Visible light photoelectrochemical responsiveness of self-organized nanoporous WO3 films

Visible light-responsive WO₃ nanoporous films with preferential orientation of the (0 0 2) planes were prepared by anodization in neutral F⁻-containing strong electrolytes. The pore diameter of the self-organized structure was estimated to be in the region of 70-90 nm. Voltages were applied by stepping, which positively influenced passivity breakdown and played a significant role in the formation of self-organized nanoporous films. Under visible light irradiation, the photocurrent density (at 1.6 V vs. Ag/AgCl) and maximum photoconversion efficiency generated by the annealed nanoporous film were 3.45 mA/cm² and 0.91%, respectively. The annealed nanoporous WO₃ films show maximum incident photon-to-current conversion efficiency of 92% at 340 nm at 1.2 V vs. Ag/AgCl. These values are higher than that of annealed compact WO₃ film due to the large interfacial heterojunction area. The photoelectrochemical activities and electronic conductivities were also enhanced by annealing crystallization, which removed the recombination centers.     

Diffusivity of anion vacancies in WO3 passive films

The WO₃ films were grown in 0.1 M HClO₄ aqueous solution, at different formation potentials (E_f) in the range of 2.0-7.0 V versus sce, on W electrode. The anion diffusion coefficient (DO) of WO₃ films was calculated from EIS spectra, following the surface charge approach (at high-field limit approximation), the Point Defect Model and the Mott-Shottky analysis. Among the parameters necessary to evaluate DO, the half-jump distance (a) is very relevant, given that a small variation in a has a great impact in the calculation of DO. In this work, it is proposed the half-jump distance (a) should be evaluated from spectroscopic data (available in the literature). The value of a (∼1.9 Å) is taken from lattice constants of a-WO₃ (amorphous-WO₃), with different values of N (coordination number), and the lattice constants of m-WO₃ (monoclinic-WO₃). The calculated value of DO was ∼3 × 10⁻¹⁷ cm²/s.     

Semiconducting properties of anodic WO3 amorphous films

The semiconducting properties of amorphous WO₃ anodic films grown in different solutions and at different current densities have been investigated. The Mott—Schottky plots have shown that the donor density, N_d, of the grown films is strongly dependent on the films thickness and is not influenced by the nature of the anodizing solutions. The possible influence of the kinetics of anodization on N_d is discussed. The intersection voltages at 1/C²_sc = 0 in the Mott—Schottky plots show a complex dependence on the film thickness. The possibility of obtaining the flat band potential from these plots is also discussed.A linear relationship between the square of the photocurrent and the electrode potential has been observed as previously reported for single crystals. The dissolution rate of anodic WO₃ films is increased under illumination and strongly decreased in presence of Fe^{$\text{2+}\text{3+}$} couple. The kinetics of electron transfer between the amorphous WO₃ anodic films and the Fe^{$\text{2+}\text{3+}$} redox couple in the electrolyte seems to occur in accordance with the theory developed for single crystal semiconductors.     

氮掺杂对SrTiO3光催化性能的影响

以尿素为氮源,利用溶胶-凝胶法制备了掺氮的N-SrTiO₃光催化剂。采用XRD、SEM和UV-Vis对N-SrTiO₃的物相、形貌和吸光性能进行表征,以高压汞灯为光源,通过甲基橙脱色率考察催化剂活性。结果表明,氮元素的掺杂增强了SrTiO₃在可见光区的吸收强度,当制备过程pH=3～4、n(N)∶n(Sr)=6∶1和焙烧温度800 ℃时,甲基橙溶液降解率达72.69%,未掺杂样品降解率为28.55%。     

The photoelectrochemical properties of anodic Bi2O3 films

Anodic oxide films on bismuth are amphoteric semiconductors with n-type and p-type behavior and an optical band gap of 2.8 eV at room temperature. The semiconducting properties were analyzed in situ during the study of electrochemical and photoelectrochemical reactions at the phase boundary oxide—electrolyte.The photopotential, photoconductivity and capacity measurements together with the electrochemical measurements have been shown to be valuable tools in the connection of bulk (electrophysical) properties with surface (electrochemical) properties.Thermodynamic stability is discussed and data are given which refer to the mechanism and kinetics of the cathodic decomposition and photodecomposition of the Bi₂O₃ layer.     

