氧化电压对多孔阳极氧化铝膜结构及形成的影响

以草酸为电解液研究了氧化电压对多孔阳极氧化铝膜的影响,采用场发射扫描电子显微镜(FE-SEM)对多孔阳极氧化铝膜的表面形貌进行表征.结果表明:氧化电压决定多孔阳极氧化铝膜纳米孔的大小;在一定电压范围内,氧化膜厚度随氧化电压的升高而增加.电流密度与氧化时间的关系曲线表明:在不同电压下多孔阳极氧化铝膜的形成历程基本相同,但形成多孔氧化铝膜时的电流密度随氧化电压的升高而增加.XRD分析结果证实:多孔氧化铝膜由非晶态的Al2O3组成,其组成不随阳极氧化电压而变化.     

高度有序多孔氧化铝模板影响因素的研究

在酸性电解液中,用阳极氧化法制备得到了多孔阳极氧化铝(anodic aluminum oxide,AAO)模板。用金相显微镜观察了铝箔退火后表面上的晶界,并结合扫描电镜对多孔氧化铝薄膜进行了观察和表征。研究了影响多孔氧化铝模板孔洞有序性的关键性因素。实验结果表明,多孔阳极氧化铝膜的有序度依赖于铝箔预处理、氧化电压和电解液等的选择。     

高度有序多孔阳极氧化铝模板制备工艺研究

在酸性电解液中,用二次阳极氧化法制备得到了高度有序的多孔阳极氧化铝(PAA)模板。采用金相显微镜观察了铝箔退火前后的表面形貌,并结合扫描电镜对多孔氧化铝薄膜的结构进行了表征。研究表明,高度有序多孔阳极氧化铝膜的制备依赖于铝箔是否经过预处理、氧化电压的大小、温度的稳定性和电解液的选择等。     

影响多孔阳极氧化铝膜结构特性因素的研究

酸性电解液中采用电化学方法可在铝表面形成多孔阳极氧化铝膜。研究了影响膜孔径和膜厚的关键因素,包括电解液、氧化电压、温度和时间。此外,通过X-射线衍射和扫描电镜,分析了形成氧化膜的微观形貌和晶体结构。实验结果表明多孔阳极氧化铝膜结构特性依赖于采用的氧化条件、电解液、氧化时间和电压的选择。     

多孔氧化铝模板的制备及应用

以磷酸溶液为电解液、以高纯铝为阳极,采用两步阳极氧化法制备氧化铝模板。扫描电子显微镜(SEM)对其表面形貌分析表明,氧化铝膜为多孔结构,膜孔径随着阳极氧化电压的增大而不断增大。对阳极氧化电流密度变化分析证实,铝的阳极氧化经历了三个阶段:阻挡层的生成、多孔层的形成和多孔层的稳定生长。以制备的氧化铝膜为阴极、锌片为阳极,以硝酸锌和硼酸的混合液为电解液,采用交流电沉积方法制备了针状氧化锌纳米线。     

高度有序的多孔型铝阳极氧化膜的制备

以硫酸为电解液研究了多孔阳极氧化铝膜的制备,并采用场发射扫描电子显微镜对多孔氧化铝膜的形貌进行表征.结果表明:氧化电压在24～26 V时能够得到孔径为25～30 nm的多孔氧化铝膜.在不同电压下进行阳极氧化时,多孔氧化铝形成过程均经历了阻挡层形成、多孔层萌生及多孔层稳定生长三个阶段,但多孔层萌生及稳定生长的电流密度随氧化电压的升高而增加.当氧化时间为6h时氧化膜厚度达到最大值38nm.对多孔氧化铝膜进行XPS分析表明,氧化铝膜的主要成分为非晶态Al2O3.     

Co-氧化铝纳米阵列的结构与磁性研究

用二次阳极氧化法制备了多孔氧化铝膜，并以之为模板，用直流电沉积法成功地将Co金属组装入多孔氧化铝膜的纳米孔洞中，观察与测试了Co—氧化铝纳米阵列结构和磁性。结果发现，二次阳极氧化法在短时间内就能制备出较为有序的多孔氧化铝膜；Co—氧化铝纳米阵列中的Co金属纳米线有一定的结晶择优取向，并且当多孔氧化铝模板的孔径减小，择优取向发生优化；Co—氧化铝纳米阵列有明显的磁各向异性。     

阳极氧化铝模板有序度影响因素的研究

在酸性电解液中,用阳极氧化法制备了多孔阳极氧化铝模板。用金相显微镜观察了铝箔退火前后的表面形貌,并结合扫描电镜对多孔氧化铝薄膜进行了形貌观察和表征。研究了影响多孔氧化铝模板孔有序性(分布均匀,大小一致)的关键性因素。实验结果表明,多孔阳极氧化铝膜结构特性依赖于铝箔预处理、氧化电压、电解液类型和温度等的选择。     

