For the selective catalytic reduction of NOx with ammonia (NH3-SCR), a V2O5WO3/TiO2 (VW/nTi) catalyst was prepared using V2O5 and WO3 on a nanodispersed TiO2 (nTi) support by simple impregnation process. The nTi support was dispersed for 0~3 hrs under controlled bead-milling in ethanol. The average particle size (D50) of nTi was reduced from 582 nm to 93 nm depending on the milling time. The NOx activity of these catalysts with maximum temperature shift was influenced by the dispersion of the TiO2. For the V0.5W2/nTi-0h catalyst, prepared with 582 nm nTi-0h before milling, the decomposition temperature with over 94 % NOx conversion had a narrow temperature window, within the range of 365-391 °C. Similarly, the V0.5W2/nTi-2h catalyst, prepared with 107 nm nTi-2h bead-milled for 2hrs, showed a broad temperature window in the range of 358~450 °C. However, the V0.5W2/Ti catalyst (D50 = 2.4 μm, aqueous, without milling) was observed at 325-385 °C. Our results could pave the way for the production of effective NOx decomposition catalysts with a higher temperature range. This approach is also better at facilitating the dispersion on the support material. NH3-TPD, H2-TPR, FT-IR, and XPS were used to investigate the role of nTi in the DeNOx catalyst.
The synthesis of porous W by freeze-casting and vacuum drying is investigated. Ball-milled WO3 powders and tert-butyl alcohol were used as the starting materials. The tert-butyl alcohol slurry is frozen at –25oC and dried under vacuum at –25 and –10oC. The dried bodies are hydrogen-reduced at 800oC and sintered at 1000oC. The XRD analysis shows that WO3 is completely reduced to W without any reaction phases. SEM observations reveal that the struts and pores aligned in the tert-butyl alcohol growth direction, and the change in the powder content and drying temperature affects the pore structure. Furthermore, the struts of the porous body fabricated under vacuum are thinner than those fabricated under atmospheric pressure. This behavior is explained by the growth mechanism of tert-butyl alcohol and rearrangement of the powders during solidification. These results suggest that the pore structure of a porous body can be controlled by the powder content, drying temperature, and pressure.
The effects of drying temperature on the microstructure of porous W fabricated by the freeze-casting process of tert-butyl alcohol slurry with WO3 powder was investigated. Green bodies were hydrogen-reduced at 800oC for 1 h and sintered at 1000oC for 6 h. X-ray diffraction analysis revealed that WO3 powders were completely converted to W without any reaction phases by hydrogen reduction. The sintered body showed pores aligned in the direction of tertbutyl alcohol growth, and the porosity and pore size decreased as the amount of WO3 increased from 5 to 10v ol%. As the drying temperature of the frozen body increased from -25oC to -10oC, the pore size and thickness of the struts increased. The change in microstructural characteristics based on the amount of powder added and the drying temperature was explained by the growth behavior of the freezing agent and the degree of rearrangement of the solid powder during the solidification of the slurry.
In this study, we prepare pure WO3 inverse opal(IO) film with a thickness of approximately 3 μm by electrodeposition, and an ultra-thin TiO2 layer having a thickness of 2 nm is deposited on WO3 IO film by atomic layer deposition. Both sets of photoelectrochemical properties are evaluated after developing dye-sensitized solar cells(DSSCs). In addition, morphological, crystalline and optical properties of the developed films are evaluated through field-emission scanning electron microscopy(FE-SEM), High-resolution transmission electron microscopy(HR-TEM), X-ray diffraction(XRD) and UV/ visible/infrared spectrophotometry. In particular, pure WO3 IO based DSSCs show low VOC, JSC and fill factor of 0.25 V, 0.89 mA/cm2 and 18.9 %, achieving an efficiency of 0.04 %, whereas the TiO2/WO3 IO based DSSCs exhibit VOC, JSC and fill factor of 0.57 V, 1.18 mA/cm2 and 50.1 %, revealing an overall conversion efficiency of 0.34 %, probably attributable to the high dye adsorption and suppressed charge recombination reaction.
