纳米氧化锌颗粒的荧光光谱特性及测试条件的影响

分别用沉淀法和有机物单源的热分解方法从溶液中生长了不同尺寸的氧化锌纳米晶体,研究了纳米晶体的荧光特性及其对测量样品状态的依赖关系.尺寸比较大的ZnO纳米晶体在固态下其荧光光谱为宽阔的发光带,并在宽阔发光带上出现一系列明显的精细结构,而分散于有机溶剂中时其荧光由激子复合发射和通过氧空位的复合发射组成.分散于有机溶剂中的中等尺寸的表面包裹的纳米ZnO晶体的荧光由激子荧光、通过浅杂质的发射和通过本征缺陷复合的荧光组成,其强度随着测量浓度的升高而增强,并且激子的荧光发生红移;尺寸比较小的表面包裹的纳米晶体的荧光为激子复合和通过氧空位复合的荧光组成,激子荧光强度、通过氧空位的发光强度及其相对强度随着纳米晶体浓度的变化而变化,测量浓度的升高,激子发光峰没有位移,但与缺陷态相关的激发光荧光发生红移.     

Two types of luminescence blinking revealed by spectroelectrochemistry of single quantum dots

Photoluminescence blinking--random switching between states of high (ON) and low (OFF) emissivities--is a universal property of molecular emitters found in dyes, polymers, biological molecules and artificial nanostructures such as nanocrystal quantum dots, carbon nanotubes and nanowires. For the past 15 years, colloidal nanocrystals have been used as a model system to study this phenomenon. The occurrence of OFF periods in nanocrystal emission has been commonly attributed to the presence of an additional charge, which leads to photoluminescence quenching by non-radiative recombination (the Auger mechanism). However, this 'charging' model was recently challenged in several reports. Here we report time-resolved photoluminescence studies of individual nanocrystal quantum dots performed while electrochemically controlling the degree of their charging, with the goal of clarifying the role of charging in blinking. We find that two distinct types of blinking are possible: conventional (A-type) blinking due to charging and discharging of the nanocrystal core, in which lower photoluminescence intensities correlate with shorter photoluminescence lifetimes; and a second sort (B-type), in which large changes in the emission intensity are not accompanied by significant changes in emission dynamics. We attribute B-type blinking to charge fluctuations in the electron-accepting surface sites. When unoccupied, these sites intercept 'hot' electrons before they relax into emitting core states. Both blinking mechanisms can be electrochemically controlled and completely suppressed by application of an appropriate potential.     

Doping semiconductor nanocrystals

Doping--the intentional introduction of impurities into a material--is fundamental to controlling the properties of bulk semiconductors. This has stimulated similar efforts to dope semiconductor nanocrystals. Despite some successes, many of these efforts have failed, for reasons that remain unclear. For example, Mn can be incorporated into nanocrystals of CdS and ZnSe (refs 7-9), but not into CdSe (ref. 12)--despite comparable bulk solubilities of near 50 per cent. These difficulties, which have hindered development of new nanocrystalline materials, are often attributed to 'self-purification', an allegedly intrinsic mechanism whereby impurities are expelled. Here we show instead that the underlying mechanism that controls doping is the initial adsorption of impurities on the nanocrystal surface during growth. We find that adsorption--and therefore doping efficiency--is determined by three main factors: surface morphology, nanocrystal shape, and surfactants in the growth solution. Calculated Mn adsorption energies and equilibrium shapes for several nanocrystals lead to specific doping predictions. These are confirmed by measuring how the Mn concentration in ZnSe varies with nanocrystal size and shape. Finally, we use our predictions to incorporate Mn into previously undopable CdSe nanocrystals. This success establishes that earlier difficulties with doping are not intrinsic, and suggests that a variety of doped nanocrystals--for applications from solar cells to spintronics--can be anticipated.     

