高效循环电弧放电法制备大量单壁纳米碳管的研究

介绍一种利用电弧放电法高效率制备大量单壁纳米碳管的新方法.以钨代替传统的石墨棒作为放电阴极，采取循环式往返放电法.同时利用高分辨透射电子显微镜及拉曼光谱对制备的单壁纳米碳管进行了观察、表征.实验证明：以钨为阴极的循环电弧放电法可以初步实现单壁纳米碳管的高效率、大批量生产. 关键词： 单壁纳米碳管 钨电极 拉曼光谱     

金属铈催化剂对单壁纳米碳管生长和结构的影响

研究了一种利用新型催化剂制备单壁纳米碳管（SWNTs）的工艺方法.将金属铈的氧化物（Ce O₂）与石墨粉按一定比例混合，填充到已打好孔的石墨棒中制成复合石墨电极 ，以其为阳 极在高温氦电弧中实施电弧放电.放电后的生成物经高分辨透射电子显微镜（HRTEM）和拉曼 光谱(Raman)的观察及分析表明：生成物中含有大量呈束状存在的单壁纳米碳管，管径均匀 ，平均直径为120—132nm. 关键词： 单壁纳米碳管 电弧放电 透射电镜分析     

高质量单壁纳米碳管的CVD法合成及催化剂酸碱性对碳管生长的影响

采用燃烧法制备了Fe/Mo/MgO催化剂,用化学气相沉积法在1000℃下催化裂解甲烷制得了单壁纳米碳管.实验结果表明,550℃下焙烧的催化剂效果最好,适宜的酸碱性应该是催化剂具有较高活性的原因.用扫描电镜、透射电镜、高分辨透射电镜、热重分析和拉曼光谱等方法对制备的纳米碳管粗产品进行了表征.结果表明,该产物确为高质量单壁纳米碳管,其形态基本都以束状存在,且单壁纳米碳管直径分布较窄(0.85～1.22nm);对反应气氛的考察表明,CH4/N2=50/300为最佳,该气氛下所制得粗产物中单壁碳管的含量接近40%,经稀盐酸室温处理后,碳管含量可达到75%以上.     

高纯单壁纳米碳管大量制备的新方法和工艺条件

在单壁纳米碳管大量制备方面提出了新方法和工艺条件.反复实验及电子显微镜分析表明,利用该方法和工艺条件,可以获得高产量、高纯度单壁纳米碳管.单根给定长度的含有金属的复合石墨阳极与阴极成一定角度在高温氦电弧中放电数分钟,即可获得1.0g以上含有60%左右的单壁纳米碳管的生成物.这为高纯单壁纳米碳管的规模化生产奠定了基础 关键词： 单壁纳米碳管 电弧放电 透射电子显微镜分析     

纳米碳管复合凝胶玻璃结构及谱学性能研究

用物理掺杂工艺将纳米碳管引入二氧化硅凝胶玻璃基质,成功制备了纳米碳管复合凝胶玻璃,采用X射线衍射、透射电子显微镜、紫外-可见吸收光谱、红外光谱、拉曼光谱等测试方法对其结构和谱学性能进行了表征。结果表明,通过优化掺杂工艺能够实现纳米碳管与基质的均匀复合,纳米碳管本身的结构在掺杂过程中并未发生改变。纳米碳管的引入对二氧化硅凝胶玻璃基质的紫外-可见吸收光谱和红外光谱未产生显著影响。     

微孔对单壁纳米碳管储氢性能的影响

用巨正则蒙特卡罗分子模拟方法研究了单壁纳米碳管中的微孔即单壁纳米碳管基本孔-内管腔和管间孔对单壁纳米碳管储氢性能的影响.与低温下氮气吸附实验结果的比较发现单壁纳米碳管的内管腔是吸附的主要位置.分析单壁纳米碳管内管腔中吸附势的叠加和利用效率，发现管径为2nm左右时单壁纳米碳管内管腔的储氢容量最高.当单壁纳米碳管阵列的管间距增加时，单壁纳米碳管的管间孔也会成为有效的氢吸附位. 关键词： Monte Carlo方法 单壁纳米碳管 储氢 微孔     