Tungsten trioxide (WO3) is a promising candidate as a photocatalyst because of its outstanding electrical and optical properties. In this study, we prepare WO3 thin films by electrodeposition and characterize the photocatalytic degradation of methylene blue using these films. Depending on the voltage conditions (static and pulse), compact and porous WO3 films are fabricated on a transparent ITO/glass substrate. The morphology and crystal structure of electrodeposited WO3 thin films are investigated by scanning electron microscopy, atomic force microscopy, and X-ray diffraction. An application of static voltage during electrodeposition yields a compact layer of WO3, whereas a highly porous morphology with nanoflakes is produced by a pulse voltage process. Compared to the compact film, the porous WO3 thin film shows better photocatalytic activities. Furthermore, a much higher reaction rate of degradation of methylene blue can be achieved after post-annealing of WO3 thin films.
W-10 wt% Ti alloys that have a homogeneous microstructure are prepared by thermal decomposition of WO3-TiH2 powder mixtures and spark plasma sintering. The reduction and dehydrogenation behavior of WO3 and TiH2 are analyzed by temperature programmed reduction and a thermogravimetric method, respectively. The X-ray diffraction analysis of the powder mixture, heat-treated in an argon atmosphere, shows W- oxides and TiO2 peaks. Conversely, the powder mixtures heated in a hydrogen atmosphere are composed of W, WO2 and TiO2 phases at 600 ℃ and W and W-rich β phases at 800 ℃. The densified specimen by spark plasma sintering at 1500 ℃ in a vacuum using hydrogen-reduced WO3-TiH2 powder mixtures shows a Vickers hardness value of 4.6 GPa and a homogeneous microstructure with pure W, β and Ti phases. The phase evolution dependent on the atmosphere and temperature is explained by the thermal decomposition and reaction behavior of WO3 and TiH2.
Composites of P25 TiO2 and hexagonal WO3 nanorods are synthesized through ball-milling in order to study photocatalytic properties. Various composites of TiO2/WO3 are prepared by controlling the weight percentages (wt%) of WO3, in the range of 1–30 wt%, and milling time to investigate the effects of the composition ratio on the photocatalytic properties. Scanning electron microscopy, x-ray diffraction, and transmission electron microscopy are performed to characterize the structure, shape and size of the synthesized composites of TiO2/WO3. Methylene blue is used as a test dye to analyze the photocatalytic properties of the synthesized composite material. The photocatalytic activity shows that the decomposition efficiency of the dye due to the photocatalytic effect is the highest in the TiO2/ WO3 (3 wt%) composite, and the catalytic efficiency decreases sharply when the amount of WO3 is further increased. As the amount of WO3 added increases, dye-removal by adsorption occurs during centrifugation, instead of the decomposition of dyes by photocatalysts. Finally, TiO2/WO3 (3 wt%) composites are synthesized with various milling times. Experimental results show that the milling time has the best catalytic efficiency at 30 min, after which it gradually decreases. There is no significant change after 1 hour.
The present study demonstrates the effect of raw powder on the pore structure of porous W-Ni prepared by freeze drying of camphene-based slurries and sintering process. The reduction behavior of WO3 and WO3-NiO powders is analyzed by a temperature programmed reduction method in Ar-10% H2 atmosphere. After heat treatment in hydrogen atmosphere, WO3- NiO powder mixture is completely converted to metallic W without any reaction phases. Camphene slurries with oxide powders are frozen at −30 oC, and pores in the frozen specimens are generated by sublimation of the camphene during drying in air. The green bodies are hydrogen-reduced at 800 oC and sintered at 1000 oC for 1 h. The sintered samples show large and aligned parallel pores to the camphene growth direction, and small pores in the internal wall of large pores. The strut between large pores, prepared from pure WO3 powder, consists of very fine particles with partially necking between the particles. In contrast, the strut densification is clearly observed in the Ni-added W sample due to the enhanced mass transport in activation sintering.
