Electrochemical characterization of amorphous LiFe(WO4)2 thin films as positive electrodes for rechargeable lithium batteries

Amorphous LiFe(WO₄)₂ thin films have been fabricated by radio-frequency (R.F.) sputtering deposition at room temperature. The as-deposited and electrochemically cycled thin films are, respectively, characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray photoelectron spectra techniques. An initial discharge capacity of 198 mAh/g in Li/LiFe(WO₄)₂ cells is obtained, and the electrochemical behavior is mostly preserved in the following cycling. These results identified the electrochemical reactivity of two redox couples, Fe³⁺/Fe²⁺ and W⁶⁺/W^x+ (x = 4 or 5). The kinetic parameters and chemical diffusion coefficients of Li intercalation/deintercalation are estimated by cyclic voltammetry and alternate-current (AC) impedance measurements. All-solid-state thin film lithium batteries with Li/LiPON/LiFe(WO₄)₂ layers are fabricated and show high capacity of 104 μAh/cm² μm in the first discharge. As-deposited LiFe(WO₄)₂ thin film is expected to be a promising positive electrode material for future rechargeable thin film batteries due to its large volumetric rate capacity, low-temperature fabrication and good electrode/electrolyte interface.     

Synthesis and characterization of highly stable optically passive CeO2-ZrO2 counter electrode

Transparent and adherent CeO₂-ZrO₂ thin films having film thicknesses ∼543-598 nm were spray deposited onto the conducting (fluorine doped tin oxide coated glass) substrates from a blend of equimolar concentrations of cerium nitrate hexahydrate and zirconium nitrate having different volumetric proportions (0-6 vol.% of Zr) in methanol. CeO₂-ZrO₂ films were polycrystalline with cubic fluorite crystal structure and the crystallinity was improved with increasing ZrO₂ content. Films were highly transparent (T ∼ 92%), showing decrease in band gap energy from 3.45 eV for pristine CeO₂ to 3.08-3.14 eV for CeO₂-ZrO₂ films. The different morphological features of the film obtained at various CeO₂-ZrO₂ compositions had pronounced effect on the ion storage capacity and electrochemical stability. CeO₂-ZrO₂ film prepared at 5 vol.% Zr concentration exhibited higher ion storage capacity of 24 mC cm⁻² and electrochemical stability of 10,000 cycles in 0.5 M LiClO₄ + PC electrolyte due to its film thickness (584 nm) coupled with relatively larger porosity (8%). The optically passive behavior of such CeO₂-ZrO₂ film (with 5 vol.% Zr) is affirmed by its negligible transmission modulation irrespective of repeated Li⁺ and electron insertion/extraction. The coloration efficiency of spray deposited WO₃ thin film is found to enhance from 47 to 107 cm² C⁻¹ when CeO₂-ZrO₂ is coupled as a counter electrode with WO₃ in an electrochromic device (ECD). These films can be used as stable ‘passive’ counter electrodes in electrochromic smart windows as they retain full transparency in both the oxidized and reduced states and ever-reported longevity.     

Electrochromic WO3−x films with reduced lattice deformation stress and fast response time

Electrochromic properties of electrochemically deposited and etched (EDE) WO_3−x films have been investigated using voltammetry and nanogravimetry to elucidate the amount of residual stress associated with lattice polarization and deformation in WO_3−x nanoparticles. The cathodic WO_3−x deposition from pertungstic acid solution and unusual properties of the cathodic electroetching of the oxide in tetraethyl ammonium chloride solution are reported and elucidated on the basis of Electrochemical Quartz Crystal Nanogravimetry (EQCN) measurements. The stress enhanced resonant frequency shift was observed upon WO_3−x film coloration. However, the stress enhancement appeared to be much lower (up to 4-6 times) than that measured for films synthesized by other methods. The stress reduction in WO_3−x films under study has been attributed to the stress relaxing propensity of EDE film to suppress the compressive stress wave. A considerable isotopic effect has been observed in nanogravimetry of the H⁺ and D⁺ ion intercalation into WO_3−x films. We have found that the isotopic effect is primarily due to the true mass loading difference between hydrogen and deuterium ions, for the same concentration of color centers (2.65 × 10²¹ cm⁻³), since EQCN frequency shifts associated with stress in the film for H⁺ and D⁺ are very close to each other.     

