Reaction mechanism of partial oxidation of methane to synthesis gas over supported ni catalysts

A mechanistic study on the partial oxidation of methane to synthesis gas (H₂ and CO) was conducted with supported nickel catalysts. To investigate the reaction mechanism, pulse experiments, O₂-TPD, and a comparison of the moles of reactants and products were carried out. From the O₂-TPD experiment, it was observed that the active catalyst in the synthesis gas production desorbed oxygen at a lower temperature. In the pulse experiment, the temperature of the top of the catalyst bed increased with the pulses, whereas the temperature of the bottom decreased. This suggests that there are two kinds of reactions, that is, the total oxidation of methane (exothermic) at the top and reforming reactions (endothermic) at the bottom. From the comparison of the moles of reactants and products, it was found that the moles of CO₂, CH₄ and H₂O decreased as the moles of H₂ and CO increased. The results support the mechanism that synthesis gas is produced through a two-step reaction mechanism: the total oxidation of methane to CO₂ and H₂O takes place first, followed by the reforming reaction of the produced CO₂ and H₂O with residual CH₄ to form synthesis gas. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Preparation of modified polyesters containing triphosphorous and their applications to PU flame-retardant coatings

Three phosphorous functional groups were introduced in one structural unit of polymer backbone to enhance the flame retardancy of PU coatings. In the first step, we synthesized tetramethylene bis(orthophosphate) (TBOP) that contained two phosphorus functional groups in one structural unit. In the next step, we synthesized modified polyesters (ATBTP-10,-20,-30) that contained triphosphorous groups by condensing polymerization of TBOP, 1,4-butanediol, trimethylolpropane, adipic acid, and phenylphosphonic acid (PPA). The amount of PPA in the ATBTPs was 10, 20, and 30 wt%. Then, flame-retardant PU coatings (AHFC−10,−20,−30) were prepared by curing ATBTPs with hexamethylene diisocyanate-biuret (curing agent) at room temperature. From the TGA analysis of diphosphorus-modified polyester (ATBT) and ATBTPs, the residues of ATBT, ATBTP-10, ATBTP-20, and ATBTP-30 were 24.6, 27.5, 29.2, and 31.9%, respectively. From this result, it was found that the residue increased in relation to the amount of PPA. Physical properties of the films of flame-retardant coatings were deteriorated with the addition of PPA (flame retarding component), however, all the films of flame-retardant coatings, except AHFC-30, met the required physical properties standard for coatings. Char lengths of the AHFCs measured by the 45° Meckel burner method were 2.9∼4.8 cm, and LOI values were 28∼31%, which indicates that the prepared AHFCs showed good flame retardancy.     

Effect of support for alcohol-hydrocarbon synthesis from syngas in Cu-based catalyst

Effects of a Cu-based catalyst on the catalytic performance in alcohol-hydrocarbon synthesis from syngas have been investigated, using various supports. Under the different porosities of three supports (zinc oxide, activation carbon, and titanium dioxide), whereas Cu/ZnO produces one liquid phase of major mixed alcohols, Cu/AC and Cu/TiO₂ create two phases, alcohol (～75%) and hydrocarbon (～25%). X-ray diffraction shows that CuO impregnated on supports undergoes a complete reduction of metallic copper Cu⁰, which is the real active phase in the catalytic process. The Cu/TiO₂ catalyst showed the highest ethanol composition in a mixed alcohol phase under GHSV 18,000 h^?1, 30 bar, and 300 °C.     

Long-term release of chlorhexidine from dental adhesive resin system using human serum albumin nanoparticles