In2O3 doped WO3 powders were prepared by a polymer solution route and their NO2 gas sensing properties were analyzed. The synthesized powders showed nano-sized particles with specific surface areas of 6.01~21.5 m2/g and the particle size and shape changed according to the content of In2O3. The gas sensors fabricated with the synthesized powders were tested at operating temperatures of 400~500 oC and 100~500 ppm concentrations of NO2 atmosphere. The particle size and In2O3 content affected on the initial sensor resistance in an air atmosphere. The highest sensitivity (8.57 at 500 oC), which was 1.77 higher than the sensor consisting of the pure WO3 sample, was measured in the 0.5 mol% In2O3 doping sample. In addition, the response time and recovery time were improved by the addition of In2O3.
Transition-metal oxide semiconductors have various band gaps. Therefore, many studies have been conducted in various application fields. Among these, methods for the adsorption of organic dyes and utilization of photocatalytic properties have been developed using various metal oxides. In this study, the adsorption and photocatalytic effects of WO3 nanomaterials prepared by hydrothermal synthesis are investigated, with citric acid added in the hydrothermal process as a structure-directing agent. The nanostructures of WO3 are studied using transmission electron microscopy and scanning electron microscopy images. The crystal structure is investigated using X-ray diffraction patterns, and the changes in the dye concentrations adsorbed on WO3 nanorods are measured with a UV-visible absorption spectrophotometer based on Beer-Lambert’s law. The methylene blue (MB) dye solution is subjected to acid or base conditions to monitor the change in the maximum adsorption amount in relation to the pH. The maximum adsorption capacity is observed at pH 3. In addition to the dye adsorption, UV irradiation is carried out to investigate the decomposition of the MB dye as a result of photocatalytic effects. Significant photocatalytic properties are observed and compared with the adsorption effects for dye removal.
Porous W-10 wt% Ti alloys are prepared by freeze-drying a WO3-TiH2/camphene slurry, using a sintering process. X-ray diffraction analysis of the heat-treated powder in an argon atmosphere shows the WO3 peak of the starting powder and reaction-phase peaks such as WO2.9, WO2, and TiO2 peaks. In contrast, a powder mixture heated in a hydrogen atmosphere is composed of the W and TiW phases. The formation of reaction phases that are dependent on the atmosphere is explained by a thermodynamic consideration of the reduction behavior of WO3 and the dehydrogenation reaction of TiH2. To fabricate a porous W-Ti alloy, the camphene slurry is frozen at -30℃, and pores are generated in the frozen specimens by the sublimation of camphene while drying in air. The green body is hydrogen-reduced and sintered at 1000℃ for 1 h. The sintered sample prepared by freeze-drying the camphene slurry shows large and aligned parallel pores in the camphene growth direction, and small pores in the internal walls of the large pores. The strut between large pores consists of very fine particles with partial necking between them.
A Nanosized WO3 and CuO powder mixture is prepared using novel high-energy ball milling in a bead mill to obtain a W-Cu nanocomposite powder, and the effect of milling time on the structural characteristics of WO3-CuO powder mixtures is investigated. The results show that the ball-milled WO3-CuO powder mixture reaches at steady state after 10 h milling, characterized by the uniform and narrow particle size distribution with primary crystalline sizes below 50 nm, a specific surface area of 37 m2/g, and powder mean particle size (D50) of 0.57 μm. The WO3-CuO powder mixtures milled for 10 h are heat-treated at different temperatures in H2 atmosphere to produce W-Cu powder. The XRD results shows that both the WO3 and CuO phases can be reduced to W and Cu phases at temperatures over 700oC. The reduced W-Cu nanocomposite powder exhibits excellent sinterability, and the ultrafine W-Cu composite can be obtained by the Cu liquid phase sintering process.