Preparation,characterization, and mechanical-optical properties of telluro-borate glasses containing tungsten

The current work is interested in the preparation, characterization, and mechanical-optical properties of the glasses in the (75-x)B₂O₃–10SrO–8TeO₂–7ZnO−xWO₃ system, with (x = 0 (BSTZW0), 1 (BSTZW1), 5 (BSTZW2), 10 (BSTZW3), 22 (BSTZW4), 27 (BSTZW5), 34 (BSTZW6), and 40 mol% (BSTZW7). The preparation of the glasses has involved the melt-quenching route. The new glasses are characterized by different characterization techniques using densimeter, microhardness, Raman spectroscopy, UV–visible absorption and emission, and X-ray diffraction. Photoluminescence can determine the impact of substituting B₂O₃ with WO₃ on the mechanical-optical parameters and the structure of the present glasses. The prepared samples’ X-ray patterns showed amorphous states. The density value rises from 2.88 to 4.50 g/cm3, with the amount of WO₃ rising from 0 to 40 mol% as a result of the difference in molecular weight between WO₃ and B₂O₃. The Vickers microhardness (Hv) rises as the amount of WO₃ increases as a result of a decrease in free volume and the formation of covalent bonds. The elastic moduli were found to increase when the WO₃ concentrations increased from 0 to 40 mol%. This increase depends on the formation of bridging oxygen atoms. The Raman bands are designed to correspond to the bonds that form the structure of the current glass and detect the insertion of WO₃ content by the attribution of the new W–O–W and W–O bonds. The UV–Visible spectroscopy analysis showed no band characteristic for the reduced species of W⁵⁺ ions identified by dark blue. However, the photoluminescence spectra showed emission bands (under excitation at 300 nm) that are associated with the active centers of W⁴⁺, W⁵⁺, and W⁶⁺ ions.     

Oxygen vacancy enhanced room temperature ferromagnetism in Ar+ ion irradiated WO3 films

Room-temperature ferromagnetism in WO₃ films was enhanced by 130 keV Ar⁺ ion irradiation. The X-ray diffraction (XRD) and Raman measurements not only confirmed the monoclinic phase of the irradiated WO₃ films, but also showed that oxygen vacancy (V_O) defects were formed. The analysis of photoluminescence spectra strongly reconfirmed the presence of oxygen vacancy. X-ray photoelectron spectroscopy (XPS) measurements revealed that the contents of V_O and induced W⁵⁺ ions increase with increasing irradiation fluence and rich W⁵⁺-V_O defect complexes in the irradiated WO₃ films were formed. Further, the magnetic measurements exhibited a 2-fold enhancement in the saturation magnetization at the largest fluence of 3 × 10¹⁶ ions/cm². At lower irradiation fluence, a bound magnetic polaron model was proposed to reveal the ferromagnetic exchange coupling resulting from overlapping of V_O⁺ and V_O⁺⁺ defect states, and 5d¹ states of W⁵⁺. At high irradiation fluence, the carrier concentration reaches 1.02 × 10²⁰/cm³ and carrier-mediated exchange interactions result in the film's ferromagnetism.     

Electrochemical reaction of lithium with orthorhombic bismuth tungstate thin films fabricated by radio-frequency sputtering

Bi₂WO₆ thin films with fast deposition rate have been fabricated by radio-frequency (R.F.) sputtering deposition, and are used as positive electrodes in rechargeable thin film lithium batteries. An initial discharge capacity of 113 μAh/cm²-μm is obtainable for Bi₂WO₆ film electrode with good capacity reversibility. A multiple-center reactive mechanism associated with both Bi³⁺/Bi⁰ and W⁶⁺/W^x+(x < 6) is investigated by ex situ X-ray diffraction patterns, transmission electron microscopy and selected area electron diffraction techniques, apart from the direct comparison of Bi₂WO₆ electrochemical performance with those of Bi₂O₃ and WO₃ thin films. A possible explanation about smooth capacity loss of Bi₂WO₆ after long-term cycling is suggested from the incomplete reaction of Bi component. The advantages of Bi₂WO₆ thin films over the singer-center Bi₂O₃ or WO₃ thin films are shown in both the aspects of volumetric capacity and cycling life.     

