SiO_2纳米孔隔热材料制备与热导率计算

以SiO_2气凝胶纳米颗粒、石英纤维和遮光剂为原料,制备了SiO_2纳米孔隔热材料.采用扫描电镜和氮气吸脱附法表征了SiO_2纳米孔隔热材料微观结构,采用瞬态平面热源法测试了材料在25～800℃, 10～10~5 Pa范围内的热导率.建立了Si02纳米孔隔热材料热导率计算方法,计算了材料在不同温度和压力下的热导率,热导率计算值和实验值相符较好,表明所发展的计算方法适用于纳米孔隔热材料的热导率计算.此外,还获得了材料气相热导率与辐射热导率随温度的变化规律,对材料结构设计及性能优化具有很好的指导意义.     

纳米孔壁面作用对蛋白质过孔影响的粗粒化分子动力学模拟

基于粗粒化分子动力学方法模拟电驱动蛋白质过孔过程，研究纳米孔-水/纳米孔-蛋白质相互作用对电泳迁移率的影响；用操控式分子动力学模拟分析蛋白质在不同相互作用下过孔摩擦系数和摩擦阻力.研究发现：蛋白质黏附纳米孔壁面对其过孔特性影响并不明显，而纳米孔-水相互作用对蛋白质过孔电泳迁移率和摩擦系数影响较大.随纳米孔-水相互作用增强，纳米孔壁面与蛋白质附近水分子运动差异显现，蛋白质过孔摩擦阻力显著增大，过孔摩擦系数随之增大，进而影响蛋白质过孔电泳迁移率.所得结果可为纳米孔材料设计提供理论指导.     

MOFs富集多环芳烃的SERS快速检测研究

多环芳烃(PAHs)是一类广泛存在于各环境介质的具有致癌致畸作用的有机污染物,对其的有效富集及超微量检测对环境监控及人类健康具有重要意义。本研究利用多孔的金属有机骨架材料对PAHs进行预富集,然后借助金属纳米粒子产生的表面增强拉曼散射(SERS)效应进行快速检测,实验操作简便,灵敏度高。     

纳米介孔ZrO2及其表面修饰的发光性质

水热合成法制备的高度有序多孔ZrO2具有规则六角排列、均匀纳米孔洞(约1．8nm)，并且其蓝、(近)紫外光发射强度比纳米微晶材料高2个数量级。本文研究了纳米介孔ZrO2这种不同于常规体材料与纳米晶材料的特殊发光性质。通过化学方法对纳米介孔ZrO2进行表面修饰后，能进一步提高其光发射聋度约3倍。通过这些发光性质的研究，以期增进对ZrO2发光机理的认识。     

纳米孔对等离激元特性及SERS性能影响

纳米孔结构在比如生物传感器、增强光谱学等领域具有多种重要应用。然而,一方面,纳米孔的制备技术还很有限,尤其对于小于10nm的微孔;另一方面,纳米孔结构的电磁场增强特性研究较少,增强能力较低。在该组最近的工作中,通过化学合成方法,直接合成了具有尺寸可调的纳米孔结构,并对其等离激元特性进行了研究。通过对二维(2D)纳米粒子超晶格结构腐蚀及SERS性能原位探测,发现该结构腐蚀初期会形成一种"纳米孔-纳米间隙"耦合结构。该结构表现出一种杂化的等离子激元模式,并贡献附加的电磁场增强。该方法可以拓宽到其他材料的纳米孔结构制备,并开发基于纳米孔结构相关的多种应用。     

无机介孔固体制备及其在纳米科技中的应用

由于量子限域和介电限域效应，固体纳米结构具有显著异于体相的量子特性，无机介孔固体作为周期性纳米结构的载 近年来备受注目，。本文综述了无机介孔固体的制备、表征、及其在纳米微结构设计中的应用，对最近的进展包括其在光子学、光电子学领域的材料设计、功能和应用进行了系统的分析。     

稀土纳米发光材料研究进展

稀土纳米发光材料明显不同于体相发光材料的特性已经成为近年来的热点研究课题,为了更好地探索其特性,综述了稀土纳米发光材料的研究进展,特别是掺杂Eu³⁺和Tb³⁺离子的稀土纳米发光材料。首先,归纳总结了稀土纳米发光粒子不同于体相材料的光谱特性,如电荷迁移带的红移、发射峰谱线的宽化、猝灭浓度的升高、荧光寿命和量子效率的改变等等;其次,概述了一维稀土纳米发光材料的制备与光谱性质,介绍了二维稀土纳米发光薄膜的图案化和介孔模板组装;最后,对其未来的发展趋势进行了展望。     