The effects of the heat treatment temperature and of the atmosphere on the dehydrogenation and hydrogen reduction of ball-milled TiH2-WO3 powder mixtures are investigated for the synthesis of Ti-W powders with controlled microstructure. Homogeneously mixed powders with refined TiH2 particles are successfully prepared by ball milling for 24 h. X-ray diffraction (XRD) analyses show that the powder mixture heat-treated in Ar atmosphere is composed of Ti, Ti2O, and W phases, regardless of the heat treatment temperature. However, XRD results for the powder mixture, heat-treated at 600oC in a hydrogen atmosphere, show TiH2 and TiH peaks as well as reaction phase peaks of Ti oxides and W, while the powder mixture heat-treated at 900oC exhibits only XRD peaks attributed to Ti oxides and W. The formation behavior of the reaction phases that are dependent on the heat treatment temperature and on the atmosphere is explained by thermodynamic considerations for the dehydrogenation reaction of TiH2, the hydrogen reduction of WO3 and the partial oxidation of dehydrogenated Ti.
선박 및 해양구조물에서의 생물학적 오손을 방지하기 위하여 나노크기의 MnOx-WO₃-TiO₂ 분말을 졸겔법으로 합성하여 특성을 제어하였고, 입자의 결정과 미세구조 등 분체특성 평가를 실시하였다. 자기마모형 방오도료의 안료에 적용하기 위하여 수지에 첨가 된 TiO₂계 나노분말 안료의 함량에 따른 표면특성 및 방오성능을 확인하였다. TiO₂계 안료의 분체특성으로 비표면적은 약 90 m²/g, 입자 크기는 약 100 ~ 150 nm을 보였다. 텅스텐 산화물은 망간산화물과 티타늄산화물과 상관관계를 통해, 삼원계 분체가 분체특성 및 표면특성이 우수하였다. 망간산화물의 첨가는 독특한 산화환원 특성으로 인하여 방오성능을 증가시키고, 텅스텐 산화물은 안료의 분체특성을 향상시킴으로, 안료와 수지의 비율을 조절하여 분산성, 표면특성 및 방오성능을 제어하였다. 그 결과로, 분산성 및 표면특성에 있어서 1, 5 wt. % 안료가 첨가된 것이 일부 우수하였으나, 5개월 동안의 해상침지시험에서는 2 wt. % 함유된 시편이 높은 방오성능을 보여 해양구조물의 방오안료 적용가능성을 확인하였다.
Porous W with spherical and directionally aligned pores was fabricated by the combination of sacrificial fugitives and a freeze-drying process. Camphene slurries with powder mixtures of WO3 and spherical PMMA of 20 vol% were frozen at −25 oC and dried for the sublimation of the camphene. The green bodies were heat-treated at 400 oC for 2 h to decompose the PMMA; then, sintering was carried out at 1200 oC in a hydrogen atmosphere for 2 h. TGA and XRD analysis showed that the PMMA decomposed at about 400 oC, and WO3 was reduced to metallic W at 800 oC without any reaction phases. The sintered bodies with WO3-PMMA contents of 15 and 20 vol% showed large pores with aligned direction and small pores in the internal walls of the large pores. The pore formation was discussed in terms of the solidication behavior of liquid camphene with solid particles. Spherical pores, formed by decomposition of PMMA, were observed in the sintered specimens. Also, microstructural observation revealed that struts between the small pores consisted of very fine particles with size of about 300 nm.
In this study, we demonstrate the photoelectrochromic devices composed of TiO2 and WO3 nanostructuresprepared by anodization method. The morphology and the crystal structure of anodized TiO2 nanotubes and WO3 nan-oporous layers are investigated by SEM and XRD. To fabricate a transparent photoelectrode on FTO substrate, a TiO2nanotube membrane, which has been detached from Ti substrate, is transferred to FTO substrate and annealed at 450°Cfor 1 hr. The photoelectrode of TiO2 nanotube and the counter electrode of WO3 nanoporous layer are assembled andthe inner space is filled with a liquid electrolyte containing 0.5 M LiI and 5 mM I2 as a redox mediator. The propertiesof the photoelectrochromic devices is investigated and Pt-WO3 electrode system shows better electrochromic perform-ance compared toWO3 electrode.
