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.     

Self Assembly and Properties of C:WO3 Nano-Platelets and C:VO2/V2O5 Triangular Capsules Produced by Laser Solution Photolysis

Laser photolysis of WCl₆ in ethanol and a specific mixture of V₂O₅ and VCl₃ in ethanol lead to carbon modified vanadium and tungsten oxides with interesting properties. The presence of graphene’s aromatic rings (from the vibrational frequency of 1,600 cm⁻¹) together with C–C bonding of carbon (from the Raman shift of 1,124 cm⁻¹) present unique optical, vibrational, electronic and structural properties of the intended tungsten trioxide and vanadium dioxide materials. The morphology of these samples shows nano-platelets in WO _x samples and, in VO _x samples, encapsulated spherical quantum dots in conjunction with fullerenes of VO _x . Conductivity studies revealed that the VO₂/V₂O₅ nanostructures are more sensitive to Cl than to the presence of ethanol, whereas the C:WO₃ nano-platelets are more sensitive to ethanol than atomic C.     

Effect of heat absorbing alumina addition on mechanochemical synthesis of WC–Al2O3 nanocomposites

It has been shown earlier that formation of undesirable W₂C phase during mechanochemical synthesis of WC–Al₂O₃ composites from WO₃–Al–C mixture is due to high temperatures caused by the large heat release during the initial aluminothermic reduction of WO₃. With the aim of preventing the formation of W₂C, in this study, Al₂O₃ was added to lower the reaction temperature. Thermodynamic calculations showed that Al₂O₃ presence in WO₃/2Al/C/xAl₂O₃ mixtures would lower the adiabatic temperature. Experimental findings revealed that with no Al₂O₃ addition, released heat in the mixture activates carbothermic reduction of WO₃ and causes carbon deficiency, which results in W₂C formation. When x?=?0·6, although product consists of W₂C phase, the coolant effect of alumina diminishes carbon deficiency phenomenon with a consequence of more WC formation. For the WO₃/2Al/C/1·2Al₂O₃ mixture, carbothermic reduction reaction was prevented, which brings about complete conversion of W to WC after milling. The TEM observations showed that the produced WC–Al₂O₃ powder contains nanosize particles.     

The synthesis of micro and nano WO3 powders under the sparks of plasma electrolytic oxidation of Al in a tungstate electrolyte

Plasma electrolytic oxidation (PEO) is commonly known as a coating technique. However, the present study shows that PEO of pure Al in 10?g?l^?1 Na₂WO₄·2H₂O leads to the synthesis of micro and nano sized powders of WO₃. The as-synthesized WO₃ powders have been characterized by SEM, TEM and photocatalytic tests. The plasma discharges during the PEO process have been investigated by real-time imaging and spectrographic method. The energetic features of the single discharge at different stages of PEO have been evaluated. It was suggested that the electrolyte species were directly decomposed into tungsten oxides within the discharge channels and then the oxides re-entered the electrolyte due to the lower melting and boiling points of WO₃, and more importantly, its tendency of sublimation.     

Electrodeposition of tungsten from ZnCl2-NaCl-KCl-KF-WO3 melt and investigation on tungsten species in the melt

The electrodeposition of tungsten in ZnCl₂-NaCl-KCl-KF-WO₃ melt at 250 °C was further studied to obtain a thicker deposit. In the ordinary electrolysis at 0.08 V vs. Zn(II)/Zn, the current density decreased from 1.2 mA cm⁻² to 0.3 mA cm⁻² in 6 h. A thickness of the obtained tungsten layer was 2.1 μm and the estimated current efficiency was 93%. A supernatant salt and a bottom salt were sampled after 6 h from the melting and were analyzed by ICP-AES and XRD. It was found that the soluble tungsten species slowly changes to insoluble ones in the melt. The soluble species was suggested to be WO₃F⁻ anion. One of the insoluble species was confirmed to be ZnWO₄ and the other one was suggested to be K₂WO₂F₄. Electrodeposition was carried out under the same condition as above except for the intermittent addition of WO₃ every 2 h. The current density was kept at the initial value and the thickness was 4.2 μm. The intermittent addition of WO₃ was confirmed to be effective to obtain a thicker tungsten film.     

