamine (TMA) sensor is demonstrated in the present paper. Intensive chemiluminescence (CL) is detected when TMA is introduced over the surface of nanosized catalysts and subsequently catalytically oxidized by O₂ from the air, and four catalysts are investigated with the strongest CL intensity obtained on nanosized Y₂O₃. This effect is utilized to develop a novel nanosized Y₂O₃-based catalytic CL sensor for TMA which under optimal conditions exhibits a wide linear range of 60-42,000 ppm and a detection limit of 10 ppm. An attractive advantage of this novel CL sensor is its high selectivity to TMA with negligible responses to many other gases such as NH₃ and organic vapors. This CL sensor has a short response time of less than 3 s, and shows good stability when examined by continual introduction of TMA into the sensor for 96 h. The applicability of this sensor to actual fish samples is also demonstrated in the paper.     

Preparation and Characterisation of Nano-Structured WO<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> Layers for Photoelectrochromic Devices

Nano-structured WO₃-TiO₂ layers were prepared by the sol-gel route. To obtain transparent, porous and crack free layers up to 0.8 μ m with a single dipping cycle a templating strategy was used. As a template three-dimensionally network based on organically modified silane was introduced to the WO₃ and TiO₂ sols. The WO₃ layers were dip-coated onto the conductive glass substrate (TCO) and the TiO₂ layers on the top of the WO₃ layer. The morphology and the structure of the layers were determined by Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HR-TEM), Energy Dispersive X-Ray Spectroscopy (EDXS), Auger and Infrared spectroscopy. SEM image of the WO₃-TiO₂ layer confirmed the nano-porosity of the layers and give the size of the particles of about 10 nm for TiO₂ and 30 nm for WO₃ layer. Further analysis indicated that the titanium sol penetrates the WO₃ layer. Particles in the WO₃ layer consist of a crystalline monoclinic WO₃ core surrounded by a 5–10 nm amorphous phase consisting of WO₃, TiO₂ and SiO₂. The WO₃-TiO₂ layers were used to assemble all solid state photoelectrochromic (PE) devices. Under 1 sun irradiation (1000 W/m²) the visible transmittance of the PE device changes from 62% to 1.6%. The colouring and bleaching processes last about 10 minutes.     

Hydrothermal preparation and visible-light photocatalytic activity of Bi2WO6 powders

Bi₂WO₆ powder photocatalyst was prepared using Bi(NO₃)₃ and Na₂WO₄ as raw materials by a simple hydrothermal method at 150 °C for 24 h, and then calcined at 300, 400, 500, 600 and 700 °C for 2 h, respectively. The as-prepared samples were characterized with UV-visible diffuse reflectance spectra, fourier transform infrared spectra (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and N₂ adsorption-desorption measurement. The photocatalytic activity of the samples was evaluated using the photocatalytic oxidation of formaldehyde at room temperature under visible light irradiation. It was found that post-treatment temperature obviously influenced the visible-light photocatalytic activity and physical properties of Bi₂WO₆ powders. At 500 °C, Bi₂WO₆ powder photocatalyst showed the highest visible-light photocatalytic activity due to the samples with good crystallization and high BET surface area.     

Highly Ordered Mesoporous Tungsten Oxides with a Large Pore Size and Crystalline Framework for H2S Sensing

An ordered mesoporous WO₃ material with a highly crystalline framework was synthesized by using amphiphilic poly(ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymers as a structure‐directing agent through a solvent‐evaporation‐induced self‐assembly method combined with a simple template‐carbonization strategy. The obtained mesoporous WO₃ materials have a large uniform mesopore size (ca. 10.9 nm) and a high surface area (ca. 121 m² g^?1). The mesoporous WO₃‐based H₂S gas sensor shows an excellent performance for H₂S sensing at low concentration (0.25 ppm) with fast response (2 s) and recovery (38 s). The high mesoporosity and continuous crystalline framework are responsible for the excellent performance in H₂S sensing.     

TiO<Subscript>2</Subscript>/WO<Subscript>3</Subscript> photoanodes with enhanced photocatalytic activity for air treatment in a polymer electrolyte cell

The application of electrochemically enhanced photocatalysis in air treatment using a Nafion-based photoelectrochemical cell and TiO₂/WO₃ photoanodes for organic vapor photooxidation under both UV and visible light irradiation is briefly presented. In that direction, the obtained results regarding the preparation and characterization of the TiO₂/WO₃ photoanodes with enhanced photocatalytic activity are reviewed. Particular emphasis is given in the comparison of the photocatalytic behavior of bilayer TiO₂/WO₃ coatings, electrosynthesized on stainless steel mesh and powder C + mixed (WO₃ + TiO₂) photoanodes. The advantages of using a high surface area C + mixed (WO₃ + TiO₂) powder catalysts as photoanodes against their plain TiO₂ + C and WO₃ + C analogues are discussed.     

