单壁碳纳米管储氢密度计算与分析

借助于分子动力学方法,对单壁碳纳米管的储氢过程进行了模拟.根据得到的管内外H2分子的分布规律,计算了H2分子密度分布曲线,对其结果给出了理论分析和物理解释,提出了单壁碳纳米管储氢的多层吸附机制,定量地计算了碳纳米管储氢量(wt.;).这些为进一步研究单壁碳纳米管储氢问题提供了必要的理论依据.     

单壁碳纳米管储氢过程的GULP模拟

利用GULP软件的蒙特卡罗模块对常温(T=300 K)下单壁碳纳米管(SWNT)管内物理吸附储氢进行了模拟.研究和讨论了5种半径的扶手椅管在T=300 K时的吸附等温线,给出了同一管径在不同压强下氢气分子在碳纳米管中分布变化的对比图,并对T=300 K,P=10 MPa时不同管径的碳纳米管储氢能力进行了对比.结果显示,常温下压强不大于10 MPa时单壁碳纳米管吸附氢气的质量储氢容量不超过1.8;,体积吸附量不超过22 kg·m-3,表明纯单壁碳纳米管具有一定的吸附氢气的能力,但其存储能力与美国能源部提出的研究目标尚有一定差距,还需通过改变碳纳米管的结构、特性等方法来改善其储氢特性.     

Ca修饰石墨烯储氢性能的第一性原理研究

使用基于密度泛函理论的DMol3程序包,研究了纯石墨烯和5种不同结构Ca修饰石墨烯的几何结构、电子结构和储氢性能.结果表明:Ca原子不同位置吸附对石墨烯结构影响微弱;随Ca原子周围氢分子吸附数目增加,费米能级处电子态密度值增大,氢分子平均吸附能减小;单Ca修饰石墨烯能稳定吸附6个氢分子,吸附能为0.635eV,储氢密度为2.77wt;;双Ca修饰石墨烯结构Ⅲ和Ⅳ的氢平均吸附能最高,分别达到0.789 eV和0.733 eV,其储氢密度为4.95wt;.     

单壁碳纳米管储氢中管外H2势能的拟合函数

H2分子与管的作用势能曲线是碳纳米管储氢模拟研究中的一项重点内容,建立势能曲线相应的函数表达式更具有理论价值和实际意义.本文从Lennard-Jones势出发,建立了H2分子与C原子之间的作用势能模型,借助于分子动力学(MD)方法,模拟计算了H2分子与管的作用势能曲线.通过对管外H2分子势能曲线的拟合,找到了最佳参数,建立了管外统一形式的势能数学表达式,为碳纳米管的储氢研究提供了相应的理论依据.     

夹心多核茂合物Cp2Mgn结构和储氢性能的第一性原理研究

使用基于密度泛函理论(DFT)的DMol3程序包,研究了夹心多核茂合物Cp2Mgn的几何结构、电子结构和储氢性能.研究表明:夹心原子对体系结构影响微弱;Mg-Mg间形成共价σ单键,Mg-Cp间形成离域π共价键;Cp2Mg2和Cp2Mg3最多可分别吸附氢分子4个和10个,吸附能分别为0.252 eV/H2和0.291 eV/H2,储氢量分别为4.32wt;和9.03wt;.     

碳纳米管电荷分布对电子发射场增强因子影响的研究

本文通过分析碳纳米管的电荷分布规律,巧妙地将处于外电场中且端口封闭的金属性碳纳米管等效成电荷非均匀分布的球面,获得了包括端部球面电荷、管壁电荷与镜像电荷共同作用的场增强因子为β=1.14 h/R 2.62.结果表明:场增强因子是碳纳米管长径比h/R的线性函数,并与电荷分布密切相关.在此基础上,研究发现35%的管壁电荷对碳纳米管电子发射的场增强因子贡献约为9.7%,但仍远大于镜像电荷的影响.根据模型中电荷非均匀分布导致碳纳米管各处局域电场大幅度变化,解释了仅在球面的一定区域才大量发射电子且发射电流密度不均匀的实验现象.     

