电场诱导氧化石墨烯的极化动力学特性研究

本文通过外加电场改变氧化石墨烯团簇分子的共振能量,利用激光激发氧化石墨烯产生的共振荧光特性测量氧化石墨烯在电场作用下的极化动力学特性. 发现存在外加电场使得荧光共振峰的半高全宽趋于饱和的时间特性,而不同的氧化石墨烯团簇分子的荧光共振峰的暂态特性同时反映了电场对氧化石墨烯产生定向极化和变形极化的动力学特性. 关键词： 氧化石墨烯 团簇分子 电场 极化动力学     

金属颗粒-半导体膜Cu:CdS的制备及结构研究

利用磁控溅射产生金属Cu团簇，同时蒸发半导体介质CdS，将Cu团簇包埋在CdS介质中，制备出金属颗粒 半导体膜．团簇大小可通过改变溅射气压控制．用TEM研究了嵌埋团簇的结构．分析表明：CdS很好地包埋了Cu团簇，都呈多晶结构；团簇尺寸在5—20nm，Cu晶格发生了膨胀，膨胀量在7%左右 关键词：     

基于极紫外自由电子激光的中性团簇红外光谱

团簇在能源催化和大气雾霾等诸多化学过程中广泛存在,团簇表征与性能研究对诠释化学反应机理至关重要. 然而,中性团簇由于缺乏电荷、难于探测,实验研究非常困难. 鉴于上述情况,发展了基于极紫外自由电子激光的中性团簇红外光谱实验方法,用于质量选择中性团簇的高灵敏探测、结构表征和性能研究. 红外-极紫外衰减和红外+极紫外增强光谱实验方法已被应用于一些中性水团簇和一些中性金属羰基化合物的研究. 由于极紫外自由电子激光的波长范围涵盖了绝大多数中性团簇的第一电离势,这一独特的实验方法为开展各类中性团簇红外谱学和结构的研究打开了大门. 本文综述了这些红外光谱实验方法及其在中性团簇研究中的应用.     

基于极紫外自由电子激光的中性团簇红外光谱（英文）

团簇在能源催化和大气雾霾等诸多化学过程中广泛存在,团簇表征与性能研究对诠释化学反应机理至关重要.然而,中性团簇由于缺乏电荷、难于探测,实验研究非常困难.鉴于上述情况,发展了基于极紫外自由电子激光的中性团簇红外光谱实验方法,用于质量选择中性团簇的高灵敏探测、结构表征和性能研究.红外-极紫外衰减和红外+极紫外增强光谱实验方法已被应用于一些中性水团簇和一些中性金属羰基化合物的研究.由于极紫外自由电子激光的波长范围涵盖了绝大多数中性团簇的第一电离势,这一独特的实验方法为开展各类中性团簇红外谱学和结构的研究打开了大门.本文综述了这些红外光谱实验方法及其在中性团簇研究中的应用.     

Au_7团簇吸附O_2和CO及其对CO的催化反应机理研究

本文采用密度泛函理论,研究了Au_7团簇催化CO的氧化反应机理.研究发现,二维平面结构的Au_7团簇更容易吸附CO和O_2分子. Au_7团簇吸附一个O_2分子的吸附能为0.64 eV,但在吸附多个O_2分子时,平均吸附能有了明显的下降,表明Au_7团簇进行多吸附O_2分子的可能性不大. Au_7团簇吸附一个CO分子的吸附能为1.26 eV,且在吸附多个CO分子时,平均吸附能虽有减少,但减小的幅度不大,说明Au_7团簇有可能吸附多个CO分子.此外,在Au_7团簇催化CO的氧化反应过程中,整个反应克服的最高势垒仅为0.34 eV,说明Au_7团簇有望成为良好的CO氧化催化剂.     