Influence of ZrO2 and WO3 doping additives on the thermal properties of porous mullite ceramics

Porous mullite-corundum refractory ceramics were produced by a patented slurry slip casting method from compositions based on commercially available α-Al₂O₃ and γ-Al₂O₃, fused SiO₂ and kaolin. Pores were formed as a result of a chemical reaction of aluminium with water. The influence of usage of raw materials and doping additives such as micro-size ZrO₂ and WO₃ on the sintering temperature, formation of crystalline phases, linear thermal expansion, thermal conductivity and thermal shock resistance of mullite-corundum ceramic was studied. The best thermal shock resistance and, simultaneously, lower thermal conductivity was achieved for the samples doped with WO₃. This was due to the influence of micro-sized WO₃ on the change in γ-Al₂O₃ modification to α-Al₂O₃ and on the structure of mullite ceramics.     

Effect of Sn doping on the electrochemical performance of NaTi2(PO4)3/C composite

In this paper, NaTi_2-xSn_x(PO₄)₃/C (x?=?0.0, 0.2, 0.3, and 0.4) composites were fabricated via facile sol-gel method, and employed as anodes for aqueous lithium ion batteries. Effect of Sn doping with various content on electrochemical properties of NaTi₂(PO₄)₃/C was investigated systematically. Sn doping on Ti site has no obvious effect on the lattice structure and morphology of NaTi₂(PO₄)₃/C. Among all samples, NaTi_1.7Sn_0.3(PO₄)₃/C (NC-Sn-3) demonstrates the best electrochemical properties. NC-Sn-3 exhibits the outstanding rate performance, delivering a discharge capacity of 103.3, 95.2, and 87.4?mAh?g^?1 at 0.5, 7, and 20?°C, respectively, 1.7, 30.5, and 56.2?mAh?g^?1 larger than those of pristine NaTi₂(PO₄)₃/C. In addition, NC-Sn-3 shows excellent cycling performance with the capacity retention of 80.6% after 1000 cycles at 5?°C. This work reveals that Sn doped NaTi₂(PO₄)₃/C with outstanding electrochemical properties are potential anode for aqueous lithium ion batteries.     

Improving electrochromic behavior of spray pyrolised WO3 thin solid films by Mo doping

The effects of molybdenum [Mo] doping on the electrochromic behavior of spray pyrolised tungsten trioxide [WO₃] thin films have been studied. It has been observed that the color-bleaching kinetics, coloration efficiency, and stability of electrochromic WO₃ films are closely related to molybdenum doping concentration, apart from their microstructure and crystallinity. While a nominal 6.0 at.% molybdenum doping produces best electrochromic response in WO₃ films, the electrochemical stability is highest when the nominal concentration of molybdenum is about 2.0 at.%. The improved electrochromic behavior of the Mo doped WO₃ films has been explained from the improved H⁺ ion diffusion coefficient in the films during coloration and decoloration process.     

Effects of fluorine doping on the electrochemical properties of LiV3O8 cathode material

A series of fluorine-doped lithium trivanadates LiV₃O_8−yF_z (z = 0, 0.03, 0.05, 0.1, 0.15, 0.2 and 0.5) were synthesized by the solid-state reaction. X-ray diffraction (XRD), Fourier transform infrared (FTIR) and scanning electron microscope (SEM) tests show that a proper amount of fluorine substituting for oxygen in LiV₃O₈ can modify its structure and surface morphology. Charge-discharge tests show that the doped samples with a proper amount of fluorine display good cycling stability, high coulombic efficiency and good rate capability, compared with undoped sample. The cyclic voltammetry (CV), area-specific impedance (ASI) and electrochemical impedance spectroscopy (EIS) tests indicate that the doped samples with a low fluorine content can stabilize the interface between the surface layer of the active particles and the electrolyte after cycling, while a high fluorine content form an unstable interface. The fluorine substitution is a convenient and effective method for improving the electrochemical performances of LiV₃O₈.     

Effect of CeO2 on the thermoelectric properties of WO3-based ceramics

The thermoelectric properties of tungsten trioxide (WO₃) ceramics doped with cerium dioxide (CeO₂) were investigated. The results demonstrated that the addition of CeO₂ to WO₃ could promote the grain growth and the densification. The magnitude of the electrical conductivity (σ) and the absolute value of the Seebeck coefficient (|s|) depended strongly on the CeO₂ content. The sample doped with 2.0 mol% CeO₂ yielded higher σ and |s|, resulting in a significant increase in the power factor (σs²). In addition, the power factor value of all samples increased abruptly at high temperatures, which revealed that WO₃-based ceramics could have greater thermoelectric properties at high temperatures.     