Fast electrochromic response and high coloration efficiency of Al-doped WO3 thin films for smart window applications

Herein, vertically aligned Al:WO₃ nanoplate arrays were directly grown on ITO glass by a facile electrodeposition method and annealed in an argon atmosphere at 450 °C for 2h. Besides, this study reports the influence of Al doping on the electrochromic properties of WO₃ film in detail. Electrochromic properties such as cyclic voltammetry, chronoamperometry and optical transmittance were analyzed by protonic insertion/extraction in the 1 M LiClO₄/propylene carbonate as an electrolyte. The noticeable reversible color changing from transparent to the blue can be realized under the potential bias of ±1.0 V. XRD studies show that the produces films have highly crystalline structure. The EDS results clearly confirm the incorporation of Al element into the WO₃ network. From the optical absorption measurement, direct band gap energies are calculated as 3.62 and 3.34 eV for the WO₃ and the Al:WO₃, respectively. Compared to the as-prepared WO₃, the Al:WO₃ film exhibits outstanding electrochromic performance, including wide optical modulation (55.9%), high coloration efficiency (148.1 cm²C^-1), quick reaction kinetics (1.23 s and 1.01 s for colored and bleaching times, respectively), good rate capability and cycle durability at a wavelength of 632.8 nm. EIS measurements based on a charge-transfer resistance reveal that the dramatic improvement in the electrochemically active surface is achieved in the Al:WO₃ film. The increase of active surface facilitates transport kinetics for electron and ion intercalation/deintercalation within the porous metal oxide to enhance coloration efficiency. Comparatively energy levels of the WO₃ and the Al:WO₃ electrochromic films are also represented. From the Mott-Schottky studies, it is estimated that the donor concentration of the films is of the order of 10²⁰ cm⁻³. Taken together, these results not only provide important insight into a promising electrode for electrochromic displays applications, but also offer an economic and effective strategy for manufacturing of other doped metal oxide films.     

Enhanced electrochromic performance of macroporous WO3 films formed by anodic oxidation of DC-sputtered tungsten layers

Self-organized macroporous tungsten trioxide (WO₃) films are obtained by anodic oxidation of DC-sputtered tungsten (W) layers on 10 mm × 25 mm indium tin oxide (ITO)-coated glass. Under optimized experimental conditions, uniformly macroporous WO₃ films with a thickness of ca. 350 nm are formed. The film shows a connected network with average pore size of 100 nm and a pore wall thickness of approximately 30 nm. The anodized film becomes transparent after annealing without significant change in macroporous structure. In 0.1 M H₂SO₄, the macroporous WO₃ films show enhanced electrochromic properties with a coloration efficiency of 58 cm² C⁻¹. Large modulation of transmittance (∼50% at 632.8 nm) and a switching speed of about 8 s are also achieved with this macroporous film.     

Enhanced visible light photocatalytic activity of QDS modified Bi2WO6 nanostructures

Bi₂WO₆ (BWO) nanostructures with QDS dispersed on single crystalline nanosheets were successfully prepared by a facile solvothermal method. The product possessed large surface area of 60 m²/g and exhibited excellent visible light absorption with a blue shift from 2.54 eV to 2.75 eV. The photocatalytic efficiency of the sample was six times that of nanoparticles assembled BWO nanostructures and three times that of nanoplates assembled BWO nanostructures. The photocatalytic mechanism for degradation of dyes over QDS modified BWO nanostructures was discussed, which revealed the important role of QDS in the generation, migration and consumption of the photogenerated electrons and holes.     

Study on the Structure of Fe/MgO Catalysts for H2S Wet Oxidation

Mg-doped WO₃ with band gap energy of about 2.6 eV is a viable photocatalyst for visible light-induced water splitting in the presence of hole scavengers. The conduction band edge position of p-type Mg-doped WO₃ was -2.7 V versus SCE at pH 12. By doping Mg on WO₃, the conduction and valence band positions were shifted by 2.25 V negatively, leading to a conduction band edge position which was negative enough for H⁺ ions to be reduced thermodynamically, with little change in band gap energy. The negative shift in band position might be ascribed to lowering of the effective electron affinity of WO₃ by doping Mg with a very low electron affinity.     