介孔材料MCM-41的导热研究

文章根据二氧化硅介孔材料MCM-41纳米孔结构特点,首先建立和验证了纳米结构单元模型,然后使用平衡分子动力学方法模拟了孔壁热导率;接着耦合孔隙内气体导热,开展了一维传热分析,最终提炼出MCM-41的有效热导率表达式;并对壁厚、孔径和孔隙率对热导率的影响进行了分析.研究结果表明,MCM-41具有良好的绝热性能,其有效热导率随孔隙率增大近似呈线性减小,且表现出各向异性;导热性能沿孔道长度方向表现出准一维特性. 关键词： 有效热导率 介孔材料 MCM-41 平衡分子动力学     

封面照片说明

 有序排列的纳米多孔材料的组装合成和功能化研究是由复旦大学承担的。这项研究基于纳米和分子组装化学、模板导向化学、表面活性剂化学,研究和建立了微孔、介孔和多级有序分子筛材料的构筑方法,在材料形貌、孔结构和孔内活性位等几个层次上,创立了“酸碱对”和电荷匹配理论,实现了材料的定向合成与宏观控制,并将所合成的新材料用于催化、蛋白分离等领域。封面是Ia3d空间群双连续螺旋结构的图片,这项成果被Nature、ChemistryofMaterials选为封面报道。     

改性光刻胶制备纳米压印模版

制备纳米压印中的模版是压印技术的基本条件.目前很多压印模版是利用高硬度材料制作的，但是这些材料比较难以加工，从而限制了纳米压印技术的发展.提出一种利用光刻胶制备纳米压印模版的方法.利用聚焦离子束对光刻胶的改性作用，控制加工的条件，将柔性的光刻胶改性为硬度很高的材料，从而形成纳米压印模版.这种方法具有速度快、制备简单等特点，是一种新颖的加工方式，扩展了聚焦离子束的加工范围，可用于其他的纳米加工领域. 关键词： 纳米压印 光刻胶 聚焦离子束 纳米孔阵列     

基于密度泛函理论的多环芳烃硝基衍生物的生物毒性预测

采用密度泛函理论（DFT）中的B3LYP方法,在6-311++G（d,p）基组水平下对16种多环芳烃（PAHs）及6种多环芳烃硝基衍生物进行了拉曼光谱、极化率、偶极矩、热力学、结构优化及能量等40种参数进行计算。以13种PAHs对发光菌的－lgEC₅₀值做因变量,以另外3种多环芳烃数据作为验证,构建了基于量子化学参数的PAHs毒性定量结构-活性相关（QSAR）模型,预测PAHs硝基衍生物的毒性。经验证,所建立的QSAR模型的模拟系数为0.816,模型预测的PAHs硝基衍生物毒性排序与文献报道的PAHs硝基衍生物对鼠伤寒沙门氏菌的毒性排序一致,表明所建模型可用于PAHs及其硝基衍生物的生物毒性预测,从而为控制和预测PAHs及硝基衍生物毒性提供理论依据。     

Simultaneous imaging of Mie scattering,PAHs laser induced fluorescence and soot laser induced incandescence to a lab-scale turbulent jet pulverized coal flame

In this study, transient soot formation processes in a small-scale jet burner (CRIEPI burner) were investigated by simultaneous measurements of coal particles, polycyclic aromatic hydrocarbons (PAHs) and soot. Pairs of simultaneous measurements of “Mie scattering measurement for coal particles with laser induced fluorescence (LIF) for PAHs” and “LIF for PAHs with laser induced incandescence (LII) for soot” were performed to understand the transitive formation processes of soot formation in pulverized coal flame, whose signals were successfully separated. Findings in the present study are as follows. Coal particles, PAHs and soot were distributed in this order in radial direction from the central axis. Existing regions of coal particles, PAHs and soot were overlapped from the time averaged viewpoint while there were few overlapping areas of coal particles, PAHs and soot from the instantaneous viewpoint. This result indicates that a long time is required for the formation of soot from 2 to 3 rings PAHs through larger PAHs.     