A functional dental adhesive resin system with antimicrobial properties was developed using human serum albumin (HSA) nanoparticles as the drug delivery carrier. HSA nanoparticles loaded with chlorhexidine (CHX) diacetate, a model antimicrobial drug, were prepared using a desolvation technique. The resulting CHX-loaded HSA nanoparticles were incorporated into a commercial methyl methacrylate (MMA)-based resin. The size of the nanoparticles ranged 50–300 nm, and the nanoparticles were dispersed homogeneously in the resin matrix. The CHX-loaded HSA nanoparticles showed an early release burst of ~20 % of the total CHX by day 5, followed by the sustained release of the remaining CHX over the next 20 days. In contrast, the resin matrix containing the HSA nanoparticles showed a sustained release of CHX without an early release burst in a 4-week immersion study. In the agar diffusion test, the resin matrix incorporating the CHX-loaded HAS nanoparticles showed a larger growth inhibition zone against Streptococcus mutans than the resin matrix alone, indicating that this delivery platform potently imparts antibacterial activity to the resins. These results also suggest that CHX, which inhibits the growth of oral bacteria, can be incorporated efficiently into the MMA-based resin matrix using HSA nanoparticles.     

One-dimensional confinement in crystallization of P(VDF-TrFE) thin films with transfer-printed metal electrode

The crystallization of thin polymer film depends on surface/interface properties, due to the fact that molecular chain motion is affected by the presence of the surface. In this work, we measured the ferroelectric properties, crystallinity, chain conformation and surface morphologies of one-dimensionally confined P(VDF-TrFE) thin films using transfer-printed Au film, annealed at elevated temperatures, from just below melting temperature up to 200 °C. Crystallization at low temperature, i.e., below melting temperature, the confinement effect has been found to be negligible. At high temperatures, however, confined crystallization has led to superior ferroelectric properties, compared to samples annealed without confinement. These observations have led to two- or three-layer model for those crystallized thin films with or without confinement, respectively. Further, the transfer-printing of metal as a confining surface has been found to be beneficial, compared to vacuum evaporation, due to deposition-induced damages on organic polymer. This confinement-induced retention of ferroelectricity in P(VDF-TrFE) thin films above its melting temperature can extend processing temperature in organic devices using the ferroelectric polymer, such as non-volatile organic memory devices.     

Isolation and characterization of a novel analyte from Bacillus subtilis SC-8 antagonistic to Bacillus cereus

In this study, an effective substance was isolated from Bacillus subtilis SC-8, which was obtained from traditionally fermented soybean paste, cheonggukjang. The substance was purified by HPLC, and its properties were analyzed. It had an adequate antagonistic effect on Bacilluscereus, and its spectrum of activity was narrow. When tested on several gram-negative and gram-positive foodborne pathogenic bacteria such as Salmonella enterica, Salmonella enteritidis, Staphylococcus aureus, and Listeria monocytogenes, no antagonistic effect was observed. Applying the derivative from B. subtilis SC-8 within the same genus did not inhibit the growth of major soybean-fermenting bacteria such as Bacillus subtilis, Bacillus licheniformis, and Bacillus amyloquefaciens. The range of pH stability of the purified antagonistic substance was wide (from 4.0 to >10.0), and the substance was thermally stable up to 60 °C. In the various enzyme treatments, the antagonistic activity of the purified substance was reduced with proteinase K, protease, and lipase; its activity was partially destroyed with esterase. Spores of B. cereus did not grow at all in the presence of 5 μg/mL of the purified antagonistic substance. The isolated antagonistic substance was thought to be an antibiotic-like lipopeptidal compound and was tentatively named BSAP-254 because it absorbed to UV radiation at 254 nm.     

In situ synthesis of thermochemically reduced graphene oxide conducting nanocomposites

Highly conductive reduced graphene oxide (GO) polymer nanocomposites are synthesized by a well-organized in situ thermochemical synthesis technique. The surface functionalization of GO was carried out with aryl diazonium salt including 4-iodoaniline to form phenyl functionalized GO (I-Ph-GO). The thermochemically developed reduced GO (R-I-Ph-GO) has five times higher electrical conductivity (42,000 S/m) than typical reduced GO (R-GO). We also demonstrate a R-I-Ph-GO/polyimide (PI) composites having more than 10(4) times higher conductivity (~1 S/m) compared to a R-GO/PI composites. The electrical resistances of PI composites with R-I-Ph-GO were dramatically dropped under ~3% tensile strain. The R-I-Ph-GO/PI composites with electrically sensitive response caused by mechanical strain are expected to have broad implications for nanoelectromechanical systems.