Structural and magnetic characterization of norbornene-deuterated norbornene dicarboxylic acid diblock copolymers doped with iron oxide nanoparticles

A series of iron oxide doped norbornene (NOR)/deuterated norbornene dicarboxylic acid (NORCOOH) diblock copolymers were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), small angle neutron scattering (SANS) and superconducting quantum interference device (SQUID) experiments. γ-Fe₂O₃ nanoparticles were synthesized within the microdomains of diblock copolymers with volume fractions of NOR/NORCOOH 0.64/0.36, 0.50/0.50 and 0.40/0.60. A spherical nanoparticle morphology was displayed in the polymer with 0.64/0.36 volume fraction. Polymers with 0.50/0.50 and 0.40/0.60 volume fractions exhibited interconnected metal oxide nanostructures. The observed changes in the shape and peak positions of the small-angle neutron scattering profiles of polymers after metal doping were related to the scattering from the metal oxide particles and to the possible deformed morphologies due to the strong interparticle interactions between metal particles, which may influence the polymer microphase separation. The combined scattering from both polymer domains and magnetic particles was depicted in SANS profiles of metal oxide doped polymers. γ-Fe₂O₃ containing block copolymers were superparamagnetic at room temperature. An increase in the blocking temperature (T_b) of interconnected nanoparticles was observed and was related to the interparticle interactions, which depends on the average distance (d) between particles and individual particle diameter (2R). The sample with volume fraction of 0.4/0.6 have the lowest d/(2R) ratio and exhibit the highest T_b at 115 K.     

氧化锌分散体光反应产生的自由基中间体

溶液中光诱导的电子转移反应已进行了大量的研究。而半导体粉末在水相或非水溶剂中的光化学研究也与自俱增。这种光化学与成像体系、太阳能转换以及光催化或污物的光降解有关。因此,越来越引起人们的重视。 Harbour和Hair用自旋捕捉技术研究了在ZnO-H_2O的分散体系中光合成过氧化氢,并检测到羟基自由基。他们认为氧化锌可能通过水的氧化将O_2还原成H_2O_2,从而使太阳能转换成化学能。人们自然会想到ZnO在其它溶剂中是否-也能观察到溶剂光氧化     

Selective gas transport in miscible PPO-PS blends

The permeation rates of He, CO₂ and CH₄ though miscible blends of polystyrene and poly(phenylene oxide) at 35°C are reported as a function of pressure. Sorption isotherms for CO₂ and CH₄ are also presented. By using ratios of the permeabilities of the pure gases the separation factors for the gas pairs He---CH₄ and CO₂---CH₄ can be estimated. For both pairs the estimated separation factor goes through a prominent maximum, thus indicating that these blends are more permselective than expected from the behaviour of polystyrene and poly(phenylene oxide). This stems from mobility considerations rather than solubility effects and a qualitative free volume argument is proposed as an explanation. The sorption and transport data have been interpreted and correlated using the dual sorption-mobility models developed previously for glassy polymers. Since the commercial polystyrene used contained a small amount of mineral oil to improve flow behaviour, the effect of this additive on polystyrene properties was explored in some detail.     

Transformation of β-Ni(OH)2 to NiO nano-sheets via surface nanocrystalline zirconia coating: Shape and size retention

Shape and size of the synthesized NiO nano-sheets were retained during transformation of sheet-like β-Ni(OH)₂ to NiO at elevated temperatures via nano-sized zirconia coating on the surface of β-Ni(OH)₂. The average grain size was 6.42 nm after 600 °C treatment and slightly increased to 10 nm after 1000 °C treatment, showing effective sintering retardation between NiO nano-sheets. The excellent thermal stability revealed potential application at elevated temperatures, especially for high temperature catalysts and solid-state electrochemical devices.     

Effect of cobalt oxide on surface structure of alumina supported molybdena catalysts studied by in situ Raman spectroscopy

A set of Co promoted 10% Mo/Al₂O₃ samples have been characterized by means of Raman spectroscopy under ambient as well as in situ dehydrated conditions. Under ambient conditions, the degree of the polymerization of surface molybdenum oxide species decreases with increasing Co loading. Under dehydrated conditions, the polymeric molybdenum oxide species is absent with the addition of only 0.2% Co. At low Co loadings (2%), before the formation of CoMoO₄ compound, the spectral features are very similar under ambient conditions. Dehydration causes the upward shift of the Mo=O symmetric stretching mode. A broad band around 920–930 cm^–1 was thus observed. This band has been suggested to be associated with the Co-Mo interaction species. In contrast to crystalline CoMoO₄, this species shows a reversibility on H₂ reduction-O₂ reoxidation treatments. From the results obtained, it is proposed that cobalt oxide interacts with the most polymerized molybdenum oxide species to form Co-Mo interaction species and/or crystalline CoMoO₄; therefore, the amount of the surface molybdenum oxide species decreases with a change in the molecular structure as a function of the Co concentration.     

Kinetics of the methanation of carbon dioxide over a supported Ni-La2O3 catalyst

The kinetics of the methanation of carbon dioxide was investigated using an alumina supported Ni-La₂O₂ catalyst in a differential and integral reactor. In the differential reactor the molar ratio of H₂ to CO₂ was varied from 0.6 to 30. In the integral reactor the rates were measured with up to 90% conversion. Both reactor tests were carried out at temperatures between 513 and 593 K. The experimental results were described by a Langmuir-Hinshelwood type equation. The kinetics can be explained by assuming equilibrium of dissociative carbon dioxide and hydrogen adsorption, and assuming hydrogenation of surface carbon as the rate determining step.     

Oxidative coupling of methane over CaO-MgO mixed oxide

Mixed oxide catalyst prepared by co-precipitating magnesium oxide and calcium oxide showed an excellent activity for the oxidative coupling of methane. The high performances were presumed to arise from the high basicity of the mixed oxide.     

Influence of silicon on the growth of barrier-type anodic films on titanium

Amorphous anodic titania, stabilised by incorporation of silicon species, is shown to grow to high voltages on sputter-deposited, single-phase Ti-Si alloys during anodizing at a constant current density in ammonium pentaborate electrolyte. The films comprise two main layers, with silicon species confined to the inner layers. An amorphous-to-crystalline transition occurs at ∼60 V on the Ti-6 at.% Si alloy, while the transition is suppressed to voltages above 140 V on alloys with 12 and 26 at.% silicon. The crystalline oxide, nucleated at a depth of ∼40% of the film thickness, is associated with the presence of a precursor of crystalline oxide in the pre-existing air-formed oxide. The modified structure of the air-formed oxide due to increased incorporation of silicon species suppresses the amorphous-to-crystalline transition until the onset of dielectric breakdown. The transport numbers of cations and anions during growth of the anodic oxides are independent of the concentration of silicon species in the inner layer, despite the marked change in the field strength.     

环氧丙烷生产工艺进展

综述了近年来环氧丙烷合成工艺的新进展,包括对现有环氧丙烷生产工艺的革新、直接氧化法、光催化环氧化等方法,并对各种方法的特点和发展前景进行了讨论.