Nonoxidative dehydrogenation and aromatization of methane over W/HZSM‐5‐based catalysts

Highly active and heat‐resisting W/HZSM‐5‐based catalysts for nonoxidative dehydro‐aromatization of methane (DHAM) have been developed and studied. It was found from the experiments that the W−H₂SO₄/HZSM−5 catalyst prepared from a H₂SO₄‐acidified solution of ammonium tungstate (with a pH value at 2–3) displayed rather high DHAM activity at 973–1023 K, whereas the W/HZSM‐5 catalyst prepared from an alkaline or neutral solution of (NH₄)₂WO₄ showed very little DHAM activity at the same temperatures. Laser Raman spectra provided evidence for existence of (WO₆)^n- groups constructing polytungstate ions in the acidified solution of ammonium tungstate. The H₂‐TPR results showed that the reduction of precursor of the 3% W–H₂SO₄/HZSM‐5 catalyst may occur at temperatures below 900 K, producing W species with mixed valence states, W⁵⁺ and W⁴⁺, whereas the reduction of the 3% W/HZSM‐5 occurred mainly at temperatures above 1023 K, producing only one type of dominant W species, W⁵⁺. The results seem to imply that the observed high DHAM activity on the W–H₂SO₄/HZSM‐5 catalyst was closely correlated with (WO₆)^n- groups with octahedral coordination as the precursor of catalytically active species. Incorporation of Zn (or La) into the W–H₂SO₄/HZSM‐5 catalyst has been found to pronouncedly improve the activity and stability of the catalyst for DHAM reaction. Over a 2.5% W–1.5% Zn–H₂SO₄/HZSM‐5 catalyst and under reaction conditions of 1123 K, 0.1 MPa, and GHSV=1500 ml/(h g−cat.), methane conversion (XCH₄) reached 23% with the selectivity to benzene at ∼96% and an amount of coke for 3 h of operation at 0.02% of the catalyst weight used. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation and characterization of WO3/SiO2 catalysts

Two sets of WO₃/SiO₂ catalysts were prepared from (NH_{4 6}H₂W₁₂O₄₀ (aqueous method) and W(³-C₃H₅)₄ (non-aqueous method). The molecular structures and dispersions of the surface tungsten oxide species for the WO₃/SiO₂ catalysts under ambient and in situ dehydrated conditions were investigated by Raman spectroscopy. The samples prepared from (NH₄)₆H₂W₁₂O₄₀ (aqueous method) exhibit very strong Raman features due to the presence of crystalline WO₃ and the samples prepared from W(³-C₃H₅)₄ (non-aqueous method) do not possess crystalline WO₃. These results suggest that the preparation method exerts an influence on the dispersion of the surface tungsten oxide species on SiO₂. The surface tungsten oxide species under ambient conditions possess polytungstate clusters, W₁₂O ₄₂ ^12– , on the silica support. Upon dehydration at elevated temperatures, the hydrated polytungstate clusters decompose and interact with the silica support via the formation of isolated, octahedrally coordinated tungsten oxide species.     

In situ reactive synthesis and plasma-activated sintering of binderless WC ceramics

Binderless micrometre tungsten carbide ceramics (～1.1?μm) were in situ synthesised and densified by plasma-activated sintering (PAS) from mixed powders of tungsten trioxide and carbon black. The influence of sintering process and powders’ composition ratio on the phase composition, microstructure and mechanical properties of as-prepared samples was clarified in detail. The phase evolution was ascertained by X-ray diffraction to be WO₃→WO_2.72→WO₂→W₂C→WC, with the formation of CO and CO₂ gases. The sample with nearly single WC phase, dense structure and excellent mechanical properties was fabricated under the optimised process with the proper composition ratio. Owing to the micrograin size, the fracture toughness (8.88?MPa?m^1/2) was enhanced while high hardness (2159 HV10) was maintained, in the absence of any ceramic toughening phase.     

