一些金属氧化物在TiO_2(锐钛矿)载体上的分散 嵌入模型的应用

一些金属氧化物在ＴｉＯ２（锐钛矿）载体上的分散＊嵌入模型的应用徐斌董林陈懿（南京大学化学系亚微观固态化学研究所，南京２１００９３）关键词嵌入模型，金属氧化物，分散容量，锐钛矿我们曾以γ－Ａｌ２Ｏ３，ＣｅＯ２和ＳｉＯ２为载体研究了离子化合物的分散，认为...     

Carotenoid incorporation into microsomes: yields, stability and membrane dynamics

The carotenoids beta-carotene (BC), lycopene (LYC), lutein (LUT), zeaxanthin (ZEA), canthaxanthin (CTX) and astaxanthin (ASTA) have been incorporated into pig liver microsomes. Effective incorporation concentrations in the range of about 1-6 nmol/mg microsomal protein were obtained. A stability test at room temperature revealed that after 3 h BC and LYC had decayed totally whereas, gradually, CTX (46%), LUT (21%), ASTA (17%) and ZEA (5%) decayed. Biophysical parameters of the microsomal membrane were changed hardly by the incorporation of carotenoids. A small rigidification may occur. Membrane anisotropy seems to offer only a small tolerance for incorporation of carotenoids and seems to limit the achievable incorporation concentrations of the carotenoids into microsomes. Microsomes instead of liposomes should be preferred as a membrane model to study mutual effects of carotenoids and membrane dynamics.     

Spectroscopic investigation of arsenate and selenate incorporation into hydroxylapatite

The mechanism(s) of arsenate and selenate incorporation into hydroxylapatite (HAP) using extended X-ray absorption fine structure (EXAFS) spectroscopy was investigated for As- and Se-doped HAP samples with concentrations between 200 and 2500 ppm. EXAFS data on As and Se K-edges have shown similar local coordination environments and are similar to that of P in HAP, suggesting the substitution of arsenate or selenate tetrahedra on the phosphate sites. EXAFS best-fitting for As-doped samples shows that the first shell is fitted with approximately 4 O atoms at 1.68 Å, showing As(V) in tetrahedral coordination, and Se K-edge EXAFS data are characterized by the backscattering contributions an oxygen shell at 1.2 Å in the Fourier transform, which can be fit with 4 O atoms at 1.65 ± 0.01 Å. This is characteristic of Se–O distances in SeO₄ tetrahedron. These findings suggest that arsenate and selenate substitute for phosphate groups with local distortions during the incorporation of these metals into the structure of HAP.     

Alloying-Triggered Phase Engineering of NiFe System via Laser-Assisted Al Incorporation for Full Water Splitting

It is challenging to design one non-noble material with balanced bifunctional performance for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) for commercial sustainability at a low cost since the different electrocatalytic mechanisms are not easily matchable for each other. Herein, a self-standing hybrid system Ni₁₈Fe₁₂Al₇₀, consisting of Ni₂Al₃ and Ni₃Fe phases, was constructed by laser-assisted aluminum (Al) incorporation towards full water splitting. It was found that the incorporation of Al could effectively tune the morphologies, compositions and phases. The results indicate that Ni₁₈Fe₁₂Al₇₀ delivers an extremely low overpotential to trigger both HER (η₁₀₀=188 mV) and OER (η₁₀₀=345 mV) processes and maintains a stable overpotential for 100 h, comparable to state-of-the-art electrocatalysts. The synergistic effect of Ni₂Al₃ and Ni₃Fe alloys on the HER process is confirmed based on theoretical calculation.     

Investigation of the incorporation of electrolyte anions in porous anodic Al2O3 films by employing a suitable probe catalytic reaction

A new method has been developed capable of describing the incorporation of electrolyte anions along the pore wall surface and across both the barrier layer and the pore wall oxide after the establishment of the steady state of growth of porous anodic Al₂O₃ where other methods cannot be applied to obtain reliable results. The knowledge of the nature/composition of anodic oxides as regards the incorporation of species like electrolyte anions is of specific importance for both the understanding of the electrochemical mechanism of oxide production and growth and the scientific and technological applications of porous anodic Al₂O₃ films. The method consists of the selection and use of a suitable catalytic probe reaction on porous anodic oxides at thicknesses varying from a value near zero up to the maximum limiting thickness and the treatment of the experimental reaction rate results by a properly developed mathematical formalism. This method was employed in anodic Al₂O₃ films prepared in H₂SO₄ anodizing electrolyte at a constant bath temperature and different current densities using as a probe reaction the decomposition of HCOOH on these oxides, which is almost exclusively a dehydration reaction, at relatively high reaction temperatures, 350 °C and 390 °C, where the effect of other species except SO₄ ²⁻ incorporated in the oxide on the reaction rate is eliminated. It has been shown that the fraction of the intercrystallite surfaces occupied by SO₄ ²⁻ follows a parabola-like distribution. It has a significant value at the pore base surface, depending on the current density, then it passes through a maximum along the pore wall surface and across both the barrier layer and the pore walls near the pore bases at positions depending on the current density and then becomes almost zero at the mouths of the pores of the oxide with the maximum limiting thickness and at both the Al₂O₃/Al interface and cell boundaries. The maximum value of the surface coverage is almost independent of the current density and is always near 1, showing an almost complete saturation of intercrystalline surfaces at these positions. The above distribution of surface coverage predicts a qualitatively similar distribution of the SO₄ ²⁻ bulk concentration across both the barrier layer and pore wall oxide around the pore bases. The method may be improved and developed further either for a more detailed investigation of the above films or to investigate films prepared in other pore-forming electrolytes. Received: 30 July 1998 / Accepted: 30 September 1998     

