Characterization of electrodeposited WO3 films and its application to electrochemical wastewater treatment

WO₃ films have been prepared on to IrO₂-coated Ti substrate by cathodic deposition, and as-deposited and annealed films have been characterized using XRD, TEM, Raman and FT-IR spectroscopy. The as-deposited film consists of nanocrystalline, orthorhombic WO₃·H₂O and this phase transforms to amorphous WO₃ by annealing at 250 °C and to monoclinic WO₃ by annealing at and above 350 °C. The as-deposited and annealed films have been used as anodes for electrochemical decomposition of phenol in aqueous solutions with and without chloride ions. The monoclinic WO₃ anodes prepared by annealing at 350 and 400 °C show relatively high electrochemical activity in the chloride-containing solution. In addition, the anodes possess high chemical and physical stabilities: very low dissolution rate of WO₃ during the electrolysis and good adhesion to the substrate. Thus, WO₃ anodes may be promising materials for anodic oxidation of bio-refractory organics in wastewater, although further improvement of electrochemical activity is needed for more effective decrease in total organic carbons in wastewater.     

Selectivity and mechanism for skeletal isomerization of alkanes over typical solid acids and their Pt-promoted catalysts

Selectivities for skeletal isomerizations of n-butane and n-pentane catalyzed by typical solid acids such as Cs_2.5H_0.5PW₁₂O₄₀ (Cs2.5), SO₄²⁻/ZrO₂, WO₃/ZrO₂, and H-ZSM-5 and their Pt-promoted catalysts were compared. High selectivities for n-butane and low selectivity for n-pentane were observed over Cs2.5 and SO₄²⁻/ZrO₂, while H-ZSM-5 was much less selective, and WO₃/ZrO₂ was highly selective for both reactions. The Pt-promoted solid acids were usually selective for these reactions in the presence of H₂ except for Pt-H-ZSM-5 for n-butane isomerization. Both the acid strength and pore structure would be factors influencing the selectivity. Mechanism of skeletal isomerization of n-butane was investigated by using 1,4-¹³C₂-n-butane over Cs2.5 and Pt–Cs2.5. It was concluded that n-butane isomerization proceeded mainly via monomolecular pathway with intramolecular rearrangement on Pt–Cs2.5, while it occurred through bimolecular pathway with intermolecular rearrangement on Cs2.5. The higher selectivity on Pt–Cs2.5 would be brought about by the monomolecular mechanism. In the skeletal isomerization of cyclohexane, Pt–Cs2.5/SiO₂ was highly active and selective, while Pt–Cs2.5 was less selective. Control in the acid strength of Cs2.5 by the supporting would be responsible for the high selectivity.     

Electrophoretic Deposition Behavior of Aqueous Nanosized Zinc Oxide Suspensions

The rheological behavior and electrophoretic deposition (EPD) of ZnO nanopowder (nano-ZnO) in aqueous media have been described. A cationic polyelectrolyte (polyethylenimine, PEI) was used to disperse and modify the surfaces of the ZnO nanoparticles. The rheological properties of the ZnO aqueous suspension were investigated by measuring the viscosity versus the pH and amount of dispersant. The EPD processing was conducted via cathodic electrodeposition, using stable suspensions with low viscosity, and the depositional behavior was investigated. Bubble-free nano-ZnO deposits with uniform microstructures were successfully obtained, which was an indication of good sintering behavior.     

Immobilization of glucose oxidase on nonwoven fabrics with bombyx mori silk fibroin gel

The enzyme glucose oxidase (GOD) was immobilized on the nonwoven fabrics, which have excellent properties in diffusivity of substrates, mechanical strength, and handling, with Bombyx mori silk fibroin gel. The nonwoven fabrics of silk fibroin, viscose rayon, poly-ethyleneterephthalate, 6-nylon, and polypropylene with activated surface by fluoline treatment were used. The stabilities of GOD to heat or pH changes were much improved by the immobilization as well as the case of the GOD immobilized in the silk fibroin membrane. Among nonwoven fabrics, silk fibroin was the most excellent support material for the immobilization of GOD although all nonwoven fabrics used here are able to be used as the support materials. The increase of the sensitivity was observed when the glucose sensor was made with the GOD immobilized on nonwoven silk fabrics as four times compared with the case of the GOD immobilized in the silk fibroin membrane.     