高度有序多孔阳极氧化铝制备工艺的研究

影响多孔阳极氧化铝(porous anodica lumina,PAA)形貌及结构等的因素有很多,如抛光铝片的表面粗糙度、电解液温度、氧化电压、氧化时间、搅拌速率等。本文采用二次阳极氧化法,以草酸为电解液,研究了高度有序AAO模板制备过程的主要工艺条件,并采用扫描电子显微镜对模板的形貌进行表征。结果表明,在电解液温度为12℃,氧化电压为40V能够得到高度有序的、孔径为80nm左右的多孔阳极氧化铝膜。     

纳米孔阵列结构阳极氧化铝模板的应用研究现状

对铝基材实施阳极氧化处理,可在其表面形成氧化铝多孔膜。当氧化铝多孔膜的纳米孔排列成规则的阵列结构时,氧化铝多孔膜将具有许多其它纳米材料无法比拟的优势。综述了以具有规则纳米孔阵列结构的阳极氧化铝薄膜作为模板,通过复制、沉积、吸附等技术,制备具有各种特殊用途纳米材料的制备工艺,使用这些方法制备的纳米材料已经广泛地应用于催化、气体吸收、分离膜、微电子器件等。     

Controlling the oxidation of organic brightener during electroplating using an ion-exchange membrane

The effect of an ion-exchange membrane combined with a dimensionally stable anode on the oxidation rate of organic brightener and electroplating performance was investigated. The oxidation rate of the brightener was measured by analyzing the total organic carbon content in the plating solution. The oxidation rate increased rapidly as the current density increased when there was no ion-exchange membrane. However, when an ion-exchange membrane was present, the oxidation rate of the brightener was significantly reduced by Neosepta CMX and CMS cation-exchange membranes. The CMS monovalent selective cation-exchange membrane in particular was the most effective in reducing organic brightener oxidation, regardless of the current density. Through-hole printed circuit board electroplating was more precise with an ion-exchange membrane than with no membrane. These results confirmed that the electroplating performance was improved by the presence of an ion-exchange membrane on the anode, effectively inhibiting the oxidation of organic brightener.     

搅拌式有限氧补偿条件下乳状液中多不饱和脂肪酸氧化模型

The oxidation of polyunsaturated fatty acids （PUFA） in emulsion with stirring and limited oxygen compensation was studied. A mathematical model of diffusion-oxidation was developed considering the mass transfer resistance of a gas-liquid boundary, the resistance of the boundary layer from the emulsifier membrane, and the autocatalytic-type autoxidation reaction of PUFA. The dynamic mass transfer coefficient of the emulsifier membrane, k0, was introduced. The model was verified by comparing the predictions of the model with the experi- mental data. The results indicated that the model was in good agreement with the oxygen diffusion and linoleic acid oxidation in the emulsion, and showed good applicability in the prediction of the effect of the emulsifier type on the oxidation of PUFA in the emulsion. It indicated that the oxidation of PUFA in emulsions, with stirring and limited oxygen compensation from the atmosphere, was controlled mostly by mass transfer resistance from the emulsifier membrane.     

Electrochemical modification of the catalytic properties of composite membranes of substituted Bi4V2O11 (BIMEVOX) for propane oxidation in a catalytic dense membrane reactor

Dense BICOVOX membrane, bulk BICOVOX/Au cermet membrane and BICOVOX membrane with a BICOVOX/Au cermet on its surfaces are investigated in the partial oxidation of propane under open circuit voltage (OCV) and under electrical bias at 700 °C. The propane conversion remains in the range 10–12% whatever the conditions of polarisation. Mostly cracking products are observed. Hydrogen is the main product with a selectivity around 55–60%. At OCV, no product of oxidation is detected except water which can not be quantified. On the membrane with BICOVOX/Au cermet electrodes on surface, traces of CO are observed as well as a small increase of propylene content under anodic polarisation. This can be explained by partial oxidation and oxidative dehydrogenation of propane, respectively. An anodic polarisation leads to a decrease of hydrogen due to its oxidation into water. In contrast, an increase of the hydrogen content is observed under cathodic polarisation. The effects on the membrane are modest, but they show the possibility that such a system offers for modifying the catalytic properties of membrane materials in a CDMR.     

A model for carbon and Ru corrosion due to methanol depletion in DMFC

A model for carbon and Ru corrosion in a DMFC anode under strong methanol depletion is developed. The model is based on current conservation equation in the membrane. In the methanol-depleted domain, methanol oxidation reaction is substituted by the carbon oxidation (corrosion). This dramatically lowers the membrane potential and creates an environment for electrochemical oxidation of Ru. Calculations show that 50–100 mV loss in the cell potential manifests quite a significant (above 50%) methanol-depleted fraction of the cell active area.     

天然气部分氧化制合成气的研究进展

综述了天然气部分氧化制合成气的研究进展,包括天然气无催化部分氧化、固定床催化部分氧化、两段转化法、膜反应器新工艺、流化床反应工艺、氧化剂研究、微波辐射加热部分氧化、部分氧化的机理,以及部分氧化工艺的催化剂研究。     

Development and Application of Oxygen Permeable Membrane in Selective Oxidation of Light Alkanes

In this paper, oxygen permeable membrane used in membrane reactor for selective oxidation of alkanes will be discussed in detail. The recent developments for the membrane materials will be presented, and the strategy for the selection of the membrane materials will be outlined. The main applications of oxygen permeable membrane in selective oxidation of light alkanes will be summarized, which includes partial oxidation of methane (POM) to syngas and partial oxidation of heptane (POH) to produce H₂, oxidative coupling of methane (OCM) to C₂, oxidative dehydrogenation of ethane (ODE) to ethylene and oxidative dehydrogenation of propane (ODP) to propylene. Achievements for the membrane material developments and selective oxidation of light alkanes in membrane reactor in our group are highlighted.     