小尺寸铜团簇冷却与并合过程中结构变化的原子尺度研究

研究Cu_N（N=57,58,59）熔融铜团簇在冷却过程以及300 K时两个具有二十面体结构Cu₅₅团簇在并合过程中的结构变化.对这些小尺寸团簇的结构变化采用基于嵌入原子方法的正则系综分子动力学进行计算机模拟.通过对模拟结果的分析表明,小团簇的冷却和并合过程存在阶段变化的特点.降温过程中Cu_N（N=57,58,59）团簇的原子运动及其微观结构变化表现出较大差异,由此导致这三类团簇内原子排布的不同,其中Cu₅₉团簇结构的有序程度最低.在两个Cu₅₅团簇并合早期阶段,这两个团簇相接触后发生变形导致原子位置出现较大改变,在随后的并合过程中,原子扩散引起原子局部位置调整导致所并合体系的结构发生变化.远离两个团簇接触区的原子仍保持其并合前的结构. 关键词： 团簇 分子动力学 计算机模拟 表面     

卤化钠对丙二酸气溶胶颗粒水溶特性影响机理研究

大气中水蒸气会影响气溶胶颗粒的生长演化动力学特性,从而改变其环境效应。当前,对包含有机组分气溶胶颗粒与水相互作用机理的认识还很局限.本文建立了纯有机气溶胶和有机-无机混合气溶胶颗粒水溶特性研究分子动力学模型,分别模拟了不同温度条件下不同卤化钠盐(NaI/NaCl/NaF)对丙二酸(C_3H_4O_4)团簇水溶特性的影响情况。重点分析了各影响因素作用下团簇结构和气粒界面特性。结果表明,温度升高,C_3H_4O_4-H_2O团簇相继出现分层结构和混合结构,加入40个卤化钠分子后,水分子对初始团簇溶解程度的排序为40 NaF40 NaCl0 NaX40 NaI,且差异随着温度的升高而变大。高温(T=300 K)时,各种团簇的表面均包含C_3H_4O_4分子和H_2O分子,且C_3H_4O_4分子的疏水基朝向气相一侧.     

不同堆积方式下碳黑颗粒氧化特性的实验研究

本文将自由堆积和DPF中错流沉积碳黑颗粒的氧化再生进行对比，从气体排放、颗粒物排放、氧化再生效率以及能量利用率进行分析，探索DPF再生时气体和颗粒排放规律和特性。实验结果表明：自由堆积碳黑颗粒受热升温快，生成的CO/CO₂气体很快达到峰值，但氧扩散受限，气体达到峰值后缓慢下降。DPF载体传热缓慢，错流沉积碳黑颗粒氧化产生气体的出峰时间延后，但来流充分与颗粒接触，生成气体峰值大，再生迅速且效率高，排出的颗粒物数量浓度升高，且存在大粒径颗粒物释放现象。提高温度，两种堆积方式的氧化再生效率增加，实时效能比先升高后下降，存在最佳的加热时间。本文研究结果将为探索DPF再生时出口颗粒排放特性，颗粒物来源分析奠定理论基础和实验参考。     

磁控溅射法制备金团簇纳米颗粒及性能表征

 采用磁控溅射法制备金团簇纳米颗粒，用透射电镜(TEM)、X射线衍射(XRD)、紫外可见光分光光度计(UV-Vis)和X射线光电子能谱(XPS)等分析手段对其表征，研究了金团簇纳米颗粒的形貌、颗粒度、结构、光吸收性质及物质成份。研究结果表明：制备的金团簇纳米颗粒呈球形，平均粒径在10 nm左右，粒径分布均匀，无团聚、氧化现象，颗粒的结构为面心立方。在519 nm处出现团簇颗粒的表面等离子共振吸收峰，测试得到Au(4f_7/2)和Au(4f_5/2)电子的结合能分别为83.3 eV和86.9 eV，并且没有出现金的氧化产物。     

氧化硅层中的锗纳米晶体团簇量子点

采用氧化和析出的方法在氧化硅中凝聚生成锗纳米晶体量子点结构. 其形成的锗晶体团簇没有突出的棱角和支晶结构，锗晶体团簇的轮廓较圆混，故可以用球形量子点模型来模拟实际的锗晶体团簇. 对比了在长时间退火氧化条件下和在短时间退火用激光照射氧化条件下所生成的锗纳米晶体结构的PL光谱和对应的锗纳米晶体团簇的尺寸分布. 短时间退火氧化条件下生成的锗纳米晶体较小(3.28—3.96nm)，长时间退火用激光照射氧化条件下所生成的锗纳米晶体较大(3.72—4.98nm)；其分布结构显示某些尺寸的锗纳米晶体团簇较稳定，适当的氧化条件可以得到尺寸分布范围较窄的锗纳米晶体团簇. 用量子点受限模型计算了锗纳米晶体团簇的能隙结构，用Monte Carlo方法模拟了PL光谱和对应的锗纳米晶体团簇的尺寸分布，分别与实验结果符合较好. 关键词： 锗晶体团簇 纳米晶体 量子点 激光照射     

