Novel g-C3N4 nanosheets/CDs/BiOCl photocatalysts with exceptional activity under visible light

We fabricated novel ternary nanocomposites through integration of C-dots (carbon dots), BiOCl, and nanosheets of graphitic carbon nitride (g-C₃N₄ nanosheets) by a cost-effective route. The fabricated photocatalysts were subsequently characterized by XRD, EDX, TEM, HRTEM, XPS, FT-IR, UV-vis DRS, TGA, BET, and PL methods to gain their structure, purity, morphology, optical, textural, and thermal properties. In addition, the degradation intermediates were identified by gas chromatography-mass spectroscopy (GC-MS). Photocatalytic performance of the synthesized samples was studied by photodegradations of three cationic (RhB, MB, and fuchsine), one anionic (MO) dyes, one colorless (phenol) pollutant and removal of an inorganic pollutant (Cr(VI)) under visible light. It was revealed that the ternary nanocomposite with loading 20% of BiOCl illustrated superlative performances in the selected photocatalytic reactions compared with the corresponding bare and binary photocatalysts. Visible-light photocatalytic activity of the g-C₃N₄ nanosheets/CDs/BiOCl (20%) nanocomposite was 42.6, 27.8, 24.8, 20.2, and 15.9 times higher than the pure g-C₃N₄ for removal of RhB, MB, MO, fuchsine, and phenol, respectively. Likewise, the ternary photocatalyst showed enhanced activity of 15.3 times relative to the g-C₃N₄ in photoreduction of Cr(VI). Moreover, the ternary nanocomposite exhibited excellent chemical stability and recyclability after five cycles. Finally, the mechanism for improved photocatalytic performance was discussed based on the band potential positions.     

Biased distribution of the branched-chain fatty acids in ceramides of vernix caseosa

The compositions of ester- and amide-linked fatty acids from ceramides of human vernix caseosa were described with emphasis on the distribution of the branched-chain fatty acid (BCFA). Two novel ceramides were isolated from vernix caseosa in the course of this study: the acylated type of esterified α-OH-hydroxyacid/sphingosine ceramide (Cer[EAS]) and nonacylated type of non-OH fatty acid/hydroxysphingosine ceramide (Cer[NH]). Their chemical structures were identified by nuclear magnetic resonance and chemical procedure. The Cer[EAS] was an acylceramide and consisted of the highest concentrations of ester- and amide-linked BCFA (62 and 67%, respectively). The iso- or anteiso-branching structures of the aliphatic chains were confirmed by the mass spectra of their picolinyl or pyrrolidide derivatives. As a whole, amide-linked fatty acids of ceramides 1–7 and Cer[NH] were normal types of straight-chain fatty acids with or without α- or ω-hydroxylation. The BCFA concentrations of amide-linked fatty acids in these ceramides (ceramides 1–7 and Cer[NH]) were low and less than 10%. The BCFA thus occurred exclusively in a novel acylceramide of Cer[EAS] in the vernix caseosa.     

Adsorption of cationic monomeric and gemini surfactants on montmorillonite and adsolubilization of vitamin E

Adsorption of a cationic gemini surfactant (1,2-bis(dodecyldimethylammonio) ethane dibromide, 12-2-12) and the corresponding monomeric surfactant (dodecyltrimethylammonium bromide, DTAB) on montmorillonite has been characterized with a combination of adsorption isotherm, interlayer spacing and FT-IR spectroscopic data. Adsolubilization of vitamin E into the adsorbed surfactant layers has also been studied. The adsorption isotherm data reveal that the adsorption of the two surfactants is driven by the two factors: one is the cation exchange that occurs on the interlayer basal planes and the other is the hydrophobic interaction between hydrocarbon chains of the surfactants. Although the adsorbed amount measured in the saturation region (in mol g(-1)) is almost identical for the two surfactants, the conformation of the intercalated surfactant molecules differs significantly from each other. The adsorption of DTAB results in a lateral bilayer arrangement in the limited interlayer space, whereas 12-2-12 gives a normal bilayer arrangement in the expanded interlayer space. Adsolubilization of vitamin E takes place into the adsorbed surfactant layers, and interestingly, all the vitamin E molecules added in the montmorillonite suspensions are hybridized at lower surfactant concentrations due to the great specific surface area of the clay material. Since the maximum adsolubilization amount is usually obtained just below the critical micelle concentration, the gemini surfactant is deemed to be more efficient than the corresponding monomeric one to achieve the great adsolubilization amount.     

Methanol decomposition to synthesis gas over supported Pd catalysts prepared from synthetic anionic clays

Supported Pd or Rh catalysts were prepared by the solid-phase crystallization method starting from hydrotalcite anionic clay minerals based on [Mg₆Al₂(OH)₁₆CO ₂ ²⁻ ]·4H₂O as the precursors. The precursors were prepared by a coprecipitation method from the raw materials containing Pd²⁺ and various trivalent metal ions which can replace each site of Mg²⁺ and Al³⁺ in the hydrotalcite. Rh³⁺ was also used for preparing the catalyst as comparison. The precursors were then thermally decomposed and reduced to form supported Pd or Rh catalysts and used for the methanol decomposition to synthesis gas. Among the precursors tested, use of Mg–Cr hydrotalcite containing Pd²⁺ resulted in the formation of efficient Pd supported catalysts for the production of synthesis gas by selective decomposition of methanol at low temperature. Although Pd²⁺ cannot well replace the Mg²⁺ site in the hydrotalcite, the Pd supported catalyst (Pd/Mg–Cr) prepared by the solid-phase crystallization method formed highly dispersed Pd metal particles and showed much higher activity than that prepared by the conventional impregnation method. When the precursor was prepared under mild conditions, more fine particles of Pd metal were formed over the catalyst, resulting in high activity. It is likely that the high activity may be due to the highly dispersed and stable Pd metal particles assisted by the role of Cr as the co-catalyst. This revised version was published online in November 2006 with corrections to the Cover Date.     