单壁碳纳米管中稳态机械波的激发条件研究

通过分子动力学模拟,对单壁碳纳米管中稳态机械波的激发条件进行了详细的研究.利用所施加的周期性机械外力,使单壁碳纳米管产生局部径向形变,该形变将以单壁碳纳米管的管壁为弹性媒质传播开去,从而在单壁碳纳米管中形成机械波;机械波产生的条件依赖于单壁碳纳米管波动系统能量的维持和受迫振动区域形变方向的控制;稳定机械波形成的最佳条件是碳纳米管的形变度和受迫振动频率之间的最优匹配,以及由此形成的单壁碳纳米管在周期性外力作用下产生的共振.     

取样时间和碳源气体流量对火焰法催化裂解乙烯制备碳纳米管的影响

采用火焰法,并使用Fe/Mo/Al2O3型载体催化剂,催化裂解乙烯制备了碳纳米管,并对取样时间和乙烯气体流量进行了实验探究.结果表明:取样温度保持1000℃,He和H2气体流量保持为经验配比He∶H2=2∶3时,取样时间越长,生成的碳纳米管数量也越多,而取样时间达到7 min时,碳纳米管的数量已经基本稳定;乙烯气体流量为0.2 L/min时,生成的碳纳米管在质量和数量上都达到较佳,乙烯流量偏低或者偏高都不利于碳纳米管的生成;实验中制备的碳纳米管以双壁或者少壁的多壁碳纳米管为主,没有单壁碳纳米管生成.     

TiCl4分子填充扶手椅型碳管的条件控制及光电性能理论研究

采用第一性原理与蒙特卡罗方法研究TiCl₄气体分子填充扶手椅型碳纳米管的吸附性能与光电性质,结果表明:扶手椅型碳纳米管对TiCl₄气体分子具有较强的物理吸附作用,研究构型的吸附能绝对值均超过0.9 eV,是TiCl₄气体分子理想的填充载体,随碳纳米管管径的增大,吸附能先增大后减小;温度升高不利于TiCl₄气体分子吸附,气体逸度增加有利于吸附,TiCl₄气体分子填充扶手椅型碳纳米管宜将温度维持在TiCl₄沸点附近,并增加气体的压力;TiCl₄的吸附对碳纳米管的电子结构进行了调控,使费米能级附近的态密度显著提高,使复合物的导电性增强,对赝能隙的大小没有明显影响,峰位仍由碳纳米管自身决定;TiCl₄的吸附对体系的光学参数影响有限,在增强复合物导电性的同时未使可见光区域吸收率、反射率、损失函数数值增大,可有效提升透明导电薄膜的性能。     

氢原子在过渡金属修饰的Mg(0001)面扩散的第一性原理研究

基于密度泛函理论(DFY)的第一性原理计算方法,对氢原子在过渡金属(Sc、Ti、Cr、Mn、Fe、Co、Ni、Cu、V、Zn)修饰的Mg(0001)表面扩散性能进行了研究.研究发现过渡金属元素Sc、Ti、V、Cr、Mn、Fe、Co、Ni和Cu选择替代在镁表面第二层稳定,而Zn则选择替代在第一层稳定.当镁表面掺杂Zn和Cu时,氢原子选择停留在表面稳定;当掺杂Sc、Ti、V、Cr、Mn、Fe、Co和Ni时,氢原子选择进入镁块体内部.值得一提的是氢原子通过从过渡金属顶部通道扩散进入镁块体内部的势垒大大降低,笔者用差分电荷密度分析后发现氢原子与过渡金属原子成键使扩散势垒降低.当氢原子进入镁块体内部后靠近Sc、Ti、V、Cu和Zn原子时,将与这些过渡金属原子成键,从而阻碍了氢原子继续向内部扩散;而氢原子靠近Cr、Mn、Fe、Co、Ni原子时,选择离开过渡金属从而促进了氢原子向块体内扩散,可以大幅改善镁基储氢材料的吸氢动力性能.     