Electrical properties of V2O5–WO3/TiO2 EUROCAT catalysts evidence for redox process in selective catalytic reduction (SCR) deNOx reaction

Electrical conductivity measurements on EUROCAT V₂O₅–WO₃/TiO₂ catalyst and on its precursor without vanadia were performed at 300°C under pure oxygen to characterize the samples, under NO and under NH₃ to determine the mode of reactivity of these reactants and under two reaction mixtures ((i) 2000 ppm NO + 2000 ppm NH₃ without O₂, and (ii) 2000 ppm NO + 2000 ppm NH₃ + 500 ppm O₂) to put in evidence redox processes in SCR deNO_x reaction.It was first demonstrated that titania support contains certain amounts of dissolved W⁶⁺ and V⁵⁺ ions, whose dissolution in the lattice of titania creates an n-type doping effect. Electrical conductivity revealed that the so-called reference pure titania monolith was highly doped by heterovalent cations whose valency was higher than +4. Subsequent chemical analyses revealed that so-called pure titania reference catalyst was actually the WO₃/TiO₂ precursor of V₂O₅–WO₃/TiO₂ EUROCAT catalyst. It contained an average amount of 0.37 at.% W⁶⁺dissolved in titania, i.e. 1.07 × 10²⁰ W⁶⁺ cations dissolved/cm³ of titania. For the fresh catalyst, the mean amounts of W⁶⁺ and V⁵⁺ ions dissolved in titania were found to be equal to 1.07 × 10²⁰ and 4.47 × 10²⁰ cm⁻³, respectively. For the used catalyst, the mean amounts of W⁶⁺ and V⁵⁺ ions dissolved were found to be equal to 1.07 × 10²⁰ and 7.42 × 10²⁰ cm⁻³, respectively. Since fresh and used catalysts have similar compositions and similar catalytic behaviours, the only manifestation of ageing was a supplementary progressive dissolution of 2.9 × 10²⁰ additional V⁵⁺ cations in titania.After a prompt removal of oxygen, it appeared that NO alone has an electron acceptor character, linked to its possible ionosorption as NO⁻ and to the filling of anionic vacancies, mostly present on vanadia. Ammonia had a strong reducing behaviour with the formation of singly ionized vacancies. A subsequent introduction of NO indicated a donor character of this molecule, in opposition to its first adsorption. This was ascribed to its reaction with previously adsorbed ammonia strongly bound to acidic sites. Under NO + NH₃ reaction mixture in the absence of oxygen, the increase of electrical conductivity was ascribed to the formation of anionic vacancies, mainly on vanadia, created by dehydroxylation and dehydration of the surface. These anionic vacancies were initially subsequently filled by the oxygen atom of NO. N^o atoms, resulting from the dissociation of NO and from ammonia dehydrogenation, recombined into dinitrogen molecules. The reaction corresponded to

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. In the presence of oxygen, NO did not exhibit anymore its electron acceptor character, since the filling of anionic vacancies was performed by oxygen from the gas phase. NO reacted directly with ammonia strongly bound on acidic sites. A tentative redox mechanism was proposed for both cases.     

Solvothermally grown WO3·H2O film and annealed WO3 film for wide-spectrum tunable electrochromic applications

Tungsten trioxide (WO₃) is a classical electrochromic (EC) material with advantages of abundant reserves, high coloration efficiency and cyclic stability. However, WO₃ films are often accompanied by a narrow spectrum of modulation due to a single-color change from transparent to blue. In this work, we report a wide-spectrum tunable WO₃·H₂O nanosheets EC film solvothermally grown on fluorine-doped tin oxide (FTO) glass. Interestingly, the crystalline WO₃·H₂O nanosheets film is transformed into amorphous WO₃ after annealing at 250 °C for 1 h. The amorphous film can be transformed into crystalline WO₃ film by increasing the annealing temperature to 450 °C. After annealing at 250 °C, the WO₃ film exhibits an optical modulation of 75.8% in a broad solar spectrum range of 380–1400 nm and blocks 88.9% of solar irradiance. Fast switching responses of 4.9 s for coloration and 6.0 s for bleaching, and a coloration efficiency of 86.4 cm² C⁻¹ are also achieved. Additionally, the WO₃ film annealed at 250 °C also demonstrates an excellent cyclic stability, where 99.6% of the initial optical modulation can be retained after 1500 cycles. This simple and mild solvothermal method used in this work provides a new idea for the preparation of wide-spectrum tunable WO₃ EC films.     