对流干燥时水分蒸发扩散过程的热力学条件

从非平衡热力学理论和相平衡原理出发,对多也南对流干燥过程中水分蒸发,扩散过程的物理机制进行了分析,结果表明：干燥操作的热力学条件是干燥介质处于未饱和状态,干燥时驱动水分蒸发、扩散过程听驱动势是广义热力学,且物料温度愈低,干燥介质温度愈高,相对湿度愈小,则驱动势愈大。     

耗散粒子动力学中固壁模型对纳米颗粒吸附模拟的影响

耗散粒子动力学(dissipative particle dynamics, DPD)方法是模拟介观流动的有力工具. 模拟中常用的FCC (face centered cubic) 固壁模型会在壁面附近产生虚假的流体密度波动. 作为纳米颗粒吸附问题的关键区域, 这个现象不可忽略. 采用随机壁面模型模拟纳米颗粒吸附问题, 并就壁面附近液体密度分布和纳米颗粒吸附的模拟与传统的FCC 壁面模型进行了比较.     

CuInS2／石墨烯混合物的合成及其在太阳能电池中的应用

在不同的溶剂中通过温和的溶剂热法,成功地合成 CuInS2纳米晶体。这些合成好的 CuInS2粉末被 X光衍射表征后,又作为对电极被组装成染料敏化太阳能电池。通过检测可以发现乙二醇是合成 CuInS2过程中最佳的溶液。这主要表现在用乙二醇合成的 CuInS2作为电池对电极时的转化率可以达到5·49％,这个值要比用其他溶液合成的 CuInS2转化率高。然后,将在乙二醇溶剂中合成的 CuInS2粉末与石墨烯的氧化物混合形成 CuInS2纳米晶体／石墨烯纳米复合材料,这种材料可以提高 CuInS2在染料敏化太阳能电池方面的性能。通过透射电子显微镜法,可以证明 CuInS2生长在石墨烯纳米网中。与传统的铂对电极电池（6·90％）相比,这种纳米复合材料具有相对较好的光电转化率（6·28％）。     

Prediction of Solid-Liquid Equilibrium for KCl in Mixed Water-Ethanol Solutions Using the LIQUAC Model

Introduction The solubilities of nearly insoluble salts in water can be calculated directly using their solubility product constants, since at low ion concentrations the required activity coefficients are very close to unity. At higher concentrations, the mean activity coefficients of the ions have to be taken into account. In 1994, Li et al.[1,2] developed the LIQUAC model for systems with strong electrolytes based on results from statistical thermodynamics taking into account the interact…     

HFC-227ea热力学物性的分子动力学模拟

利用分子动力学模拟算法研究了七氟丙烷 (HF C-2 2 7ea)的热力学物性。通过将 HFC-2 2 7ea作为极性的两质点 L ennard-Jones流体处理建立了相应的势能模型。利用等温等压系综 +测试粒子 (NPT+ Test Particle)算法对 HF C-2 2 7ea的气液相平衡性质、过冷液和过热蒸气性质进行了模拟。模拟结果与美国国家标准研究所 (NIST)的数据库的最大相对偏差分别在 1.3 % (单相区 )和 1.6% (气液平衡区 )以内 ,表明该模拟方法已可用于物性的预测和工程实际     

反应物粒度对化学反应平衡常数的影响

在纳米颗粒化学反应热力学理论模型的基础上,以纳米氧化铜与硫酸氢钠溶液的反应体系为例,研究了纳米氧化铜颗粒的粒度对其化学反应平衡常数的影响规律。研究结果表明:在纳米氧化铜作为反应物的高分散多相反应体系中,平衡常数不仅是温度的函数,而且还与反应物(或产物)分散相的粒度有关;以纳米氧化铜颗粒为反应物,其粒度对化学反应平衡常数有很大影响,即随着反应物颗粒的粒度减小,化学反应的平衡常数增大;实验结果与理论分析的规律一致。     

柔性预应力索杆钢结构张拉过程跟踪计算方法

柔性的预应力索杆钢结构在张拉过程中，构件同时发生刚体运动和弹性变形，这一问题不能用传统的有限元方法来求解．基于柔性多体系统动力学，建立了一种索杆单元的动力学模型，同时考虑了构件的刚体运动与弹性变形，推导了相应的运动学方程、几何约束方程和动力学控制方程．该方法可以对张拉全过程进行跟踪，找到结构的运动稳定路径和最终的静平衡构形，计算出构件内力的连续变化过程．数值算例表明该方法实用有效，计算精度高．     

