Photoelectrochemical energy conversion system modeled on the photosynthetic process

Photo-excitable electrodes were prepared by incorporating magnesium chlorophyll (MgChl) or manganese chlorophyll (MnChl) into the thin layer of such liquid cyrstals as N-(p-methoxybenzylidene)-p-butylaniline (MBBA) and 4′-heptyl-4-cyanobiphenyl (HCB), being attached to the platinum surface. The MgChl—MBBA electrode gave the positive photo-induced potential shift in an acidic solution. In sharp contrast, the negative photo-induced potential shift was developed by the MnChl—HCB electrode in an alkaline solution. The involvement of a liquid crystal prominently enhanced the photo-response of the immobilized chlorophylls. The photoelectrochemical energy conversion system modeled on the photosynthetic process was assembled by employing the MgChl—MBBA and the MnChl—HCB electrodes as a cathode and an anode, respectively. The photocurrent derived from the system was concluded to result from the decomposition of water, since an evidence for the molecular oxygen evolution at the MnChl—HCB electrode was obtained. Furthermore, the incorporation of β-carotene was found to markedly enhance the stability of the MnChl—HCB electrode.     

Studies on the nuclear magnetic resonance spectra of olefinic protons of conjugated fatty acid methyl esters

The NMR spectra of olefinic protons in the four representative conjugated fatty acid methyl esters, methylcis-9,trans-11-octadecadienoate, methyltrans-9,trans-11-octadecadienoate, methyl α eleostearate, and methyl β eleostearate, were studied. The chemical shift of each olefinic proton in these compounds was determined by considering their intramolecular environment. Coupling constants were also obtained as the results of spectral analysis.     

Partial oxidation of ethane to synthesis gas over Co-loaded catalysts

Attention has been increasingly paid to the partial oxidation of lower alkanes to synthesis gas, due to its intrinsic energy saving process. We studied the partial oxidation of ethane (POE) on Co loaded on various supports. The POE performance varied as follows: Y₂O₃, CeO₂, ZrO₂, La₂O₃  SiO₂, Al₂O₃, TiO₂ > MgO. Comparing Y₂O₃ and CeO₂, the carbon deposition during the POE was negligible on CeO₂ and therefore CeO₂ was the most preferable support. By changing space velocity and O₂ partial pressure, reaction mechanism of POE was studied and it was revealed that two-step mechanism was prevailing; combustion of ethane to H₂O and CO₂ and subsequent reforming of ethane with H₂O and CO₂ to synthesis gas. Co/CeO₂ catalyst exhibited high and stable catalytic activity for 10 h; high ethane conversion of 18% (maximum ethane conversion 20% at O₂/C₂H₆ = 0.2) with H₂ and CO selectivities of 93 and 84%, respectively.     

Thermal Behavior of BaTiO3 Particles Synthesized by Plasma Chemical Vapor Deposition

The thermal behavior of nanoparticles BaTiO₃, prepared by a radio-frequency plasma chemical vapor deposition (RF-plasma CVD) method, was characterized by various analysis methods. The BaCO₃ phase was included in the powder as byproducts, which is also observed in hydrothermal BaTiO₃ powder. The BaCO₃ phase decomposed and disappeared by annealing at 873 K for 30 min. H₂O, N₂, CO₂ and H₂, were detected by a thermal desorption spectra measurement from BaTiO₃ powder. The annealed powder became well-crystallized particles without grain growth, although as-prepared powder included polycrystalline particles. We successfully observed in-situ grain growth for BaTiO₃ nanoparticles by thermal transmission electron microscope. At the initial step of normal grain growth, very fine particles with 40–60 nm diameters started to merge into the larger grains around 1083 K. The migration rate was measured by video images and a grain boundary diffusion coefficient D_gb was calculated.     

Fate of the chlorine and fluorine in a sub-bituminous coal during pyrolysis and gasification

The fate of the chlorine and fluorine present in a sub-bituminous coal from Indonesia during pyrolysis and gasification has been studied with fixed and entrained bed reactors. The rate profile for HCl evolved in the temperature programmed pyrolysis exhibits the main and shoulder peaks at 480 and 600 °C, respectively. Model experiments and subsequent Cl 2p XPS measurements show that HCl reacts with metal impurities and carbon active sites at 500 °C to be retained as inorganic and organic chlorine forms, from which HCl evolves again at elevated temperatures. It is suggested that the HCl observed in the coal pyrolysis may originate from the above-mentioned chlorine functionalities formed by secondary reactions involving the nascent char. In the CO₂ gasification of the 900 °C char at 1000 °C and 2.5 MPa, any measurable amounts of HCl and HF could not be detected even at a high conversion of 75 wt% (daf), suggesting the accumulation of these halogens in the residual char. When the coal is injected into an O₂-blown, entrained bed gasifier at 1200-1400 °C under 2.6 MPa, the partial oxidation proceeds to a larger extent at a higher O₂/coal ratio, whereas the chlorine and fluorine are enriched in the remaining char, and the extent of the enrichment at the latter stage of gasification is larger with the fluorine. The XPS measurements of the chars reveal the presence of the broad F 1 s peak, which can cover a wide range of binding energies attributable to inorganic and organic fluorine. The halogen enrichment during gasification is discussed in terms of secondary reactions of HCl and HF with char.     