Preparation of multihollow polystyrene particles by seeded emulsion polymerization using seed particles with incorporated nonionic emulsifier: effect of temperature

Seeded emulsion polymerizations of styrene using polystyrene (PS) seed particles with incorporated nonionic emulsifier were carried out at 40 and 70 °C to investigate the influence of temperature during the polymerization process including the swelling step of the seed particles with monomer on the formation of multihollow PS particles. An increase in the temperature during the polymerization process caused an increase in the rate of coalescence (i.e., the degree of coalescence at any given time) of the small water domains in the inside. After the coalescence proceeded excessively, the water domains were eventually discharged from the particles to the medium, resulting in nonhollow particles. The results show that it is important for the preparation of the multihollow PS particles to control the coalescence of a lot of small water domains inside the seed particles with the incorporated nonionic emulsifier, and strongly support the formation mechanism previously proposed. Part CCCXX of the series “Studies on Suspension and Emulsion”.     

高分子共混物中氢键的作用Ⅱ.氢键对高分子共混物性能的影响以及引入方法

高分子共混物中氢键的存在能促进共混组分具有更好的可混和性.因此,研究高分子共混物中的氢键对高分子的共混改性具有重要的理论和实用价值.本文是<高分子共混物中氢键的Ⅰ.氢键的特征描述以及影响因素>的下篇,将继续介绍高分子共混物中氢键的作用,主要包括氢键对高分子共混物性能的影响以及主要的引入氢键的方法.特别地,本文通过将高分子共混物分为合成高分子与合成高分子共混物,合成高分子与天然高分子共混物以及合成高分子与其它物质共混物,总结了氢键存在对共混物性能的影响.     

Unique incorporation behavior of amino acid-type surfactant into phospholipid vesicle membrane

The incorporation behavior of some anionic surfactants, including amino acid-type surfactants, on phospholipid vesicles was investigated. This was done by measuring the release of a vesicle-entrapped fluorescence probe and the scattered light intensities of vesicle particles in the surfactant solution as a function of surfactant concentration and time. Sodium dodecyl sulfate, sodium dodecanesulfonate, sodium dodecanoyl sarcosinate, and sodium dodecanoyl glutamate were employed in this study. All surfactants ruptured the phospholipid vesicle at around each critical micelle concentration by mixed micelle formation with phospholipid. While leakage of the fluorescence probe took place at a very low concentration in the sulfate- or sulfonate-type surfactant systems, it occurred at the concentration just below the CMC in the amino acid-type surfactant systems. Kinetic analysis of the release of the probe from the vesicles showed that the former surfactants adsorbed independently and homogeneously onto the phospholipid vesicles, while the latter surfactants were cooperatively incorporated.     

A novel strategy to prepare LDH networks loaded carbon structure by C-MEMS techniques for glucose detection

NiAl-layered double hydroxide (NiAl-LDH) networks loaded carbon microcylinder (CMC) hybrid was synthesized for the first time using typical carbon based microelectromechanical systems (C-MEMS) techniques combined with in situ growth progress. The incorporation of NiAl-LDH on C-MEMS structures via a simple pyrolysis of modified photoresist was investigated. With proper control of parameters in lithography and hydrothermal processes, the NiAl-LDH/CMC composites with suitable morphology were fabricated. When the composites applied as new catalytic material for glucose detection, this simple sensor showed satisfying electrocatalytic properties towards glucose oxidation owing to its unique structure and excellent electric conductivity. It is also worth pointing out that this novel fabrication process can equip carbon microfeatures with various nanostructures, and have wide potential applications in scaling up carbon based nanocomposites.     

“嵌入模型”在γ-Al2O3负载单组分和双组分金属氧化物催化剂中的应用

探讨负载型金属氧化物催化剂的表面组分与载体之间的相互作用, 有助于理解相关催化剂的催化作用本质. 近年来, 我们对单组分CuO以及双组分CuO-Mn₂O₃, CuO-CoO等金属氧化物在γ-Al₂O₃载体表面的分散行为和存在状态, 及其物理化学性质和催化性能(CO+O₂和NO+CO模型反应)进行了研究. 结果表明, 这些金属氧化物在γ-Al₂O₃载体表面的分散行为和所得负载型催化剂样品的一些物理化学性质及其催化性能均可参照“嵌入模型”来解释. 在此基础上, 我们讨论了这些样品的“组成-结构-性质”间的关系, 并针对表面负载双组分金属氧化物样品提出了表面协同氧空位参与的NO+CO反应机理.