基于光谱诊断的烃类火焰碳烟形成机理研究综述

碳烟主要是烃类燃料不完全燃烧生成的产物,其对人类健康、空气质量以及燃烧装置的使用寿命都会产生有害影响。碳烟生成是一个复杂的物理化学过程,控制碳烟排放,需要克服碳烟生成和燃烧过程中物理和化学演化的巨大差异,这些差异表现为对碳烟纳观结构和表面官能团随碳烟氧化活性反应变化的深入探索研究。近些年,研究人员对碳烟的生成机理开展了系列研究,对碳烟生成各个物理化学反应阶段有了一定认识。结合光谱诊断技术可深入了解燃烧系统碳烟形成过程,确定碳烟颗粒分子组成、精细结构、浓度分布等特征,也可从碳烟结构变化、黑体辐射强度等方面详细了解碳烟形成过程。该文旨在阐述光谱诊断技术对烃类火焰碳烟表征的研究进展和发展趋势,探讨LIBS, LII和LIF等作为诊断工具在包含背景辐射的火焰中检测碳烟生成过程产生辐射强度准确性等问题。主要介绍了烃类火焰碳烟的形成机理(从前驱体产生、生长到颗粒生成、凝聚,最后进行颗粒氧化)。总结了探测碳烟性质光谱诊断方法的应用以及光谱诊断技术对燃烧过程中碳烟表征的研究现状,包括对碳烟体积分数、温度和基于图像处理的碳烟结构表征,反应碳烟前驱体(多环芳烃)、反应气氛、温度等对碳烟颗粒物生成的影响。最...     

Influence of complex component and particle polydispersity on radiative properties of soot aggregate in atmosphere

The effects of morphological structure, water coating, dust mixing and primary particle size distribution on the radiative properties of soot fractal aggregates in atmosphere are investigated using T-matrix method. These fractal aggregates are numerically generated using a combination of the particle-cluster and cluster-cluster aggregation algorithms with fractal parameters representing soot aggregate in atmosphere. The radiative properties of compact aggregate notably deviate from that of the branched one, and the effect of morphology changes on the radiative properties in wet air cannot be neglected. However it is reasonable to use realization-averaged radiative properties to represent that of the aggregates with certain morphology. In wet air, the scattering, absorption and extinction cross-section and symmetry parameter of soot aggregates coated with water notably increase with water shell thickness. The mixing structures of dust have little effect on radiative properties of aggregates, but the volume fraction of dust has an obvious effect on extinction, scattering and absorption cross-section of aggregates when the size parameters are above the Rayleigh limit. Although the primary particle size distribution of soot aggregate has mild effect on the scattering albedo and asymmetry parameter, the deviations of the extinction, scattering, absorption cross-section among the three size distributions are significant in this study. The size distribution has a significant effect on forward scattering of phase function, while the effect can be neglected as the size parameter approaches to the Rayleigh limit.     

随机分布烟尘簇团粒子缪勒矩阵的数值计算

利用蒙特卡罗方法根据团簇-团簇凝聚（CCA）模型对由球形原始粒子凝聚而成的烟尘簇团粒子进行了模拟,用离散偶极子近似（DDA）方法对随机分布的烟尘簇团粒子的缪勒矩阵元素进行了数值计算,给出了不同入射波长情况下随机分布烟尘簇团粒子的缪勒矩阵元素与组成簇团粒子的基本粒子的粒径和数目的数值关系,为进一步研究随机分布簇团粒子的形成机理、形态特性、散射特性提供了一种理论方法. 关键词： 烟尘簇团粒子 缪勒矩阵 离散偶极子近似方法     

Arc discharge sputtering of schungites

The schungite structure is shown to be modified in an arc discharge in an inert gas atmosphere. As a result of the direct effect of the arc discharge, some portion of the schungite material transforms locally into rhombohedral graphite. The spectral dependence of the optical transmission of the solutions of graphite soot and schungite soot in toluene is measured. X-ray diffraction patterns of the schungite soot and graphite soot contain a broad maximum at small scattering angles, which indicates the presence of fullerene molecules.     