Electrochromism and reversible changes in the position of fundamental absorption edge in cathodically deposited amorphous WO3

Amorphous WO₃ (a-WO₃) films have been produced by electrodeposition from a sodium tungstate-based aqueous electrolyte. Their coloration under the action of cathode current in 1N H₂SO₄ is accompanied by a reversible shift of ∼0.42 eV in the fundamental absorption edge of the oxide towards higher quantum energies. The shift of the edge is proportional to the change in the potential of the WO₃ electrode being colored and is caused by the sequential filling, by injected electrons, of levels in the energy spectrum of electronic states formed by the unoccupied d-orbitals of W⁶⁺ centers. The optical characteristics of the W⁵⁺ centers which are formed in this case (color centers of electrochromic material) depend on whether a particular tungsten atom has a double bond to the oxygen atom (WO type bond). At the initial stage of coloration, injected electrons are captured mainly by the W⁶⁺ centers that have no such bonds. Then, W⁶⁺ centers with WO bonds, which have a higher position of the unoccupied d-orbitals on the energy scale, are also filled; this is accompanied by the appearance of an extra absorption band with maximum at ∼2 eV in the optical spectrum of films.     

Characterization of New Bimetallic Oxycarbide (MoWC0.5O0.6) for Bifunctional Isomerization of n-Heptane

A new bimetallic oxycarbide was synthesized and characterized by XRD, TEM, EDS, XPS and adsorption–desorption of probe molecules. All the molybdenum was reduced and 35% of tungsten was present as WO_x. The number of metallic sites, Lewis and Br?nsted acid sites were estimated. A turnover rate of 0.1 s⁻¹ was measured at 300 °C for the first order n-heptane isomerization.     

Effect of Surface Tungstate W<Superscript>5+</Superscript> Species on the Metathesis Activity of W-Doped Spherical Silica Catalysts

The high surface area W-doped spherical silica (SSP) catalysts were prepared with different sequences of W and Si addition (W–Si_(Alt), Si₁–W_2, and W₁–Si₂) by the sol–gel method with CTAB as a structure directing agent and compared with the impregnated one (W/SSP). All the catalysts exhibited high specific surface area (～?1100 m² g^?1) with a closely perfect spherical shape. The presence of surface/sub-surface tungstate W⁵⁺ species, crystalline bulk WO₃, and tetrahedral tungsten oxide species on the prepared catalysts was investigated by means of X-ray photoelectron spectroscopy depth profile analysis, X-ray diffraction, and Raman spectroscopy. Without in situ reduction by the reactants/products, tungstate W⁵⁺ species was found on the top surface of the as-prepared W–Si_(Alt) whereas for the Si₁–W₂, W/SSP, and W₁–Si₂, the W⁵⁺ appeared only on the sub-surface of the catalysts after 5 and 15 s Ar⁺ etching. The abundance of surface W⁵⁺ species is suggested to facilitate the establishment of the active tungsten carbenes and was correlated well to the catalytic activity in propene metathesis. The surface W⁵⁺-activity relationship of the WO₃-based metathesis catalysts is useful especially when the catalyst activity did not depend solely on the amount of active tetrahedral coordinated tungsten oxides.     

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.     