Effect of TiO2 on morphology and mechanical properties of PVDF/PMMA blend films prepared by melt casting process

Effect of titanium dioxide (TiO₂) on morphology and mechanical properties of poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blend films prepared at different TiO₂ contents by a melt casting process was studied. The results showed that tensile moduli in both the machine direction (MD) and the transverse direction (TD) increased with increasing TiO₂ content, and calculated tensile moduli based on the Halpin–Tsai and the Kerner model were consistent with experimental ones in both the MD and TD of films containing 10 wt % TiO₂. However, experimental tensile moduli exhibited smaller values compared with calculated ones, as the TiO₂ content increased to 30 wt %_, and it was assumed that this is due to the decrease of crystallinity of PVDF. Morphological observations indicated that TiO₂ particles did not affect crystal structures of PVDF and the morphology of PVDF/PMMA amorphous phase, but hindered the crystallization of PVDF. The MD and TD elongation at break exhibited >200 and <20%, respectively. The SEM micrographs revealed that spherulites could deform along the MD when the tensile force was applied along the direction. By contrast, spherulites could not deform along the TD and fractured at very small elongation, owing to the anisotropic morphology of spherulites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40454.     

Influence of Ag doping on electrical and magnetic properties of La0.625(Ca0.315Sr0.06)MnO3 ceramics

Polycrystalline Ag-doped [La_0.625(Ca_0.315Sr_0.06)MnO₃]_1-x:Ag_x (LCSMO) ceramics with (x = 0, 0.03, 0.05, 0.10, 0.15, and 0.20) were prepared by sol-gel method, and their structures and properties were characterized. X-ray diffraction results indicated that all bulk samples had single phase with orthorhombic phase (space group of Pbnm) without impurities. With the increase of Ag doping content, the resistivity of the samples decreased, while the remanent magnetization and coercive field increased. The metal to insulator transition temperature (T_p), temperature coefficient of resistance (TCR) and Curie temperature (T_c) for x = 0.20 were determined as 300 K, 9.38% (292.6 K) and 291.86 K respectively. The highest MR value of 28.36% (295.03 K) was obtained at x = 0.15. XPS data revealed that substitution between A-site ions and Ag⁺ could increase the ratio of Mn⁴⁺ ion. Double exchange effect (DE) enhanced by changing Mn–O bond distance, Mn–O–Mn bond angle, and increasing Mn⁴⁺ ion concentration. These features promoted the transfer of itinerant electron between Mn³⁺ and Mn⁴⁺ ions. However, the magnetization obtained at x = 0.20 was less than that at x = 0, as diamagnetic Ag released magnetism of the samples. The results suggested that the LCSMO polycrystalline ceramics could be used as a candidate to prepare room temperature infrared detectors, magnetic sensors or magneto-electric devices, and so on.     

Optical and electrical properties of thin films of WO3 electrochemically coloured

Strong blue colouration has been induced in rf sputtered thin films of WO₃ by electrochemical injection of H⁺, Li⁺, and Ag⁺ ions from various solid and liquid electrolytes. Electrical conductivity and optical properties of the coloured films are reported. Comparison of these properties with those of single crystal tungsten bronzes of equivalent composition is made. Evidence, electrical and optical, for a non-uniform distribution of injected ions produced by relatively fast diffusion down grain boundaries in these polycrystalline WO₃ films is presented. A model for the optical absorption consisting of two components, due to (i) conduction electron intra-band transitions (in states close to crystalline surfaces) and (ii) transitions from unionized donor states to the conduction band (in the grain boundary phase), is tentatively proposed.     

Thermoelectric properties of Bi2O3-added WO3 ceramics

Tungsten trioxide (WO₃) ceramics were prepared by firing Bi₂O₃-added WO₃ compacts with atomic ratios of Bi/W?=?0.00, 0.01, 0.03, or 0.05, in which Bi₂O₃ was mixed as a sintering agent. Dense ceramics consisting of remarkably grown WO₃ grains were obtained for Bi-containing samples with Bi/W?=?0.01, 0.03, and 0.05. The grain growth was enhanced by the liquid phase of Bi₂W₂O₉ formed among the WO₃ grains while firing. The XRD patterns did not show evidence for Bi inclusion into the WO₃ lattice, but the SEM-EDX showed an intensive distribution of Bi into the grain boundaries. Electrical conductivity σ and Seebeck coefficient S were measured in a temperature range of 373–1073?K. The temperature dependences indicated that the Bi₂O₃-added WO₃ ceramics were n-type semiconductors. It was considered that the electron carriers were generated from oxygen vacancies included into the WO₃ grains. The thermoelectric power factors S²σ for the ceramics ranged from 1.5?×?10^?7 W?m^?1 K^?2 to 2.8?×?10^?5 W?m^?1 K^?2, and the highest value occurred at 970?K for the ceramic with Bi/W?=?0.01.     

