多孔硅的制备条件对其光致发光特性的影响

不同的实验条件下制备的多孔硅的光致发光(PL)特性是不同的,这是许多研究产生分歧的主要原因。对比分析了阳极氧化电流密度、阳极氧化时间、溶液浓度以及自然氧化时间对多孔硅光致发光光谱的影响。认为在一定的范围内,多孔硅的发光峰位会随电流密度的增大而蓝移,要获得较强的发光,需要选择合适的电流密度;随着腐蚀时间的延长,多孔硅的发光峰位也发生蓝移。当HF酸的浓度较小时,峰位随浓度的增大表现为向低能移动;而当HF酸的浓度较大时,峰位随浓度的增大则表现为移向高能。多孔硅在空气中自然氧化,其发光峰位发生蓝移,而发射强度随放置时间的延长而降低。并用量子限制模型和发光中心模型对实验结果进行解释。     

多孔硅/多孔氧化铝与PVK复合光致发光特性

用旋涂法实现了多孔硅、多孔氧化铝与聚乙烯咔唑(PVK)的复合,研究了多孔硅／PVK、多孔氧化铝／PVK复合体系的光致发光性能。PL谱的测试发现,多孔硅／PVK复合体系的PL谱同时具有多孔硅和PVK的发射峰。此外,在485nm的位置出现了一个新峰,讨论了这个峰的来源。而多孔氧化铝与PVK复合后,没有产生新的峰。但多孔氧化铝与PVK复合后,由于多孔氧化铝纳米孔的纳米限制效应使PVK的发光峰出现大幅度蓝移。从多孔硅与多孔氧化铝发光机制的不同出发,讨论了多孔硅、多孔氧化铝与PVK复合后产生不同结果的原因。     

多孔硅的光致发光机制

人们已经提出了许多解释多孔硅发光的理论模型,每个模型都可以针对某些实验现象做出合理的解释,而对其他的实验结果就可能无法解释甚至相悖,因此多孔硅的发光机制至今仍是需要进一步研究和解决的问题。通过改变阳极氧化的条件,制得了一系列样品,其光致发光谱主要有四个峰。随着制备条件的改变,各个峰位的变化不大,但峰值强度比的变化比较大。随着自然氧化时间的延长,各个峰位的变化很小,有红移也有蓝移,有的则基本不变;而峰值强度的减弱幅度较大,但对应于各个峰位幅度的减弱是均衡的。分析实验现象产生的原因,认为多孔硅的发光是多种发光机制共同作用的结果;多孔硅纳米量子线的一定尺寸分布,不仅使光致发光谱存在一定的带宽,而且也是产生多峰现象的原因之一;多孔硅的结构特征对其发光特性起着决定性的作用。     

纳米碳材料负载铂催化剂在环己烷脱氢反应中的催化性能研究

制备了纳米碳材料负载铂的催化剂,通过N₂吸附、TEM、XRD技术分别对载体的BET比表面积和催化剂结构、形貌和粒径大小进行了表征。考察了不同催化剂在环己烷脱氢反应中的催化性能以及温度对纳米碳颗粒负载铂催化剂活性的影响。结果表明,锚定在不同碳载体上的铂有较好的分散性,粒径较小,粒度分布范围较窄并且具有相同的晶型结构。孔状纳米碳颗粒负载铂催化剂的活性高于碳纳米管和高比表面的活性炭负载铂催化剂,并且在低温条件下已经显示了较高的活性,尤其是中空碳颗粒负载铂催化剂在环己烷脱氢反应中显示了好的活性和稳定性。     

Kinetic and Stoichiometric Parameters in the Production of Carotenoids by <Emphasis Type="Italic">Sporidiobolus salmonicolor</Emphasis> (CBS 2636) in Synthetic and Agroindustrial Media