基于3D荧光光谱分析和多维偏最小二乘的PAHs浓度优化检测

多环芳烃(PAHs)具有强致癌性,威胁人类身体健康。在复杂水质检测环境中,利用荧光光谱检测PAHs浓度时,由于测量光谱中存在瑞利散射影响,使得PAHs光谱信号包含明显的非平稳噪声,常用的多次采样求均值法容易使PAHs光谱存在明显的测量误差,导致PAHs检测精度下降。为此,提出了一种基于3D荧光光谱分析和多维偏最小二乘(N-PLS)的PAHs浓度优化检测方法,首先分析了菲、芴、苊与荧蒽4种PAHs溶液的光谱特性,通过拟合散射带数据点值消除光谱中的瑞利散射噪声,同时尽可能地保留原光谱信息。提取4种PAHs光谱的均值、方差和一维边际分布等特征参数,利用聚类分析方法对其光谱数据做样本分类,将相似光谱数据样本进行合并;然后根据校正集的光谱信号与不同PAHs浓度之间的关系,建立N-PLS模型,对各类PAHs的浓度进行预测分析,并且验证PAHs浓度与光谱数据荧光强度的关系;最后利用双线性分解对浓度残差进行修正,对含有各类PAHs的水溶液与实际水样进行浓度残差验证,分析了不同参数下PAHs的预测误差。实验结果表明,溶剂菲有2个明显的荧光峰值,激发与发射波长分别为285/245和315/345 nm;芴与荧蒽均存在6个明显的荧光特征峰值,分别为265/255,325/345,335/325,365/355,385/395和405/415 nm,且与其他PAHs的荧光峰值相距较远; 溶液苊在发射波长300~485 nm的范围内存在连续波峰,且对应激发波长在255~360 nm范围内;N-PLS方法对不同水质环境下的PAHs预测误差较小,其中菲与芴均方根误差均小于0.4 μg·L-1,相对误差小于6%,苊与荧蒽均方根误差均小于1.0 μg·L-1,相对误差均小于9%。对4种不同的PAHs在河流中的扩散趋势进行了仿真分析,确定出了其扩散程度,其中芴与菲扩散速率约为51 mg·L-1,苊与荧蒽扩散速率为21 mg·L-1,且扩散速率在一定范围内呈线性增长趋势,PAHs与其浓度之间符合朗伯比尔定律的线性关系; 通过不同迭代次数下N-PLS方法的均方根误差分析,得到了均方根误差精度最高时的迭代次数;对比了不同主因子数时N-PLS方法对PAHs预测的适应度与相关系数,结果表明当主因子数为3时,适应度可达96.5%,此时N-PLS预测模型效果最佳。相比其他检测方法,本文方法检测精度较高,回收率较好,具有较强的鲁棒性。     

表面增强拉曼光谱技术在多环芳烃检测中的应用

多环芳烃(polycyclic aromatic hydrocarbons,PAHs)是一类致癌性很强的环境污染物.由于PAHs分子不含有能与金属配位或键合的官能团,因此很难利用SERS技术对其进行直接检测.本文综述了近年来表面增强拉曼散射(surface-enhanced Raman scattering,SERS)...     

Structural and electronic properties of linear and angular polycyclic aromatic hydrocarbons

The structural and electronic properties of linear and angular polycyclic aromatic hydrocarbons (PAHs) have been studied by ab initio calculations. We show that the HOMO–LUMO gaps of linear and angular PAHs are inversely proportional to their width and length and angular PAHs always exhibit larger HOMO–LUMO gaps than their linear isomers, indicating the relative higher kinetic stability for angular PAHs. The frontier orbitals of HOMO and LUMO are localized at the zigzag edges in linear PAHs, while they are distributed uniformly over the molecules in angular PAHs. These results offer key insight for understanding the size and topology depending effects, which is of great use for experimental syntheses of PAHs with specific electronic properties.     

煤燃烧过程中铜对多环芳烃生成的影响

研究了两种燃烧方式煤燃烧过程中金属铜的添加对多环芳烃生成的影响。结果表明:随着铜煤质量比的增加,管式炉煤燃烧多环芳烃生成浓度是减少的;流化床煤燃烧多环芳烃生成浓度是增加的,但要小于管式炉条件下两个数量级。多环芳烃生成毒性分布类似于多环芳烃生成浓度分布。而单个多环芳烃生成有着较大区别,同燃烧方式、存在状态、铜的含量等有较大关系。在燃烧温度下,铜的添加主要对高环物质的催化作用较为明显。     

Lowest Π–Π* electronic transitions in linear and two-dimensional polycyclic aromatic hydrocarbons: enhanced electron density edge effect