Influence of the cumulative effects of multiple laser pulses on laser-induced incandescence signals from soot

The effect of multiple laser pulses reaching soot particles before an actual laser-induced incandescence (LII) measurement is investigated in order to gain some insights on soot morphological and fine structure changes due to rapid laser heating. Soot, extracted from a premixed and a quenched diffusion flames, is flowing through a tubular cell and undergoes a variable number of pulses at different fluence. The response of soot is studied by the two-color LII technique. Transmission electron microscopy (TEM) analysis of laser-modified soot aggregates from the diffusion flame is also presented. The results indicate that even at low laser fluences a permanent soot transformation is induced causing an increase in the absorption function E(m). This is interpreted as an induced graphitization of soot particles by the laser pulse heating. At high fluences the vaporization process and a profound restructuring of soot particles affect the morphology of the aggregates. Soot from diffusion and premixed flames behaves in a similar way although this similarity occurs at different fluence levels indicating a different initial fine structure of soot particles.     

Numerical simulation aided relative optical density analysis of TEM images for soot morphology determination

The relative optical density (ROD) method provides a means to measure three-dimensional information about soot aggregates from two-dimensional transmission electron microscopy (TEM) micrographs of soot. The method is dependent on accurate calibration of the relationship between the measured soot ROD in TEM images and the actual soot thickness perpendicular to the imaging plane. A novel calibration method based on the comparison between probability distributions of measured soot ROD in TEM images and that of virtual soot thickness of numerically simulated soot is introduced. Soot aggregates of various prescribed fractal structure parameters were numerically generated using a tunable cluster-cluster aggregation model. The probability histograms of the local soot thickness for the simulated soot aggregates and ROD of the TEM images of flame generated soot aggregates were found to be quite similar and were used as a basis to establish a quantitative relationship between ROD and the local soot thickness. The calibration constant obtained from the analysis of the simulated soot was found to be insensitive to the fractal structure parameters over a wide range. The calibrated ROD method is successfully applied to the morphology analysis of soot aggregates generated in an atmospheric laminar co-flow ethylene-air diffusion flame based on thermophoretic sampling (TS) and TEM analysis techniques. With the ROD method, an overlap coefficient is introduced to identify and eliminate non-soot-aggregate structures and the selection of a cut-off overlap coefficient was found to have little influence on the final results over a relatively wide range. ROD is independent of empirical constants and human judgments and has been found to be an accurate and reliable TEM image analysis method for studying the morphology of soot aggregates.     

Measurement of Inherent Material Density of Nanoparticle Agglomerates

We describe a new technique to measure the size dependent inherent material density of chain agglomerate particles. Measurements were carried out for diesel soot and aluminum/alumina agglomerate particles in the nanometer size range. Transmission electron microscopy was used to measure the volumes of agglomerate particles that were preselected by mass using an aerosol particle mass analyzer. We found that the density of diesel exhaust particles increased from 1.27 to 1.78g/cm³ as particle mobility size increased from 50 to 220nm. When particles are preheated to remove volatile components, the density was 1.77±0.07g/cm³, independent of particle size. The densities measured after heating correspond to the inherent material density of diesel soot. Measurements with aluminum nanoparticles were made downstream of a furnace where aluminum (Al) was converted to alumina (Al₂O₃). From measurements of inherent material density we were able to infer the extent of reaction, which varied with furnace temperature.     