Preparation of tungsten borides by combustion synthesis involving borothermic reduction of WO3

An experimental study on the preparation of two tungsten borides, WB and W₂B₅, was conducted by self-propagating high-temperature synthesis (SHS), during which borothermic reduction of WO₃ and elemental interaction of W with boron proceeded concurrently. Powder mixtures with two series of molar proportions of WO₃:B:W = 1:5.5:x (with x = 1.16–2.5) and 1:7.5:y (with y = 0.5–1.33) were adopted to fabricate WB and W₂B₅, respectively. The starting stoichiometry of the reactant compact substantially affected the combustion behavior and the phase composition of the final product. The increase of metallic tungsten and boron reduced the overall reaction exothermicity, leading to a decrease in both combustion temperature and reaction front velocity. The initial composition of the reactant compact was optimized for the synthesis of WB and W₂B₅. In addition to small amounts of W₂B and W₂B₅, the powder compact of WO₃ + 5.5B + 2 W produced WB dominantly. Optimum formation of W₂B₅ was observed in the sample of WO₃ + 7.5B + 0.85W. Experimental evidence indicates that an excess amount of boron about 10–13% is favorable for the formation of WB and W₂B₅.     

Synthesis of high-performance electrochromic thin films by a low-cost method

Metal-doping is an effective method to adjust the physical and chemical properties of semiconductor metal oxides. This work adopts a simple solvothermal method to synthesize Mo-doped tungsten oxide nanoparticles. The high-performance electrochromic films can be homogenously formed on ITO glass without post-annealing. Compared with pure WO₃ films, the optimized Mo-doped WO₃ films show improved electrochromic properties with significant optical contrast (68.3% at 633 nm), the short response time (6.3 s and 3.9 s for coloring and bleaching, respectively), and excellent coloration efficiency (107.2 cm² C^?1). The improved electrochromic behavior is mainly due to the increasing diffusion rate of Li⁺ in Mo-doped WO₃ films (increased 20% than that of pure WO₃ films). The porous surface of Mo-doped WO₃ film shortens the diffusion path of Li⁺. Besides, Mo doping reduces the resistance and improves conductivity. Furthermore, 2at% Mo-doped WO₃ films indicate satisfactory energy-storage properties (the specific capacitance is 73.8 F g^?1), resulting from the enhanced electrochemical activity and fast electrical conductivity. This work presents a practical and economical way of developing high-performance active materials for bifunctional electrochromic devices.     

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.     

Enhanced photoelectrochemical activity of electro-synthesized CdS-Bi2S3 composite films grown with self-designed cross-linked structure

In the present investigation thin semiconductor films of CdS, Bi₂S₃ and their intermixed composite films have been electro-synthesized onto conducting glass substrate from nonaqueous bath containing various levels of the precursor salts of Cd²⁺ and Bi³⁺. Spectrophotometric measurements determine the band gap energies of the composite films at ∼2.53 eV and ∼1.37 eV corresponding to the binary systems CdS and Bi₂S₃, respectively. The film matrices exhibit a unique structure of cross-linked nanoporous Bi₂S₃ mesh containing spherical shaped CdS crystals distributed uniformly on the top of the surface as detected from the morphological studies through scanning electron microscopy and transmission electron microscopy. X-ray diffraction studies show crystalline structure of the films of which the chemical compositions were determined through energy dispersive analysis of X-ray. The film matrices enriched with Cd exhibit high dielectric property as obtained from the capacitance measurement and substantial thermal stability derived from thermogravimetry and differential thermal analysis. These films are found to be highly fluorescent in nature when subjected to spectrofluorimetric analysis. The Raman spectral data exhibit characteristic peaks that are associated with Cd-S and Bi-S bonds as well as the defects created by metal oxides. The spectrum also demonstrates that the changes in the relative position of the overtone bands are associated with compositional variation of the film surface. The study of electrochemical polarization of different films, derives the inherent stability of the matrices towards dissolution. This was followed by anodic stripping voltammetry to estimate the dissolved cations during polarization. Photoelectrochemical measurements demonstrate n-type semiconductivity of the films with high order of donor density and reasonable photoactivity under illuminated condition. It may be summarized that the blended intermix of CdS-Bi₂S₃ film acquires tailor made properties desirable for photoelectrochemical application and displays solar conversion efficiency of the order of ∼1%.     

Effect of laser power density on the electrochromic properties of WO3 films obtained by pulsed laser deposition

Pulsed laser deposition (PLD) was used to prepare tungsten trioxide (WO₃) films on ITO substrates with a varying laser power density of 4.0–5.5 W/cm². XPS indicated that when the laser power density decreased, the peak positions of the W 4f and O 1s orbits shifted slightly to low energy due to the difference in oxygen vacancies. As the laser power density decreased, W⁶⁺ gradually replaced the lattice position of O^2?, increasing oxygen vacancies in the lattice. The transmittance modulated values (ΔT) were over 44% at 830 nm, indicating strong absorption by the WO₃ thin films in the near-infrared ray. The switching time of the WO₃ thin films between bleached states and coloured states decreased as the laser power density increased due to the amorphous structure, morphology, and lower oxygen deficiency at a high power density. The high ΔT and very fast switching time of t_b (1.09 s) and t_c (6.01 s) demonstrated the excellent electrochromic (EC) properties of the WO₃ films prepared by PLD.     

