Selective decomposition of isopropanol using as prepared and oxidized graphite nanofibers

Three types of as prepared and treated graphite nanofibers (GNFs) were used as catalysts in the decomposition of isopropanol to propene and acetone in the presence of oxygen to evaluate the surface chemistry of the fibers. As prepared herringbone fibers were found to produce higher selectivity for propene compared to the as prepared platelet and ribbon fibers at all temperatures explored. Herringbone fibers that had undergone oxidative treatment with nitric acid, phosphoric acid, ruthenium tetroxide or potassium permanganate were also evaluated at a 290 °C. Effects of oxidation treatments on fiber structure were evaluated using a host of analytical techniques including BET, SEM/EDS, TGA, XPS, and fluorescence labeling of surface species. Selectivity for acetone dehydrogenation product or propene dehydration product could be achieved by the appropriate surface treatment. Nitric acid was the mildest treatment and the treated fibers showed minimal changes. (Potassium permanganate was a harsh treatment that almost completely degraded fiber structure, creating amorphous carbon.) Phosphoric acid treated fibers were found to produce very high conversions and almost pure selectivity for propene. Ruthenium tetroxide did not appear to have a large affect on fiber morphology; however, selectivity for acetone was much higher when GNFs were treated with ruthenium tetroxide.     

Surface decorated platinum carbonyl clusters

Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt(13)(CO)(12){Cd(5)(μ-Br)(5)Br(2)(dmf)(3)}(2)](2-) (1), [Pt(19)(CO)(17){Cd(5)(μ-Br)(5)Br(3)(Me(2)CO)(2)}{Cd(5)(μ-Br)(5)Br(Me(2)CO)(4)}](2-) (2), [H(2)Pt(26)(CO)(20)(CdBr)(12)](8-) (3) and [H(4)Pt(26)(CO)(20)(CdBr)(12)(PtBr)(x)](6-) (4) (x = 0-2), have been obtained from the reactions between [Pt(3n)(CO)(6n)](2-) (n = 2-6) and CdBr(2)·H(2)O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt(26)Cd(12) metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters.     

Preparation of water‐repellent silks by a reaction with octadecenylsuccinic anhydride

Silk fibers and membranes were acylated with octadecenylsuccinic anhydride (ODSA) at 75°C for different times. Swelling [N,N‐dimethylformamide (DMF) and dimethyl sulfoxide (DMSO)] and nonswelling (xylene) solvent media were used for the reaction. Silk membranes that reacted in DMF or DMSO displayed faster reaction kinetics and attained higher weight‐gain values than fibers. The effect of the solvent on the reaction yield was in the following order: DMSO > DMF ? xylene. The Fourier transform infrared spectra of acylated silk samples showed the characteristic absorption bands of the anhydride at 2990, 2852, 1780–1700, and 1170 cm^?1. The intensity of the latter band, which increased linearly with the weight gain, was used as a marker for evaluating the reaction kinetics of the samples acylated in the nonswelling medium. The moisture regain and water retention of silk fibers acylated with ODSA decreased significantly, regardless of the solvent system used. Accordingly, the water repellency increased. Acylation induced an increase in the thermal stability of the silk fibers and membranes. Fine particles adhering to the surfaces of the silk fibers acylated in xylene were detected by scanning electron microscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 324–332, 2003     

Innovative method to produce large-area freestanding functional ceramic foils

Using thick and thin films instead of bulk functional materials presents tremendous advantages in the field of flexible electronics and component miniaturization. Here, a low-cost method to grow and release large-area, microscale thickness, freestanding, functional, ceramic foils is reported. It uses evaporation of sodium chloride to silicon wafer substrates as sacrificial layers, upon which functional lead titanate zirconate ceramic films are grown at 710?°C maximum temperature to validate the method. The freestanding, functional foils are then released by dissolution of the sacrificial sodium chloride in water and have the potential to be integrated into low-thermal stability printed circuits and flexible substrates. The optimization of the sodium chloride layer surface quality and bonding strength with the underlying wafer is achieved thanks to pre-annealing treatment.     