With the objective of determining the kinetic behavior (growth, substrate, pH, and carotenoid production) and obtain the stoichiometric parameters of the fermentative process by Sporidiobolus salmonicolor in synthetic and agroindustrial media, fermentations were carried out in shaken flasks at 25°C, 180 rpm, and initial pH of 4.0 for 120 h in the dark, sampling every 6 h. The maximum concentrations of total carotenoids in synthetic (913 μg/L) and agroindustrial (502 μg/L) media were attained approximately 100 h after the start of the fermentative process. Carotenoid bioproduction is associated with cell growth and the ratio between carotenoid production and cell growth (Y _P/X) is 176 and 163 μg/g in the synthetic and agroindustrial media, respectively. The pH of the agroindustrial fermentation medium varied from 4.2 to 8.5 during the fermentation. The specific growth rate (μ _X) for S. salmonicolor in synthetic and agroindustrial media was 0.07 and 0.04 h⁻¹, respectively. The synthetic medium allowed for greater productivity, obtaining maximum cell productivity (P _x) of 0.08 g L⁻¹ h⁻¹ and maximum total carotenoid productivity (P _car) of 14.2 μg L⁻¹ h⁻¹. Knowledge of the kinetics of a fermentative process is of extreme importance when transposing a laboratory experiment to an industrial scale, as well as making a quantitative comparison between different culture conditions.     

Preparation and characterization of porous cordierite for potential use in cellular ceramics

Cordierite porous ceramics Z, X, and K were prepared using three mixtures of clay minerals: Z from kaolinite, talc, and aluminum hydroxide, X from kaolinite, talc, vermiculite, and aluminum hydroxide, and K from kaolinite, talc, and magnesium oxide. Ceramics were different in porosity, specific surface area, cordierite polymorphs, and secondary crystalline phases. Vermiculite influenced textural architecture of calcined cordierite ceramics X and predestinated crystallization of the high-temperature hexagonal α-cordierite with secondary minerals enstatite, spinel and corundum. Ceramics Z contained low-temperature orthorhombic β-cordierite, enstatite, and corundum, K was diphase of β-cordierite and forsterite. Total pore area (TPA) and specific surface area (SSA) of X, in spite of the higher porosity and the pore size distribution in the range of 300–1000 nm, were smaller in comparison with TPA and SSA of Z. Ceramics K retained high porosity, two maxima at 300–1000 nm and 50–200 nm in the pores size distribution, and the highest TPA and SSA compared to those observed in ceramics Z and X. Presented at the 8th Conference on Solid State Chemistry, 6-11 July 2008, Bratislava, Slovak Republic.     

Adsorption and separation of light alkane hydrocarbons by porous hexacyanocobaltates (III)

The adsorption and separation of light n‐alkane hydrocarbons (propane, butane, pentane, hexane and heptane) by zinc and cadmium hexacyanocobaltates (III) were studied from inverse gas chromatographic data. These two solids are representative of the porous frameworks found for transition metals hexacyanometallates. For cadmium, the porous framework is related to the presence of systematic vacancies for the building block, [Co(CN)₆], while for Zn it is a consequence of a tetrahedral coordination for the Zn atom. These linear light hydrocarbons (paraffins) are effectively separated by these two porous frameworks. The involved differential adsorption heats and the related separation coefficients were estimated from the recorded chromatographic data. No significant differences for the separation ability of light n‐alkane hydrocarbons by the evaluated materials were observed. Copyright © 2009 John Wiley & Sons, Ltd.     

水相Reformatsky反应研究进展

近30年来,在水介质中形成碳-碳键一直是有机合成的研究热点.本文综述了水相中Reformatsky反应的研究进展,并对反应机理和应用作了简要的阐述.     

General capillary pressure and relative permeability expressions for through-plane fluid transport in thin fibrous sheets

The rate of fluid transport in partially saturated porous media depends on the media's instantaneous (function of saturation) relative permeability, k_r(S), and capillary pressure, P_c(S). Obtaining functional relationships for relative permeability and capillary pressure is only possible via experimentation or expensive microscale simulations, and needs to be repeated for different media having different fiber diameters, thicknesses, or porosities. In this concern, we conducted series of 3-D microscale simulations to investigate the effect of the above parameters on the relative permeability and capillary pressure of fibrous porous sheets. The results of our parameter study are utilized to develop general expressions for k_r(S) and P_c(S). Our general expressions are based on the existing empirical correlations of two-phase flow in granular media, and can easily be included in macroscale fluid transport equations to predict the rate of fluid release from partially saturated fibrous sheets in a time and cost-effective manner.