Macroporous WO3: Tunable morphology as a function of glycine concentration and its excellent acetone sensing performance

Materials-by-Design symbolizes the development of advanced materials with cost and time -effective experimentation. Here, we show the single and unique strategy of developing macroporous WO₃ with different morphologies (nano to micro) using glycine as structure assisting agent. The developed structures were analyzed with various characterizing tools, and tested for practical application as acetone gas sensor (83.87% for 10?ppm). The morphological correlation with the sensitivity is described.     

Gas-Sensing Properties of Nanocrystalline WO3 Films Made by Advanced Reactive Gas Deposition

Nanocrystalline WO₃ films were produced by advanced reactive gas deposition onto alumina substrates. The as-deposited films had a tetragonal crystal structure and a mean grain size of around 6 nm, as found by X-ray diffraction and electron microscopy. Sintering at a temperature τ_s > 770 K yielded monoclinic films. We investigated the gas-sensing properties of films sintered up to 870 K. After an initial "activation" at τ_s= 750 K, the nanocrystalline WO₃ films showed excellent gas-sensing properties, even at room temperature, on exposure to low concentrations of H₂S in air. As little as 10 ppm of H₂S made the conductance increase by a factor of about 10³ within 10 min. The initial properties could be restored by heating the films to 530 K for 1 min.     

Influence of the morphology and microstructure on the photocatalytic properties of titanium oxide films obtained by sparking anodization in H3PO4

The aim of this paper is to investigate changes in morphology and microstructure of TiO₂ films, prepared by sparking anodization of Ti in a H₃PO₄ solution, by applying different formation charges. We show that although films obtained by this technique are rarely used in photocatalytic applications, the morphological and microstructural changes during sparking anodization produce TiO₂ films that can be used as photocatalysts. In contrast to qualitative analysis commonly found in the literature, we used quantitative methods of analysis to quantify average pore diameter and pore density from the morphology and structural parameters from X-ray diffraction (XRD) patterns using the Rietveld refinement. The results indicated that changes in both the morphology and crystalline structure have a strong influence on the photoactivity of the films. From this investigation, we concluded that, for films prepared in early stages of anodization, the morphology had the biggest influence on photoactivity, and after applying 72C of charge, crystalline properties dominated the photocatalytic characteristics of the films.     

反应溅射条件对WO3薄膜光电性能的影响与探索

使用反应溅射法在FTO导电玻璃基底上制备了附着力强、表面光滑、均匀的WO3光电薄膜,系统地研究了氩气与氧气流量比和溅射功率对该薄膜光电性能的影响。通过XRD、AFM、Mott-Schottky(M-S)分别分析薄膜的物相、形貌、光电性质。光电转化效率(IPCE)测试表明:当氩氧流量比为2和溅射功率250 W时,WO3薄膜的光电性能最好。该薄膜在400 nm波长处的IPCE值高达40%。     

Catalytic reduction of NO by C3H6 over Rh/TiO2 catalysts: Effect of W-cation doping of TiO2 on morphological characteristics and catalytic performance

The effect of W⁶⁺-cation doping of TiO₂ on its physicochemical characteristics has been examined and related to the catalytic performance of dispersed rhodium crystallites for the selective catalytic reduction (SCR) of NO by propylene in the presence of excess oxygen. It was found that doping of TiO₂ with small amounts of W⁶⁺ cations results in materials with increased surface areas and anatase-to-rutile contents, in a manner which depends on dopant concentration and calcination temperature. The acidity of the doped supports, measured by adsorption of ammonia, increases with increasing W⁶⁺-cation concentration and goes through a maximum for dopant contents of ca. 0.45 at.% W⁶⁺. The catalytic performance of supported rhodium for the SCR of NO by propylene is significantly improved over the doped carriers and varies with W⁶⁺-content in a way which is qualitatively similar to that of acidity. Results are explained evoking the beneficial effect of acidity on adsorption and partial oxidation of propylene, which results in faster regeneration of the catalytically active Rh⁰ sites, and the dopant-induced modifications of the electronic structure of rhodium crystallites which result in higher dissociation rates of adsorbed NO. Under the experimental conditions employed, the conversion of NO over the 0.5%Rh/TiO₂(0.45% W⁶⁺) catalyst is significantly improved and reaches 52%, compared to 38% over the undoped one. A further increase of conversion to 65% is achieved with increasing Rh loading to 1.5 wt.%. Measurements of the specific reaction rates show that the turnover frequency (TOF) of the reaction is only affected by electronic-type modifications and not by the geometric properties of the active sites.