Oxygen Storage Behavior of Ceria–Zirconia-Based Catalysts in the Presence of SO2

This paper investigates the effect of the presence of SO₂ in the dynamics of oxygen storage on ceria and ceria–zirconia. The introduction of SO₂ under reaction conditions at T<873 K negatively affects CO conversion under oscillating conditions on all the supports studied, owing to the formation of sulfate species. Deactivation is observed on all supports and activity is recovered only after desorption of SO₂, which occurs at 950<T<1000 K, depending on catalyst composition (Ce/Zr ratio) and treatment atmosphere. The amount of sulfur adsorbed is higher over solid solutions, reaching a maximum with Ce _x Zr_1–x O₂ (0.5<x<0.68). However this does not adversely affect activity compared to ceria. In the presence of Rh and Pd, reactivation is favored under reaction conditions. More generally, it appears that the removal of sulfates is facilitated in reductive atmospheres (both hydrogen and CO) over mixed oxides. No differences are observed following regeneration under oxidizing conditions.     

Production of antimicrobially active silk proteins by use of metal‐containing dyestuffs

The work presented here discusses a new technique for preparing silk fibers and films with persistent antimicrobial activity through use of metallic dyestuffs during the fiber dyeing process. The length of the silk fibers investigated contracted when the fibers were immersed in concentrated neutral salt solutions, such as calcium or potassium nitrate, at elevated temperature levels. The birefringence and molecular orientation of the silk fibroin molecules became less ordered by the action of the neutral salt solutions, resulting in increased dyestuff absorption. Subsequently, contracted silk fibers were dyed with metallic dyestuffs containing Cr or Cu for the purpose of obtaining silk fibers with antimicrobial activity. Silk fibers dyed with metallic dyestuffs showed significant antimicrobial activity against the plant pathogen Cornebacterium and the human pathogen Coli bacillus. Tensile strength of the silk fibers after the salt shrinking and dyeing processes did not show a significant change, whereas the elongation at break was increased slightly. The techniques described here for preparing significantly active antimicrobial silk fibers are effective and economic ways of providing new materials for industrial and biomedical applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1181–1188, 2002     

High and low surface area NiO–MgO and CoO–MgO solid solutions: a study of XPS surface composition and CO oxidation activity

Oxide solid solutions NiO–MgO of high surface area were studied by XPS. The surface Ni²⁺ concentration was found to be equal, within experimental errors, to the bulk concentration. The result is analogous to that found previously for the low surface area NiO–MgO system and for both the high and low surface area systems of CoO–MgO. The catalytic oxidation of CO by O₂, on high and low surface area NiO–MgO and CoO–MgO materials, was investigated with the aim of relating the catalytic activity with transition metal ion nature and concentration. Turnover frequency data (CO₂ molecules produced per second per surface atom) show that the activity is due primarily to the transition metal ions and is not subject to the ions being in special configurations (dimers or trimers) or in special positions (edges, corners). The activity of CoO–MgO is higher than that of NiO–MgO solid solution. This revised version was published online in June 2006 with corrections to the Cover Date.     

Influence of temperature on continuous high gravity brewing with yeasts immobilized on spent grains

Flavor compounds’ formation and fermentative parameters of continuous high gravity brewing with yeasts immobilized on spent grains were evaluated at three different temperatures (7, 10 and 15 °C). The assays were performed in a bubble column reactor at constant dilution rate (0.05 h⁻¹) and total gas flow rate (240 ml/min of CO₂ and 10 ml/min of air), with high-gravity all-malt wort (15°Plato). The results revealed that as the fermentation temperature was increased from 7 to 15 °C, the apparent and real degrees of fermentation, rate of extract consumption, ethanol volumetric productivity and consumption of free amino nitrogen (FAN) increased. In addition, beer produced at 15 °C presented a higher alcohols to esters ratio (2.2–2.4:1) similar to the optimum values described in the literature. It was thus concluded that primary high-gravity (15°Plato) all-malt wort fermentation by continuous process with yeasts immobilized on spent grains, can be carried out with a good performance at 15 °C.