CeO2纳米燃油单液滴蒸发数值模拟研究

基于单液滴蒸发可视化试验,应用ANSYS FLUENT计算流体力学模拟软件,建立纳米燃油单液滴蒸发模型,探究纳米粒子质量浓度和粒径对燃油液滴蒸发过程中温度和燃油蒸气质量浓度的影响. 结果表明,纳米燃油液滴中的纳米粒子质量浓度越高、粒径越小,燃油液滴的蒸发平衡温度越高,相同时间内的燃油蒸气气相体积分数越高. 在环境温度573 K下,纳米燃油液滴从外界环境吸收热量使自身温度不断升高,在计算域内沿液滴表面向外延伸形成质量浓度边界层和温度边界层,促进液相向气相的转化.在蒸发初始阶段,蒸发速率较低,燃油蒸气气相体积分数较小;随着蒸发过程持续进行,由于纳米粒子增强传热传质的作用,液相组分蒸发汽化加快,液滴蒸发速率加快.     

ZnSe/5B2O3-95SiO2纳米复合材料的制备及性能表征

采用溶胶凝胶工艺在室温合成合有Zn、Se成分和玻璃相成分的均匀透明凝胶，并通过CO还原气氛热处理，在凝胶玻璃中原位生长出ZnSe纳米晶体．利用BET比表面积、透射电镜、吸收光谱、荧光光谱等分析手段对ZnSe纳米复合材料的组成结构及量子尺寸效应影响下的光学性能进行了表征，结果表明：5B2O3—95SiO2凝胶玻璃的多孔结构可有效地分散ZnSe纳米晶粒；纳米复合材料中ZnSe纳米晶粒呈球形，粒径约为3．5nm；吸收光谱中，ZnSe纳米复合材料的吸收边相对于ZnSe体材料发生蓝移，随着ZnSe在凝胶玻璃中摩尔分数的增大，蓝移量减小，相应ZnSe纳米晶粒尺寸增大；在荧光光谱中，500nm附近的发光带是凝胶玻璃中的ZnSe纳米晶体表面态复合和缺陷发光，当ZnSe的摩尔分数达到0．07时，观测到了浓度的荧光淬灭现象．     

Prediction of Solid-Liquid Equilibrium for KCI in Mixed Water-Ethanol Solutions Using the LIQUAC Model

The LIQUAC model is often used to predict vapor-liquid equilibria, osmotic coefficients, and mean ion activity coefficients for electrolyte systems. This paper describes a thermodynamic method to analyze solid-liquid equilibrium for electrolytes in mixed solvents solutions using the LIQUAC model. The KCI solubilities in mixed water-ethanol solutions are predicted with the LIQUAC model and its original interaction parameters. This method is also used to obtain new K^＋-ethanol interaction parameters in the LIQUAC model from the solubility data. The new interaction parameters accurately predict the vapor-liquid equilibrium data of K^＋ salts （including KCI, KBr, and KCOOCH3） in mixed water-ethanol solutions. The results illustrate the flexibility of the LIQUAC model which can predict not only vapor-liquid equilibrium but also solid-liquid equilibrium in mixed solvent systems.     

不同溶剂中制备单分散量子点

选用比较缓和反应条件,用无毒、价廉、稳定性好的无机化合物作为反应前驱体制备半导体量子点材料．通过选择不同的反应溶剂,可以得到粒径大小不同从而发光波长可“调谐”的一系列CdSe量子点材料．用紫外吸收光谱（UV—Vis）,荧光发射光谱（PL）跟踪了反应的过程,用X射线衍射（XRD）和透射电镜（TEM）对得到的量子点材料的结构进行了表征．对量子点材料在有机溶剂和水溶液中的转相进行了研究,为量子点与生物分子的连接,进而在生物标记方面的应用提供材料基础．该方法是对传统高温条件下有机金属化合物前驱体分解制备方法的补充,是一种环境友好的半导体量子点材料的制备方法．     

Water conduction through the hydrophobic channel of a carbon nanotube.