NATURAL CONVECTION IN A DIFFERENTIALLY HEATED SQUARE CAVITY WITH INTERNAL HEAT GENERATION

A high-resolution, finite-difference numerical study is reported on natural convection in a square cavity. The vertical sidewatts of the cavity are differentially heated, and a uniform internal heat generation is also present. Two principal parameters are considered, the internal Rayleigh number Ra_I, which represents the strength of the internal heat generation, and the external Rayleigh number Rag, which denotes the effect due to the differential heating of the side walls. The internal Rayleigh number varies in the range 10¹⁰ Ra_I ≤ 10⁷, while the external Rayleigh number is set at Ra_E = 5 x 10⁷ for most computations. As the relative strength of the internal heat generation increases, the flows near the tap portion of the heated sidewall are directed downward. When the effect of the internal heat generation is dominant, the thermal energy leaves the system for the surroundings over the top portion of the heated wall. Only in the bottom pari of the heated wall is heat transfer directed into the system. These numerical solutions are in qualitative agreement with the available experimental measurements.     

Application of microbial genes to recalcitrant biomass utilization and environmental conservation

Recent papers concerning the application of microbial genes to recalcitrant biomass utilization and environmental conservation are reviewed. Microbial genes have been integrated and expressed in plants and microorganisms. When cellulose-degrading enzyme genes are expressed in rice plants, the transgenic plants exhibit swollen cell walls which increases the digestibility of rice straw in the rumen. When genes encoding aromatic compound-degrading enzymes are expressed in plants, it is expected that aromatic compounds contaminating soil would be degraded during the growth of the transgenic plants. The former transgenic plants are utilized as feed and the latter for phytoremediation. Dockerin and cohesin interactions occurring in the cellulase complex, cellulosome, are applied to the construction of artificial enzyme complexes and protein purification by expressing the genes in transformed bacteria and/or silkworms, respectively. In the case of the forced expression of bacterial genes encoding chitinase and/or hydrogenase in the wild-type bacteria, chitin degradation and hydrogen gas production in the transformed bacteria occur at much higher rates than in the wild type.     

Properties of poly(vinyl chloride) fibers crosslinked by 2-dibutylamino-4,6-dimercapto-1,3,5-triazine

PVC fibers, fastened to a needle frame, were crosslinked by 2-dibutylamino-4, 6-dimercapto-1,3,5-trizine in the presence of tetra-n-butylammonium bromide and alkali in water at 96°C. Solvent resistance, characterized by the gel fraction of THF, improves markedly. Mechanical properties of the fibers investigated by tensile tests at 20°C show that both the modulus and tensile strength at break increase, while elongation at break decreases over 40% gel content. Creep tests indicate that the resistance to heat deformation improves by crosslinking. The heat distortion temperature increases by 12°C at 75% gel content. Results of dynamic tests show that the T_g of PVC fibers determined by a peak in the loss modulus (E'') increases from 40% gel content. Dynamic modulus (E') increases by 74% at 23°C and the T_g by 37°C in the case of crosslinked PVC fibers having a 92% gel content. The shrinkage of PVC fibers in hot water at 94°C for 30 min decreases more than 50% over 75–80% gel content indicating the improved resistance to heat deformation.     

Numerical simulation on the dynamics of photoinduced cooperative phenomena in molecular crystals

We develop a new simulation method to study the dynamics of initial nucleation processes of photoinduced structural change of molecular crystals. In order to describe the nonadiabatic transition in each molecule, we employ a model of localized electrons coupled with a fully quantized phonon mode, and the time-dependent Schrödinger equation for the model is numerically solved. By applying a mean-field approximation in solving the Schrödinger equation, the calculation method is quite efficient on parallel computing systems. We show that coherently driven molecular distortion plays an important role in the successive conversion of electronic states which leads to photoinduced cooperative phenomena.     

Effect of Composition and Size of Crystallite on Crystal Phase in Lead Barium Titanate

Lead titanate, barium titanate, and lead barium titanate powders (>99.9% pure), the particle size of which varied from 0.03 to 0.15 μm depending on the calcination temperature and the composition, was prepared from barium lead titanyl oxalate, which was previously prepared by reacting high-purity ammonium titanyl oxalate with barium and lead acetate. The critical crystallite size of BaTiO₃ powder from the cubic to the tetragonal phase is around 1 μm. Pb_0.3Ba_0.7TiO₃ powder with an average size of 0.057 μm showed the tetragonal phase.     

Densification of rare-earth (Lu, Gd, Nd)-doped alumina nanopowders obtained by a sol-gel route under seeding

Rare-earth (RE: Lu, Gd, Nd, 0.10 mol%)-doped alumina nanopowders were prepared by a new sol-gel route using polyhydroxoaluminum (PHA) and RECl₃ solutions under α-alumina (∼ 75 nm) seeding. Among the rare-earth dopants studied, Lu yields the most suitable nanopowders for low-temperature densification. The 0.10 mol% Lu-doped nanopowders, which were obtained at a calcination temperature of 900 °C under 5 mass% α-alumina seeding, consisted of ∼ 80-nm α-alumina particles and γ-alumina nanoparticles. Using these Lu-doped alumina nanopowders, fully densified alumina ceramics with a uniform microstructure composed of fine grains with an average size of 0.61 μm could be obtained at 1400 °C by pressureless sintering. Clearly, the Lu-doped nanopowders obtained here represent a viable option for fabricating dense, finer-grained alumina ceramics because an undoped sample with 5 mass% seeds gave a microstructure with an average grain size of 1.78 μm at 1400 °C.