Laser-induced anchoring of WO3 nanoparticles on reduced graphene oxide sheets for photocatalytic water decontamination and energy storage

In this work, the synthesis of tungsten oxide/reduced graphene oxide (WO₃-rGO) nanocomposite, using a simple method of pulsed laser ablation in liquids (PLAL) is reported. The pulsed laser beam of 355 nm wavelength carries out two simultaneous processes: the reduction of graphene oxide and at the same time the anchoring of nanostructured WO₃ on reduced graphene oxide. In the photo-catalytic application, WO₃-rGO shows much better visible light absorption and less photo-generated charge recombination than pure WO₃, as indicated by optical absorption and photoluminescence spectra. These improved features in WO₃-rGO significantly enhanced the photo-catalytic decontamination of methylene blue (MB) dye in the water, compared to the use of pure WO₃ as a photocatalyst. A Poly 2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS) based electrolyte together with the high electrical conductance and porosity of rGO which were produced after anchoring WO₃ on the graphene oxide, were harnessed for the energy storage application using this material for a supercapacitor. The specific capacitance for WO₃-rGO based device is achieved to be 577 F g⁻¹ measured by the galvanostatic charge-discharge (GCD) method. Also, at a power density of 1000 W kg⁻¹, the as-synthesized WO₃-rGO demonstrated a large energy density value of 76.3 Wh Kg⁻¹ that is much larger than obtained, using WO₃ alone. Besides these photocatalytic and energy storage performance evaluation of WO₃-rGO, the optical, morphological and elemental characteristics of synthesized WO₃-rGO were also investigated to study the improved performance of the nanocomposite in these two applications.     

Catalytic hydrolysis of chlorofluorocarbon (CFC-12) over WO3/ZrO2

The catalytic decomposition of CFC-12 (CCl₂F₂) in the presence of water vapor was investigated over a series of solid acids WO₃/ZrO₂. Compared with tungstic acid, ammonium metatungstate is a better source of tungsten oxide for the preparation of WO₃/ZrO₂ catalysts. CFC-12 decomposition activities of WO₃/ZrO₂ catalysts are in good agreement with their acidities. Enhancing the acidities of catalysts is favorable to increase their CFC-12 decomposition activities. WO₃/ZrO₂ catalysts calcined at higher temperature exhibit good catalytic activity and stability for the hydrolysis of CFC-12, and show better structural stability during the reaction.     

Towards highly transparent tungsten zinc sodium borate glasses for radiation shielding purposes

The impact of tungsten oxide (WO₃) additions on the structure, some physical and radiation shielding parameters of sodium zinc borate glasses have been scrutinized. These glasses were properly produced by the melt quenching method. The amorphous state was affirmed by X-ray diffraction (XRD) data. The internal structure within the short-range order of the glassy network was studied by the method of infrared spectroscopy (IR). The results of IR showed that the BO₄ units are transformed to BO₃ accompanied by the formation of nonbridging oxygens with further WO₃ doping. This transformation of BO₄ to BO₃ and nonbridging oxygens is employed to explain the increase in the molar volume values with changing WO₃/ZnO amount. Further, the optical transmittance was measured within the visible range to assure the transparency of the prepared glasses. The transmittance results confirm the absence of W⁵⁺, W⁴⁺, W³⁺ states; based on the absence of their absorption bands. Also, the transmittance results indicate that the only oxidation state in the present glasses is hexavalent tungsten (W⁶⁺). Additionally, the parameters of radiation protection of the manufactured glasses were investigated. It was found that, the addition of WO₃ improves not only the radiation protection parameters (such as the linear attenuation coefficient) but also the transparency of the prepared glasses. Finally, we concluded that, the addition of WO₃ to the glass samples leads to transparent glasses with an improved shielding ability at low energies but effects slightly at high energies. Due to the high transparency and the increased values of the linear attenuation coefficient of the prepared glasses, they are considered promising glasses in the field of nuclear radiation protection, especially at low energies.     