Confinement of matter on the nanometre scale can induce phase transitions not seen in bulk systems. In the case of water, so-called drying transitions occur on this scale as a result of strong hydrogen-bonding between water molecules, which can cause the liquid to recede from nonpolar surfaces to form a vapour layer separating the bulk phase from the surface. Here we report molecular dynamics simulations showing spontaneous and continuous filling of a nonpolar carbon nanotube with a one-dimensionally ordered chain of water molecules. Although the molecules forming the chain are in chemical and thermal equilibrium with the surrounding bath, we observe pulse-like transmission of water through the nanotube. These transmission bursts result from the tight hydrogen-bonding network inside the tube, which ensures that density fluctuations in the surrounding bath lead to concerted and rapid motion along the tube axis. We also find that a minute reduction in the attraction between the tube wall and water dramatically affects pore hydration, leading to sharp, two-state transitions between empty and filled states on a nanosecond timescale. These observations suggest that carbon nanotubes, with their rigid nonpolar structures, might be exploited as unique molecular channels for water and protons, with the channel occupancy and conductivity tunable by changes in the local channel polarity and solvent conditions.     

室温常压溶液法合成烯丙基功能化的正六边形硅纳米晶体

室温常压下,以氢化铝锂为还原剂在溶液中还原烯丙基三氯硅烷和四氯化硅体系,制备了烯丙基功能基团修饰的正六边形硅单晶.采用透射电子显微镜（Transmission Electron Microscopy,TEM）和傅里叶变换红外光谱（Fourier Transform Infrared,FTIR）对产物进行表征.研究了硅晶体的尺寸分布、晶面取向及表面组成,推测了可能的反应机理.结果表明,三氯硅烷与四氯化硅浓度比为1：3时经过还原可生成尺寸为20~50nm,表面有烯丙基基团的（111）晶向的单晶硅.     

纳米ZnO的制备及其光催化活性研究

采用直接沉淀法、微乳法及乙醇锌合成法制备了不同晶粒尺寸的ZnO纳米粒子,用XRD和TEM技术对样品进行表征.取粒径最小的纳米ZnO作光催化剂,以太阳光为光源,并以光催化降解罗丹明-B为模型反应,探讨用纳米ZnO光催化降解有机污染物的途径.     

均相单一化学反应的不可逆过程热力学

根据质量守恒方程,基于不可逆过程热力学中通量和力之间的关系,将不可逆过程热力学线性理论推广应用于既远离平衡又没有产生耗散结构的均相存在单一化学反应的体系,建立了远离平衡的化学反应动力学方程及其对于理想气体体系的表达式,沟通了热力学和动力学之间的联系·将动力学方程应用于水煤气反应,得到了和实测数据吻合的五次关系式·结果说明考虑了高次项后,可将不可逆过程热力学应用于远离平衡体系,并为化学动力学的研究提供了一种新的手段·     

QSL炼铅过程的计算机模型

借助于多相、多成分系统中平衡计算的计算机辅助手段，提出了ＱＳＬ炼铅过程的计算机模型．利用该模型，可快速地、有效地、经济地分析了ＱＳＬ炼铅法在工业上得不到弃渣而失败的根本原因，同时，利用该模型对直接炼铅的操作条件进行鉴定和优化，为开发炼铅新方法和最佳冶炼操作条件提供决策依据     

基于BaLuF5 颐Yb3+ ,Er3+ 纳米晶掺杂的聚合物光波导放大器

为提高聚合物光波导放大器的增益性能, 利用高温法合成了BaLuF5 颐Yb3+ ,Er3+纳米晶, 并分别对纳米晶的形貌、晶体结构和近红外发射特性进行了表征。测试结果表明, 纳米晶平均粒径为13 nm, 并在1 530 nm 处具有较强的发射, 荧光半高宽为50 nm。将合成的纳米晶掺杂入SU-8 聚合物作为光波导放大器的芯层材料, 使
用光刻显影等工艺, 在表面长有二氧化硅的硅衬底上制备出了聚合物光波导放大器。当980 nm 波长泵浦光功率为280 mW、信号光波长为1 530 nm 且功率为0. 1 mW 时, 在长度为1. 1 cm 的光波导放大器中, 获得了3. 95 dB的相对增益。