Polycyclic aromatic hydrocarbons (PAHs) form an important class of molecules as they are ubiquitous, pollute air and cause severe health problems. Lowest vertical π–π* singlet–singlet or triplet–triplet excitation energies and corresponding oscillator strengths were studied for several linear and two-dimensional PAHs employing time-dependent density functional theory. Excited-state electron density, molecular electrostatic potential (MEP) and spin density distributions in the PAHs, along with ground-state chemical hardness, were also studied. It has been found that, generally, excitation energies and oscillator strengths decrease with increase in PAH size, and excitation energies and chemical hardness are strongly linearly correlated. Enhanced electron density edge effect, which was found to occur in the ground states of the molecules, continues to hold in their excited states also. A strong similarity between the ground and π–π* excited-state MEP maps suggests that σ electrons are the main contributors to the enhanced electron density at the edges. Due to their strong electronic absorption transitions in the visible and infrared regions, the PAHs can be used for harnessing solar energy efficiently.     

层流预混火焰PAHs形成的反应机理模型

本文着重讨论层流预混火焰中,碳黑的先驱多环芳烃(PAHs)形成的化学反应动力学机理。该机理包括101种组分、546个基元反应。通过与实验结果的比较表明,该模型能够较好地预报碳氢燃料预混火焰中PAHs的生成过程。计算结果还表明当量比和压力PAHs的生成与排放具有重要影响,且存在一个化学当量比,在此当量比下,PAHs的浓度达到极大值。     

Molecular Emission Spectrohetry ih a Low Pressure Electrical Discharge

A low pressure electrical discharge for excitation of polycyclic aromatic hydrocarbons, PAHs, without fragmentation is described. The discharge characteristics as well as the plasma background spectra are given. The application of the discharge for the excitation of molecular spectra of PAHs is described. Difficulties with correction of the analyte emission spectrum for the background emission spectrum of the gas (He) are mentioned. Analytical use of the discharge for detection of PAH3 introduced by gas chromatography is described and is shown to be of marginal analytical use because of the rather poor detection limits of about 1 μg.

Jurgensen and Winefordner¹ have reviewed both reduced pressure and atmospheric pressure nitrogen discharges for detection of atomic and molecular species. The same authors² have also described an active nitrogen-induced chemiluminescence system for detection of polycyclic aromatic hydrocarbons, PAHs, and achieved detection limits in the range of 0.01 - 2000 ng. The intriguing aspect of the active nitrogen—induced chemiluminescence approach² for detection of PAHs was that the discharge was gentle resulting in little fragmentation of the PAHs and in the appearance of emission spectra characteristic of the parent molecules. Because of the poor understanding of the mechanism of excitation of the large organic molecules and the minimal fragmentation and because of the lack of control of the direct discharge as opposed to the afterglow in the studies of Jurgensen and Winefordner², the present authors began a careful study of the physical and analytical characteristics of this discharge in the fall of 1984. The physical characteristics were reported by Yu and Winefordner³ and indicated that the previous workers², were using the direct discharge plasma as a result of llpoorlv grounding. In addition, the same workers³ showed that the active nitrogen afterglow was not capable of exciting PAHs. In this note, we report on the analytical capabilities of an improved active gas (nitrogen or helium) electrical discharge system for gaseous PAHs.     

不同环数芳香烃激光诱导荧光光谱研究

为了更好地区分测量小分子芳香烃,利用一台Nd∶YAG激光器提供能量为0.085 J·cm-2、波长为266 nm的入射光。针对苯、甲苯、萘、菲、蒽、芘和屈不同环数的芳香烃,使用激光诱导荧光法研究了单一芳香烃及不同芳香烃混合物的荧光光谱。结果表明,芳香烃的苯环数是荧光发射光谱的主要决定因素;相同苯环数不同结构的芳香烃对荧光光谱范围基本没有影响;由于266 nm波长的吸收效率差异,导致相同环数的芳香烃的荧光光强存在差异;而且吸收效率相近且浓度相同时,环数越大,荧光光强越强。随着芳香烃环数的增加,荧光光谱波段和峰值都出现从紫外波段向可见光波段红移的现象,同时吸收效率相近时,荧光光谱范围变宽;一环至四环芳香烃的较好的荧光光谱区分范围分别为275~320,320~375,375~425和425~556 nm。针对不同芳香烃混合物研究表明,由于辐射能量传递机制导致混合物中有3环或4环芳香烃存在时,紫外波段的光被损失,所以1环或2环芳香烃混入混合物后,混合物中的1环或2环荧光光谱不能被检测到,但荧光光谱强度增大;当混合物中只包含3环和4环芳香烃时,荧光发射光谱具有两种芳香烃的特点;当混合物中存在3环和4环芳香烃时,荧光发射光谱和各自的浓度相关,从而可以一定程度区分不同环数物质。