Hydrogen storage in boron nitride and carbon clusters studied by molecular orbital calculations

Possibility of hydrogen gas storage in carbon (C) and boron nitride (BN) clusters was investigated by molecular orbital calculations. Chemisorption calculation was carried out for C₆₀, B₂₄N₂₄ and B₃₆N₃₆ with changing position of hydrogen atom to compare the bonding energy at carbon, nitrogen and boron, tetragonal and hexagonal rings. Chemisorption calculation of hydrogen for BN clusters showed that hydrogen bondings with nitrogen atoms and tetragonal rings were the most stable. Stability of H₂ molecules inside BN and C clusters was also investigated by molecular orbital calculations. C and BN clusters showed possibility of hydrogen storage of 6.5 and 4.9 wt%, respectively.     

Substituted propenyl end groups as reactive intermediates in radical polymerization

The addition of propagating radicals of methyl acrylate (MA) and styrene (St) to CH₂?C(CO₂CH₃)CH₂? and CH₂?C(C₆H₅)CH₂? ω‐end groups of poly(methyl methacrylate) (PMMA) and polystyrene (PSt) was investigated. The end groups were as reactive as MA and St toward the poly(methyl acrylate) (PMA) and PSt radicals, respectively. The adduct radical derived from the two types of PMMA end groups and PMA radicals underwent β fragmentation exclusively to yield PMMA radicals and end groups bound to PMA chains. The addition of PSt radicals to PMMA with CH₂?C(CO₂Me)CH₂? end groups resulted in adduct radicals that underwent β fragmentation and addition to St or coupling with PSt radicals. Adduct radicals formed by the addition of PMA radicals to both types of end groups of PSt exclusively formed C? C bond by coupling with PMA radicals to form branched structures or by addition to MA monomer to give a copolymer. The fate of the adduct radicals was highly dependent on the type of polymer chain and the substituent bound to the end group. Steric congestion of the adduct radical arising from the α‐methyl group of the PMMA chain was considered to be crucial for fragmentation to expel the PMMA radical. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 645–654, 2003     

The first stereospecific arylation of (Z)‐germyl(stannyl)ethenes with an aryl halide or heteroaryl halide under palladium‐catalysis

A combination catalyst of Pd(dba)₂‐PPh₃‐CuI‐LiCl or Pd(dba)₂‐P(2‐furyl)₃‐CuI‐LiCl effectively catalyzed the cross‐coupling of (Z)‐germyl(stannyl)ethenes with aryl halides, providing novel triethyl(2,2‐diarylethenyl)germanes in good to high yields. The reaction proceeds with retention of configuration. Cross‐coupling results in the formation of phenylene or phenyleneethynylene derivatives with terminal stereochemically defined vinylgermane unit(s). Copyright © 2008 John Wiley & Sons, Ltd.     

Structures and photovoltaic properties of copper oxides/fullerene solar cells

Copper oxide (CuO_x) thin films were produced by spin-coating and electrodeposition methods, and their microstructures and photovoltaic properties were investigated. Thin film solar cells based on the Cu₂O/C₆₀ and CuO/C₆₀ heterojunction or bulk heterojunction structures were fabricated on F-doped or In-doped SnO₂, which showed photovoltaic activity under air mass 1.5 simulated sunlight conditions. Microstructures of the CuO_x thin films were examined by X-ray diffraction and transmission electron microscopy, which indicated the presence of Cu₂O and CuO nanoparticles. The energy levels of the present solar cells were also discussed.     

Formation and Properties of Boron Nitride Nanocapsules with Metals and Semiconductor Nanoparticles

Abstract

Boron nitride nanocapsules with gold, iron oxide and germanium nanoparticles were produced. High-resolution electron microscopy and electron energy-loss spectroscopy showed the gold, iron oxide and germanium nanoparticles were encapsulated in the boron nitide sheets. Weak peaks of photoluminescence spectrum were observed from the nanocapsules with germanium nanoparticles. The present work indicates that the boron nitide nanocapsules with conducting, magnetic and semiconductor nanoparticles can be produced by are melting method, and models for the formation mechanism and nano-structures of the boron nitide nanocapsule were proposed.     

Concentration determination of oxygen nanobubbles in electrolyzed water

Water electrolysis is well known to produce solutions supersaturated with oxygen. The oxygen in electrolyzed solutions was analyzed with a dissolved oxygen meter and the Winkler method of chemical analysis. The concentration of oxygen measured with the dissolved oxygen meter agreed with that obtained using the Winkler method. However, measurements using a 10-fold dilution method showed a larger concentration of dissolved oxygen compared to the above methods. We developed a modified Winkler method to measure total oxygen concentration more accurately, which agreed with the results obtained from the 10-fold dilution experiment. The difference in measurements is due to the existence of oxygen nanobubbles, as confirmed by the observation of dynamic light scattering using a laser. Further analysis of the oxygen nanobubbles demonstrated that the stability of the nanobubbles was sufficient for chemical reaction and solvation to bulk solution.     

Role of electrolytes in the preparation of nanoparticles via the emulsion polymerization of vinyl pivalate

By controlling both the kind of ion and the ionic strength of electrolytes in an emulsion polymerization system of vinyl pivalate containing about 1% sodium lauryl sulfate as a surfactant, nanoparticles of polyvinylpivalate having a diameter of about 25 nm were successfully prepared. The use of high concentrations of lithium chloride and lithium sulfate (1.0 mol L⁻¹) prevented the nanoparticles from aggregating and produced nanoparticles sizes of 25–50 nm. Ammonium acetate and sodium acetate, on the other hand, accelerated the aggregate of the nanoparticles. These phenomena were examined in detail and found to be similar to the Hofmeister phenomena and the combination rule proposed by Craig et al.     

Superhydrophilicity and XPS study of boron-doped TiO2

This study examines the superhydrophilicity and chemical state of boron-doped TiO₂ prepared by the ion implantation method and explores the effect of annealing on them. XRD measurements show that the implanted sample forms a polycrystalline structure of anatase with no trace of rutile. Their water-contact angles are significantly reduced upon irradiation with ultraviolet light. The Ti 2p XPS spectra of the oxide exhibit a shoulder peak at the lower binding energy side of the main peak, whereas no shoulder is observed in single-crystal and annealed TiO₂. This suggests that the titanium ions with lower valences are produced by boron doping and they disappear on subsequent annealing. The SIMS depth profile of boron in the as-implanted TiO₂ exhibits a peak at a depth of 15-20 nm, whereas this peak disappears upon annealing. The water-contact angles increased on annealing under ultraviolet light illumination. It is concluded that the improvement in the superhydrophilicity by boron doping is due to the reduction of titanium, and the deterioration of superhydrophilicity with the subsequent annealing is due to the oxidation of reduced titanium and the inward diffusion of boron.     

Application of esca to semi-quantitative surface and state analysis of iron oxides

In order to study oxidation states in the surface analysis of solids, a semi-quantitative ESCA (X-ray photoelectron spectroscopy-XPS and X-ray-excited Auger-electron spectroscopy-XAES) method was proposed. Taking iron-oxygen compounds as examples, the summation or subtraction technique was utilized in the analysis of ESCA spectra to identify the co-ordination type and crystal structure. The "XAES intensity factors" for the lines Cr L(3)M(2,3)M(4,5), Ti L(3)M(2,3)M(4,5) and from Fe L(3)M(4,5)M(4,5) to Zn L(3)M(4,5)M(4,5) were estimated and their occurrence discussed.