Carbon nitride films by RF plasma assisted PLD: Spectroscopic and electronic analysis

Carbon nitride (CNx) thin films have been grown on Si 〈1 0 0〉 by 193 nm ArF ns pulsed laser ablation of a pure graphite target in a low pressure atmosphere of a RF generated N₂ plasma and compared with samples grown by PLD in pure nitrogen atmosphere. Composition, structure and bonding of the deposited materials have been evaluated by X-ray photoelectron spectroscopy (XPS), and Raman scattering. Significant chemical and micro-structural changes have been registered, associated to different nitrogen incorporation in the two types of films analyzed. The intensity of the reactive activated species is, indeed, increased by the presence of the bias confined RF plasma, as compared to the bare nitrogen atmosphere, thus resulting in a different nitrogen uptake in the growing films. The process has been also investigated by some preliminary optical emission studies of the carbon plume expanding in the nitrogen atmosphere. Optical emission spectroscopy reveals the presence of many excited species like C⁺ ions, C atoms, C₂, N₂; and CN radicals, and N₂⁺ molecular ions, whose relative intensity appears to be increased in the presence of the RF plasma. The films were also characterised for electrical properties by the “four-probe-test method” determining sheet resistivity and correlating surface conductivity with chemical composition.     

A comparative reactivity study of 1-alkene fuels from ethylene to 1-heptene

A comparative reactivity study of 1-alkene fuels from ethylene to 1-heptene has been performed using ignition delay time (IDT) measurements from both a high-pressure shock tube and a rapid compression machine, at an equivalence ratio of 1.0 in ‘air’, at a pressure of 30 atm in the temperature range of 600–1300 K. At low temperatures (< 950 K), the results show that 1-alkenes with longer carbon chains show higher fuel reactivity, with 1-pentene being the first fuel to show negative temperature coefficient (NTC) behavior followed by 1-hexene and 1-heptene. At high temperatures (> 950 K), the experimental results show that all of the fuels except propene show very similar fuel reactivity, with the IDTs of propene being approximately four times longer than for all of the other 1-alkenes. To analyze the experimental results, a chemistry mechanism has been developed using consistent rate constants for these alkenes. At 650 K, flux analyses show that hydroxyl radicals add to the double bond, followed by addition to molecular oxygen producing hydroxy?alkylperoxy radicals, which can proceed via the Waddington mechanism or alternate internal H-atom isomerizations in chain branching similar to those for alkanes. We have found that the major chain propagation reaction pathways that compete with chain branching pathyways mainly produce hydroxyl rather than hydroperoxyl radicals, which explains the less pronounced NTC behavior for larger 1-alkenes compared to their corresponding alkanes. At 1200 K, flux analyses show that the accumulation of hydroperoxyl radicals is important for the auto-ignition of 1-alkenes from propene to 1-heptene. The rate of production of hydroperoxyl radicals for 1-alkenes from 1-butene to 1-heptene is higher than that for propene, which is due to the longer carbon chain facilitating hydroperoxyl radical formation via more efficient reaction pathways. This is the major reason that propene presents lower fuel reactivity than the other 1-alkenes at high temperatures.     

Modeling soot formation in flames and reactors: Recent progress and current challenges

The study of soot has long been motivated by its adverse impacts on health and the environment. However, this combustion knowledge is also relevant to the production of carbon black and hydrogen via methane pyrolysis which are important commodities. Over the last decade, steady progress has been made in the development of detailed continuum models of soot formation in flames and reactors. Developing more comprehensive models has often been motivated by the need for predicting soot formation over a wider range of conditions (e.g., temperature, pressure, fuels). Measurements with novel experimental techniques have given us new insights into the chemistry, particle dynamics and optical properties of soot particles and even molecules and radicals forming them. Also, multi-scale modeling has enabled us to translate the detailed mechanisms of soot processes based on first principles into computationally efficient but accurate continuum models of soot formation in flames and reactors. However, important questions remain including (1) what is the mechanism of soot inception and surface growth, (2) which gas-phase species are involved in soot inception and surface growth (3) how surface growth and oxidation are affected by soot surface properties. Proposed models need to be evaluated against experimental data over a wide range of conditions to determine their predictive strength. These questions are critical for the accurate prediction of soot formation in flames and its emissions from engines. However, this knowledge can also be used to develop predictive process design and optimization tools for carbon black and other nanocarbon formation in reactors.