The possibility of using the chemical precipitation method of up-cycled ammonium paratungstate (APT) was studied and compared with the thermal decomposition method. WO3 particles were synthesized by chemical precipitation method using a 1: 2 weight ratio of APT: Di-water. For thermal decomposition, APT powder was heated for 4h at 600 oC in air atmosphere. The reaction products were characterized by X-ray diffraction (XRD), X-ray fluorescence spectrometer (XRF), particle size analyzer (PSA), and field emission-scanning electron microscopy (FE-SEM). Thermogravimetric analysis (TGA) of the upcycled APT allowed for the identification of the sequence of decomposition and reduction reactions that occurred during the heat treatment. TGA data indicated a total weight loss of 10.78% with the reactions completed in 658 oC. The XRD results showed that APT completely decomposed to WO3 by thermal decomposition and chemical precipitation. The particle size of the synthesized WO3 powders by thermal decomposition with 2 h of planetary milling was around 2 μm. During the chemical precipitation process, the particle size of the synthesized WO3 powders showed a round-shape with ~0.6 μm size.
Porous W with controlled pore structure was fabricated by thermal decomposition and hydrogen reduction process of PMMA beads and WO3 powder compacts. The PMMA sizes of 8 and 50 μm were used as pore forming agent for fabricating the porous W. The WO3 powder compacts with 20 and 70 vol% PMMA were prepared by uniaxial pressing and sintered for 2 h at 1200oC in hydrogen atmosphere. TGA analysis revealed that the PMMA was decomposed at about 400oC and WO3 was reduced to metallic W at 800oC. Large pores in the sintered specimens were formed by thermal decomposition of spherical PMMA, and their size was increased with increase in PMMA size and the amount of PMMA addition. Also the pore shape was changed from spherical to irregular form with increasing PMMA contents due to the agglomeration of PMMA in the powder mixing process.
In the present work, WO3 and WO3-TiO2 were prepared by the chemical deposition method. Structural variations, surface state and elemental compositions were investigated for preparation of WO3-TiO2 sonocatalyst. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and transmission electron microscopy (TEM) were employed for characterization of these new photocatalysts. A rhodamine B (Rh.B) solution under ultrasonic irradiation was used to determine the catalytic activity. Excellent catalytic degradation of an Rh.B solution was observed using the WO3-TiO2 composites under ultrasonic irradiation. Sonocatalytic degradation is a novel technology of treating wastewater. During the ultrasonic treatment of aqueous solutions sonoluminescence, cavitaties and "hot spot" occurred, leading to the dissociation of water molecules. In case of a WO3 coupled system, a semiconductor coupled with two components has a beneficial role in improving charge separation and enhancing TiO2 response to ultrasonic radiations. In case of the addition of WO3 as new matter, the excited electrons from the WO3 particles are quickly transferred to TiO2 particle, as the conduction band of WO3 is 0.74 eV which is -0.5 eV more than that of TiO2. This transfer of charge should enhance the oxidation of the adsorbed organic substrate. The result shows that the photocatalytic performance of TiO2 nanoparticles was improved by loading WO3.
The most general photocatalyst, TiO2 and WO3, are acknowledged to be ineffective in range of visible light. Therefore, many efforts have been directed at improving their activity such as: band-gap narrowing with non-metal element doping and making composites with high specific surface area to effectively separate electrons and holes. In this paper, the method was introduced to prepare a photo-active catalyst to visible irradiation by making a mixture with TiO2 and WO3. In the TiO2-WO3 composite, WO3 absorbs visible light creating excited electrons and holes while some of the excited electrons move to TiO2 and the holes remain in WO3. This charge separation reduces electron-hole recombination resulting in an enhancement of photocatalytic activity. Added Ag plays the role of electron acceptor, retarding the recombination rate of excited electrons and holes. In making a mixture of TiO2-WO3 composite, the mixing route affects the photocatalytic activity. The planetary ball-mill method is more effective than magnetic stirring route, owing to a more effective dispersion of aggregated powders. The volume ratio of TiO2(4) and WO3(6) shows the most effective photocatalytic activity in the range of visible light in the view point of effective separation of electrons and holes.