Effects of ultrasonic irradiation on crystallization behavior of tripalmitoylglycerol and cocoa butter

Effects of application of ultrasonic power (20 kHz, 100 W) on the crystallization behavior of tripalmitoylglycerol (PPP) and cocoa butter have been examined in terms of rate of nucleation and polymorphic control. High-purity PPP (>99%) and low-purity PPP (>80%) samples were employed to mimic real fat systems, which usually have higher concentrations of minor components in addition to the main component. For both the high-purity and low-purity PPP, the application of ultrasonic power accelerated the rate of nucleation as measured by induction time for the occurrence of crystals and by the number of crystals nucleated. As for the polymorphic influences, the nucleation of both the β′ and β forms was accelerated by the ultrasound, yet the β′ form nucleation was more accelerated when the low-purity PPP samples were employed. As for cocoa butter, sonication for a short period accelerated the crystallization of Form V. The present results indicate that ultrasound irradiation is an efficient tool for controlling polymorphic crystallization of fats.     

EFFECT OF DRYING METHOD ON MESOPOROSITY OF RESORCINOL-FORMALDEHYDE DRYGEL AND CARBON GEL

Resorcinol-formaldehyde hydrogels were synthesized by sol-gel polycondensation of resorcinol with formaldehyde in a slightly basic aqueous solution. RF cryogels, RF xerogels, and RF xerogels (MW gels) were respectively prepared from RF hydrogels by freeze drying, hot air drying, and microwave drying. Carbon cryogels, carbon xerogels and carbon MW gels were subsequently obtained by pyrolyzing RF drygels in an inert atmosphere. Freeze drying and microwave drying were effective to prepare mesoporous RF drygels and carbon gels. RF cryogels and carbon cryogels showed high mesoporosity over wide ranges of the molar ratio of resorcinol to catalyst (R/C) and the ratio of resorcinol to water (R/W) used in sol-gel polycondensation. Although RF xerogels had a few mesopores, carbon xerogels had no mesopores. RF MW gels and carbon MW gels showed mesoporosity if appropriate values of R/C and R/W were selected.     

Microstructure of a Molybdenum Nitride Layer Formed by Nitriding Molybdenum Metal

For pure molybdenum nitrided at 1373 K in NH₃ gas, microstructural observations of a molybdenum nitride layer were conducted through a transmission electron microscope. The molybdenum nitride layer consisted of two molybdenum nitrides: an outer one of γ-Mo₂N and an inner one of β-Mo₂N. A great number of (011)[0     1] type twins were observed in the β-Mo₂N phase, whereas the microstructure of the γ-Mo₂N phase was almost free from lattice defects except for slightly observed {111}〈112〉 type twin.     

Phase Relations and Volume Changes of Hafnia under High Pressure and High Temperature

Using multi-anvil high-pressure devices and synchrotron radiation, X-ray in situ observations of HfO₂ under high pressure and high temperature have been performed to investigate its phase relations and compression behavior. An orthorhombic phase (orthoI) is stable from 4 to 14.5 GPa below 1250°–1400°C and transforms to a tetragonal phase, which is one of the high-temperature forms of HfO₂, above these temperatures. Another orthorhombic phase (orthoII) with a cotunnite-type structure appears above 14.5 GPa. OrthoII is stable up to 1800°C at 21 GPa. OrthoII is quenchable to ambient conditions. The orthoI-to-orthoII transition is accompanied by ∼8 vol% decrease. The bulk moduli of orthoI and orthoII at room temperature are 220 and 312 GPa, respectively. This low compressibility of orthoII indicates that it is a potential candidate for very hard materials.