Electrocatalytic activities of metal electrodes in anodic oxidation of hydrazine in alkaline solution

The electrocatalytic activities of various metals and alloys in the anodic oxidation of hydrazine in alkaline solution have been studied by means of palladium membrane method in which the contact side of the membrane was electrodeposited with a thin layer of the electrocatalytic metals. The electrode materials studied can be divided into two groups. In the first group, platinum, rhodium, cobalt, cobalt—phosphor and cobalt—boron, anodic current of hydrogen oxidation on the diffusion side decreased remarkably with an increase of the electro-oxidation of hydrazine on the contact side. The anodic oxidation of hydrazine occurs through the preliminary stepwise dehydrogenation on this group metals.On the other hand, the amount of sorbed hydrogen in the palladium, gold, nickel and nickel—phosphor electrodes increased with an increase of the electro-oxidation of hydrazine on the contact side. Thus, the anodic oxidation of hydrazine on the latter group metals may proceed through the anodic formation of the intermediate radicals which readily decompose into hydrogen and the related compounds.     

Oxidative interactions of cholesterol in the milk fat globule membrane

The effects of oxidative interactions between cholesterol and milk fat globule membrane (MFGM) components,i.e., nonlipid fraction, total lipid, nonpolar lipid and polar lipid, on cholesterol oxidation were studied in the presence and absence of water. In the dry state, cholesterol natively present in MFGM appeared to be protected at 135°C. The nonpolar lipid and nonlipid fraction contributed to the protective effect of MFGM. Added cholesterol accelerated the oxidation of membrane lipid fractions. At 75°C, pure cholesterol and membrane lipid fractions did not show significant interaction. However, cholesterol and other lipids in MFGM were less stable than when these were heated separately. When cholesterol and membrane lipids were mixed in an aqueous medium at 75°C, each accelerated the oxidation of the other. The MFGM exhibited a high protective effect on cholesterol oxidation in an aqueous environment. The nonlipid fraction protected cholesterol against oxidation, whereas the lipid fraction was destructive. In the absence of water, the net balance between these two opposing factors was destructive. The presence of water reversed the balance in favor of protection. Based on a paper presented at the Symposium on Milk Lipids held at the AOCS Annual Meeting, Baltimore, MD, April 1990.     

Oxidation of vitamin E in red cell membranes by fatty acids,hydroperoxides and selected oxidants

Our laboratory previously reported that vitamin E (tocopherol) in human blood platelets was oxidizedin vitro by various oxidants. This paper shows that diamide, superoxide, hydroperoxides and polyunsaturated fatty acids induced oxidation of tocopherols in red cell membranes. In contrast to platelets, red cell membrane tocopherol was oxidized by hydrogen peroxide and tertiary butyl hydroperoxide. Alpha tocopherolquinone was one of the products of oxidation. Among the fatty acids, thecis polyunsaturated acids were the most potent oxidizing agents with monounsaturated andtrans compounds relatively ineffective. The oxidation is not a detergent effect of the fatty acids since neither the detergents Brij and Lubrol, when present in concentrations under 0.5 mM, nor sodium arachidate (1.25 mM), could oxidize the membrane tocopherol. When red cell membrane samples were incubated with 0.5 mM arachidonate, 47±11% (S.D.) of the tocopherol lost was converted to tocopherolquinone. Unlike arachidonate, oxidants such as diamide, hydrogen peroxide and tertiary butylhydroperoxide are unable to oxidize all of the membrane tocopherol and produce less tocopherolquinone from oxidation (10–15%) under the experimental conditions of this study. Linoleic acid hydroperoxide is a much more potent oxidant and produces less quinone than arachidonate. The mechanisms of tocopherol oxidations induced by the various compounds seem to be different since the yields of quinone during oxidation vary with the nature of the oxidant. Tocopherol is consumed by oxidation as it protects the membrane from oxidant damage induced by compounds such as unsaturated fatty acids and hydroperoxides.     

无外界氧补偿条件下乳状液中多不饱和脂肪酸氧化模型

建立了在无外界氧补偿条件下乳状液中多不饱和脂肪酸(PUFA)氧化的数学模型。该模型综合考虑了乳化剂形成的液膜边界层阻力、PUFA自催化氧化反应以及油水相比表面积等因素的影响。实验验证了该模型能较好地拟合无外界氧补偿条件下乳状液中氧的扩散和亚油酸的氧化过程,并模拟计算了乳化剂膜传质系数和油水相比表面积等因素对扩散-氧化的影响程度。结果表明,乳化剂膜传质系数和油水相比表面积是影响乳状液中PUFA的氧化的主要因素。