化学气相沉积法制备平直多壁碳纳米管的研究

本文研究了用焦炭还原二氧化碳后的一氧化碳作碳源,化学气相沉积法合成平直的多壁碳纳米管的工艺.研究表明在化学气相沉积条件下,用焦炭还原二氧化碳得到的一氧化碳在适当的铁基催化剂作用下,采用催化剂/碳原子共沉积的工艺可以生产出平直、并且内径很大的多壁碳纳米管.碳源中催化剂的浓度影响着纳米管的形成,而沉积温度对其没有影响.     

V型热解火焰合成碳纳米管的影响因素研究与分析

介绍了用V型热解火焰燃烧器制备碳纳米管的实验条件,利用扫描电子显微镜和透射电子显微镜对碳纳米管进行表征,详细研究和分析了温度、反应物成分、催化剂、燃氧比等影响因素对碳纳米管形态的影响.结果表明:温度在800～1000 ℃之间,采用CO/H_2/He作为反应气体,用Fe(CO)_5作为催化剂时,可以得到的形态较好、杂质较少的碳纳米管.     

Electrical conductivity improvement of aeronautical carbon fiber reinforced polyepoxy composites by insertion of carbon nanotubes

An increase and homogenization of electrical conductivity is essential in epoxy carbon fiber laminar aeronautical composites. Dynamic conductivity measurements have shown a very poor transversal conductivity. Double wall carbon nanotubes have been introduced into the epoxy matrix to increase the electrical conductivity. The conductivity and the degree of dispersion of carbon nanotubes in epoxy matrix were evaluated. The epoxy matrix was filled with 0.4 wt.% of CNTs to establish the percolation threshold. A very low value of carbon nanotubes is crucial to maintain the mechanical properties and avoid an overload of the composite weight. The final carbon fiber aeronautical composite realized with the carbon nanotubes epoxy filled was studied. The conductivity measurements have shown a large increase of the transversal electrical conductivity. The percolative network has been established and scanning electron microscopy images confirm the presence of the carbon nanotube conductive pathway in the carbon fiber ply. The transversal bulk conductivity has been homogenized and improved to 10^? 1 S·m^? 1 for a carbon nanotubes loading near 0.12 wt.%.     

Studies of hydrogen interaction with carbon deposit containing carbon nanotubes

Nanocarbon materials were obtained by catalytic decomposition of ethylene on nanocrystalline iron at 500 and 550 °C. The increase in the carbon mass was controlled using the thermogravimetric method. After synthesis the samples were analyzed using the HRTEM and X-ray diffraction methods and contained iron carbide (cementite) and nanocarbon materials (carbon nanofibers, carbon nanotubes and amorphous carbon). Cementite crystallites were observed at the end of filamentous structures. In order to remove amorphous carbon and thick carbon nanofibers the samples were reduced under hydrogen atmosphere. As a result of the hydrogenation treatment, the cementite was decomposed into iron and carbon. The samples contained mainly multi-walled carbon nanotubes with open ends and had diameters in the range of approx. 10–30 nm.     

Observation of the growth of carbon nanotubes prepared at low temperature

Lack of information during the growth of carbon nanotubes has hindered efforts to understand the growth mechanism of these unique nanoscale structures. Here, we report that Multi‐walled carbon nanotubes with bamboo‐shaped structure may be synthesized by solvothermal method at 300°C using benzene as carbon source and Zn as catalyst. We have obtained direct experimental information on the growth under Transmission electron microscopy. It has been shown that all the compartments of bamboo‐like tube successively joined leading to the formation of regularly segmented nanobamboos. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structures of Complex Crystals of Alkylammonium Salts with Aromatic Molecules

Abstract

The complex crystal structures of dodecyltrimethylammonium chloride (DTAC) with catechol and hydroquinone were analysed by an X-ray diffraction method. Both complexes have isomorphous layered structures. The guest molecules locate between the interdigitated host molecules. Crystal structures are stabilized by mainly hydrogen bonds including water molecules. A cross-section balance between hydrophilic and hydrophobic parts is important for an energetically stable packing. DTAC can form the crystalline complexes with catechol and hydroquinone by both crystallizing from the solution and mixing host and guest powders in a mortar. In addition, DTAC can also make a complex with resorcinol. Powder diffraction pattern indicates that this complex has similar layered structure with complexes of DTAC / catechol and DTAC / hydroquinone. However, it is unstable in atmospheric condition.