Evolution of TiOx-SiOx nano-composite during annealing of ultrathin titanium oxide films on Si substrate

This paper discusses the formation of the TiO_x-SiO_x nano-composite phase during annealing of ultrathin titanium oxide films (~27 nm). The amorphous titanium oxide films are deposited on silicon substrates by sputtering. These films are important for high-k dielectrics and sensing applications. Annealing of these films at 750 °C in the O₂ environment (for 15–60 min) resulted in the polycrystalline rutile phase. The films exhibit Raman peaks at 150 cm⁻¹ (B_1g), 435 cm⁻¹ (E_g), and 615 cm⁻¹ (A_1g) confirming the rutile phase. The signature TO (1078 cm⁻¹) and LO (1259 cm⁻¹) infrared active vibrational modes of Si–O–Si bond confirms the presence of silicon-oxide. The X-ray photoelectron spectra of the TiO_x films show multiple peaks corresponding to Ti metal (453.8 eV); Ti⁴⁺ state (458.3 eV (Ti 2p_3/2) and 464 eV (Ti 2p_1/2)); and Ti³⁺ state (456.4 eV (Ti 2p_3/2) and 460.8 eV (Ti 2p_1/2)). The O1s XPS spectra peaks at 530–533 eV can be attributed to Ti–O and Si–O bonds of the TiO_x-SiO_x nano-composite phase in the annealed films. The depth profiling XPS study shows that the top surface of the annealed film is mainly TiO_x and the amount of SiO_x increases with the depth.     

Detection of Reduced W n+ Sites on WO3–ZrO2 and Pt/WO3–ZrO2 Catalysts by Infrared Spectroscopy of Adsorbed NO

Adsorption of NO on oxidized WO₃–ZrO₂ catalysts leads to formation of adsorbed N₂O, surface nitrates, NO⁺, and Zr⁴⁺(NO^- ₃)–NO species. When NO is adsorbed on a sample reduced at 523 K, W⁵⁺ –NO (1855 cm^-1) and W⁴⁺(NO)₂ (1785 and 1700 cm^-1) species are formed in low concentration. Reduction at 573 K increases the density of W⁴⁺ sites and this density remains unchanged after reduction up to 673 K. The W⁴⁺(NO)₂ species are stable towards evacuation and in the presence of oxygen; however, they quickly disappear in the simultaneous presence of NO and O₂ as a result of the oxidation of the W⁴⁺ cations to W⁶⁺. The density of the W⁴⁺ sites on a Pt/WO₃–ZrO₂ sample is significant even after reduction at 523 K. This is explained by the promotion effect of platinum on the support reduction. The use of NO as a probe molecule for detection of reduced W ⁿ⁺ sites on tungstated zirconia is discussed.     

Electrical and optical properties of a polyblend electrolyte

A potassium ion conducting polyblend electrolyte based on polyvinyl pyrrolidone (PVP)+polyvinyl alcohol (PVA) complexed with KBrO₃ was prepared using solution cast technique. The electrical conductivity increased with increasing dopant concentration. Optical absorption studies were made in the wavelength range (200-600 nm) on pure (PVP+PVA) and KBrO₃ doped (PVP+PVA) films. The absorption edge was observed at 5.13 eV for undoped (PVP+PVA) while it ranged from 4.88 to 5.0 eV for differently KBrO₃-doped samples. The direct band gaps for undoped and KBrO₃ doped (PVP+PVA) films were found to be, respectively, 5.05 and 4.95, 4.86 and 4.90 eV while the indirect band gaps were 5.03 and 4.88, 4.79 and 4.83 eV, respectively. The absorption edge and the band gaps moved towards lower energies as the dopant concentration was increased up to 20 wt% of the dopant. For further increase in dopant concentration these values started increasing again. This is explained in terms of formation of charge transfer complexes between the dopant and the host matrix. The thermal properties of these films were investigated with differential scanning calorimetry (DSC). The variation in film morphology is examined by scanning electron microscopic examination.