Gas transport properties of 6FDA-TAPOB hyperbranched polyimide membrane

Physical and gas transport properties of the hyperbranched polyimide prepared from a triamine, 1,3,5-tris(4-aminophenoxy)benzene (TAPOB), and a dianhydride, 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), were investigated and compared with those of linear-type polyimides with similar chemical structures prepared from diamines, 1,4-bis(4-aminophenoxy)benzene (TPEQ) or 1,3-bis(4-aminophenoxy)benzene (TPER), and 6FDA. 6FDA-TAPOB hyperbranched polyimide exhibited a good thermal stability as well as linear-type analogues. Fractional free volume (FFV) value of 6FDA-TAPOB was higher than those of the linear-type analogues, indicating looser packing of molecular chains attributed to the characteristic hyperbranched structure. It was found that increased resistance to the segmental mobility decreases the gas diffusivity of 6FDA-TAPOB, in spite of the higher FFV value. However, 6FDA-TAPOB exhibited considerably high gas solubility, resulting in high gas permeability. It was suggested that low segmental mobility and unique size and distribution of free volume holes arising from the characteristic hyperbranched structure of 6FDA-TAPOB provide effective O₂/N₂ selectivity. It is concluded that the 6FDA-TAPOB hyperbranched polyimide has relatively high permeability and O₂/N₂ selectivity, and is expected to apply to a high-performance gas separation membrane.     

Shape memorizing properties of a hydrogel of poly(vinyl alcohol)

Hydrogel prepared by repetitive freezing and thawing of poly(vinyl alcohol) aqueous solution was chemically crosslinked with glutaraldehyde. The chemically crosslinked hydrogel hardly changed its physical appearance, and showed good elasticity and strength as original gel. However, after treating in boiling water, it swelled a little, depending on the condition of the chemical treatment. The melted gel thus obtained showed shape memorizing property, that is, it could firmly hold nearly 200% of strain, keeping its original high elasticity. The strain could be released very quickly (< 1 s) in boiling water, and the gel was suggested to be applied to a new type of gel actuator. X-ray diffraction study revealed that the melted gel does not necessarily reform the physical crosslinks in exactly the same manner as the original gel in the process of shape restoring, but the distribution of the physical crosslinks can be restored as they were. It was suggested that the chemical crosslinks which remember the distribution of the physical crosslinks plays a critical roll in the shape restoring process.     

Residual amounts of chlorophylls and pheophytins in refined edible oils

The quantities of chlorophyll (CHL) A and B, and pheophytin (PHY) A and B in 10 kinds of refined edible oils were estimated by the fluorometric method. The results revealed that CHL and PHY were present in commercial edible oils. PHY A showed the highest content at ca. 67% in total pigments. Compositional ratios of CHL and PHY were similar in different kinds of plant oils. Through the analysis of rapessed oils at every refining step, we determined that PHY is not formed during oil refining. In the autoxidation of soybean oils to which various amounts of CHL mixtures had been added, the peroxide value of tested oils increased in proportion to the total chlorophyll content. In addition, the compositional changes of the 4 components during autoxidation were investigated.     

Two-stage pyrolysis of heavy oils. 3. Pyrolysis of tar-sand bitumens. Relation between ethylene yield and structural characteristics of heavy oils

Thermal cracking of tar-sand bitumens has been carried out using a two-stage pyrolysis reactor with temperature zones of 440°C and 750–800°C, respectively. Feedstocks were pyrolysed in the first stage into cracked oils, which were carried to the second stage for subsequent pyrolysis. Only 12–14 wt% of ethylene was obtained from tar-sand bitumens at the residence time of 1.2 s in the second stage, although 27 and 16 wt% were obtained from Taching and Iranian heavy vacuum residues, respectively. The tar-sand bitumens contain shorter paraffinic straight-chains and have more branched molecules than the vacuum residues of petroleum. A straight-chain paraffin index is proposed, with which a good correlation was obtained between ethylene yield and the fraction of straight-chain paraffin carbons in the heavy oil.     

Gelation of poly(vinyl alcohol)/phenol/water solutions and gel spinning

The light transmittance of the gels of poly(vinyl alcohol) (PVA)/phenol/water solutions was examined for the entire range of phenol/water content. Excellent transparency was found for the gels with phenol contents of 70–95 vol %. In full consideration of the results for the transparency and melting temperature of the gels and the viscosity and gelation ability of solutions, the PVA solutions of 75 vol % phenol content were selected for the gel spinning. The maximum dynamic moduli of drawn filaments at 25°C (room temperature) were 42 GPa (15x) for atactic PVA and 45 GPa (14x) for syndiotacticity-rich PVA. © 1995 John Wiley & Sons, Inc.