Highly sensitive Fe3O4 nanobeads/graphene-based molecularly imprinted electrochemical sensor for 17β-estradiol in water

A novel molecularly imprinted electrochemical sensor based on Fe₃O₄ nanobeads immobilized on graphene (Fe₃O₄-MIP@RGO) has been developed for detecting 17β-estradiol (17β-E2) in water using reversible addition fragmentation chain transfer (RAFT) polymerization technique. 17β-E2 can be detected by this electrochemical sensor through the response current change before and after binding 17β-E2. The Fe₃O₄-MIP@RGO-based sensor amplifies the response current in differential pulse voltammetry measurement, allowing the detection limit reaching 0.819 nM in a wide linear range from 0.05 to 10 μM. Moreover, Fe₃O₄-MIP@RGO-based sensor exhibits high selectivity and sensitivity towards 17β-E2. This MIP electrochemical sensor has a promising potential in the detection of 17β-E2 in water.     

The fluorination of scheelite with ammonium bifluoride

The interaction of scheelite with ammonium bifluoride was studied. It was shown that sheelite reacts with NH₄HF₂ at room temperature, in contrast with tungstic oxide and other tungsten compounds. Two complexes are formed (NH₄)₃WO₃F₃ and the previously unknown (NH₄)₂WO₃F₂. The compounds obtained were fluorinated to (NH₄)₃WO₂F₅ (endothermic peaks at 170° and 90°C, respectively).Cubic monocrystals of (NH₄)₃WO₂F₅ were obtained. The cubic form is unstable and underwent a lattice transformation at room temperature to the more stable tetragonal form, which was transformed reversibly into the cubic form at 140°C. The thermal decomposition of (NH₄)₂WO₃F₂ was studied.

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Zusammenfassung Es wird die Wechselwirkung von Scheelit und Ammoniumhydrogenfluorid untersucht. Im Gegensatz zu Wolframoxid und anderen Wolframverbindungen geht Scheelit mit Ammoniumhydrogenfluorid bei Raumtemperatur eine chemische Reaktion ein, wobei zwei verschiedene Komplexe gebildet werden: (NH₄)WO₃F₃ und der bisher unbekannte Komplex (NH₄)₂WO₃F₂. Die erhaltenen Verbindungen werden zu (NH₄)₃WO₂F₅ fluoriert (endotherme Peaks bei 170° bzw. 90°C).Man erhält die kubischen Einkristalle (NH₄)₃WO₂F₅. Die unstabile kubische Form wandelte sich bei Raumtemperatur in die stabilere tetragonale Form um, die bei 140°C reversibel wieder in die kubische Form überführt werden kann.Es wird weiterhin die thermische Zersetzung von (NH₄)₂WO₃F₂. untersucht.

     

聚甲基丙烯酸甲酯包覆(CH3NH3)PbBr3纳米晶静电纺丝膜的制备及对氨气的荧光传感

采用原位合成法制备了聚甲基丙烯酸甲酯包覆MAPbBr₃纳米晶(MAPbBr₃@PMMA,MA=甲铵离子)静电纺丝膜。当氨气(NH₃)通入MAPbBr₃@PMMA纤维膜时与MAPbBr₃中的MA发生取代,能显著降低MAPbBr₃@PMMA纤维的荧光强度,以此构建了基于MAPbBr₃@PMMA纤维荧光猝灭的NH₃传感器。通过扫描电镜、透射电镜、粉末X射线衍射和红外对静电纺丝膜的形貌和结构进行表征,通过紫外可见光谱、荧光光谱对其光学特性进行表征。结果表明,传感器的荧光强度与NH₃浓度在8~90 mg·L^-1之间呈现出良好的线性关系(r=0.995 9),NH₃的检出限低(3 mg·L^-1),且具有良好的重现性和选择性。在实际样品气体的测定中,加标回收率为92.2%~102.1%,相对标准偏差(RSD)为1.8%~3.2%。     

Phase equilibria up to the solidus line in the system Fe2WO6−Fe8V10W16O85

Phase equlibria in the solid state in the system Fe₂WO₆?Fe₈V₁₀W₁₆O₈₅ were studied by means of X-ray phase powder diffraction and differential thermal analysis, This system is one of the intersections of the three-component system Fe₂O₃?V₂O₅?WO₃. The investigation demonstrated that the system is not a real two-component system even below the solidus line.