An HREM study of the WO3/TiO2 monolayer catalyst system. Proposals for the overlayer structure

High resolution electron microscopy (HREM) has been used to characterise the WO₃/TiO₂ (anatase) catalyst system. Comparisons between pure samples of TiO₂ in the uncalcined and calcined states with titania in the catalyst (loaded with 10 wt% WO₃) indicate that the tungsten oxide overlayer preserves the surface roughness of the support (as observed in the pure uncalcined material). The calcination of pure anatase results in significant grain growth and surface smoothing. In the electron microscope, the tungsten oxide overlayer is revealed as 2D pseudo-hexagonal shaped clusters which appear to be epitaxially related to the support. After noting that the anatase support predominantly exposes {112}, {011}, {110} and (001) type facets we have combined this information with structural data on the overlayer derived from a previous EXAFS and XANES study by Hilbrig et al. that reported the presence of WO₄ species and six-coordinate WO₅ groups. By considering the arrangement of terminating oxygen atoms on each of the aforementioned anatase surfaces, we suggest ways in which the WO _x species may be linked together to form the tungsten oxide overlayer. This approach has led us to conclude that, with the exception of the (001) surface, the overlayer may consist of WO₄ dimers rather than chains of linked WO₅ groups terminated by WO₄ species.     

Metallo-organic deposition of tungsten oxide films from alkylammonium tungstate solutions

This paper describes a simple and inexpensive metallo-organic deposition (MOD) process for forming electrochromic tungsten oxide (WO₃) films on glass. The thin films of WO₃ were made by air firing (500–700°C) films from xylene/2-propanol solutions of bis-(di-n-octylammonium) tetratungstate, [(n-C₈H₁₇)₂NH₂]₂[W₄O₁₃]. The process coats glass with undoped films ranging in colour from faint yellow to dark brown, and can be used to make gradients of these colours. The colour is determined by the firing parameters and results from residual carbon and tungsten suboxides in the film due to incomplete firing. Increased firing temperatures or longer firing times removes the carbon and produces films with higher crystallinity. Electrochemical doping with acid (H⁺) switches the colour gradient films to a uniformly blue colour.     

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.     

The Effects of Al2O3 Addition and WO3 Modification on Catalytic Activities of NiO/TiO2 for Acid Catalysis

NiO/Al₂O₃–TiO₂/WO₃ catalysts for acid catalysis were prepared by the addition of Al₂O₃ and the modification with WO₃. The strong acid sites were formed through the bonding between dispersed WO₃ and TiO₂. The larger the dispersed WO₃ amount, the higher both the acidity and catalytic activity. The addition of Al₂O₃ up to 5 mol% enhanced acidity and catalytic activity of NiO/Al₂O₃–TiO₂/WO₃ gradually due to the interaction between Al₂O₃ and TiO₂ and consequent formation of Al–O–Ti bond. The presence of NiO may attract reactants and enhance the local concentration of reactants near acid sites and consequently increase catalytic activity.     

Influence of WO3‐Doping on the Microstructure and Electrical Properties of ZnO–Bi2O3 Varistor Ceramics Sintered at 950°C

The phase evolution, microstructure, and electrical properties of WO₃‐doped ZnO–Bi₂O₃‐based varistors were investigated for different amounts x (0 ≤ x ≤ 1.60 mol%) of the dopant. When x was less than 0.40, the dissolved W⁶⁺ in the β‐Bi₂O₃ acted as a donor in the grain boundaries and reduced the electrical properties of the ZnO varistors. However, when x was 0.40 mol%, which meant an amount of WO₃ equal to that of Bi₂O₃, the electrical properties dramatically increased, which means the W⁶⁺ donor effect is removed at the grain boundaries because a new Bi₂WO₆ phase was formed in the grain‐boundary regions. The Bi₂WO₆ phase has high oxygen conductivity at high temperatures; it transfers more oxygen to the grain boundaries in order to further enhance the electrical properties. For x values higher than 0.40 (i.e., an addition of WO₃ that is greater than the content of Bi₂O₃), the electrical properties were steadily reduced in comparison to the composition with x = 0.40. This could be explained by the reduced amount of Co, Mn, and Al at the grain boundaries and in the ZnO grains as a result of their incorporation into the ZnWO₄ phase. The electrical properties of the ZnO grains and the grain boundaries were in agreement with the results of the impedance spectroscopy analysis.