纳米碳管的电化学贮锂性能

用透射电镜、高分辨透射电镜、X射线衍射和拉曼光谱表征了用催化热解法制备的纳米碳管的结构,研究了纳米碳管的电化学嵌脱锂性能。以纳米级铁粉为催化剂热解乙炔气得到的纳米碳管石墨化程度较低,结构中存在褶皱的石墨层、乱层石墨和微孔等缺陷,具有国交高的贮锂容量,初始容量为640mAh/g,但循环稳定性较差。而以纳米级氧化铁粉为催化剂热解乙烯得到的纳米碳管结构比较规则,循环稳定性较好,但贮锂容量较低,初始容量为282mAh/g。讨论了纳米碳管的结构对其温度特性和不同电流密度下的充放电容易的影响。     

在氢气氛围下利用电弧放电法大量制备纳米碳管的研究

利用以石墨为电极的直流电弧放电法,在氢气氛围下制备出了纳米碳管.实验结果表明,在阴极上形成的碳素堆积物中,其前端表面及其内部都生成了纳米碳管.经扫描电子显微镜和透射电子显微镜观察分析发现,所生成的纳米碳管其形态构造在氢气的压强和直流电弧电流发生变化时,没有显著差异.在氢气压强为11999Pa,直流电弧电流为60A时,得到了大量的、管径较均匀、直而长的纳米碳管. 关键词：     

利用微波等离子体增强化学气相沉积法定向生长纳米碳管的研究

利用微波等离子体增强化学气相沉积法在氢气和甲烷的混合气体中定向生长纳米碳管.经扫描电子显微镜观察与分析，发现纳米碳管在与基板垂直的方向上整齐排列，管径较均匀且长度基本相同. 关键词： 微波等离子体 纳米碳管     

纳米碳管作为氧扩散电极催化层第二相碳载体的电极特性

以纳米碳管和活性碳二元碳材料为催化层碳载体制备了氧扩散电极,采用稳态极化和电化学阻抗技术对其在碱性介质中氧还原反应的电催化活性进行了研究.结果表明,双载体电极比单载体纳米碳管、活性炭电极具有更高的电催化活性,纳米碳管和活性炭质量比为50∶50时双载体电极的催化活性最好;电极动力学参数测试表明,催化层中引入第二相纳米碳管载体提高了电极比表面积、电子导电性和氧还原反应速度;采用浸渍还原法在第二相纳米碳管载体中负载纳米级Pt催化剂,即使在低Pt负载量下(45.7μg/cm2)也明显改善了双载体电极的催化活性.阻抗测试表明,载Pt与未载Pt催化剂的双载体电极均受氧在薄液膜中的扩散控制.     

Raman scattering of light in silicon nanostructures: First-and second-order spectra

First-and second-order Raman scattering spectra in Si nanocrystals have been studied. The shift to lower frequencies and the substantial broadening of first-order Raman scattering lines observed to occur with decreasing nanoparticle size were established to correlate with those in second-order spectra. It is shown that the experimentally observed shifts of peaks and their broadening cannot be predicted based only on the phenomenological model of strong phonon wave function localization. The anharmonic effect originating from the heating of the nanoparticle surface by laser radiation should also be included. Proper fitting of experimental data revealed that the anharmonic constants depend strongly on nanoparticle size. The shape and spectral positions of maxima in second-order Raman scattering spectra have been theoretically described.     

Raman spectral features of longer polyynes HC2 nH ({\sf n=4}–8) in SWNTs

Size-selected linear hydrocarbon molecules, polyynes HC_2nH, were contacted in solutions with single-wall carbon nanotubes (SWNTs) prepared from laser-ablated metal/carbon composite rods (Rh/Pt/C) to produce polyyne-encapsulating SWNTs, HC_2nH@SWNT(RhPt). New Raman spectral features were observed at 2120, 2061, 2017, 1982, and 1963 cm^-1 for five polyynes of n=4–8, respectively, and identified as the vibrational excitation of symmetric stretching modes of the molecules inside the SWNTs. The Raman spectra were compared with those observed for polyynes on Ag islands (SERS) and in solutions. The filling factor was investigated from the concentration dependence of the Raman intensity for HC₁₀H@SWNT(NiCo) to give an estimate of one polyyne molecule per ~350 carbon atoms of SWNTs, providing a picture for head-to-tale filling of aligned C₁₀H₂ molecules inside the SWNTs.     

Resonance Raman spectra of carbon nanotubes by cross-polarized light

Resonance Raman studies on single wall carbon nanotubes (SWNTs) show that resonance with cross polarized light, i.e., with the E(mu,mu+/-1) van Hove singularities in the joint density of states needs to be taken into account when analyzing the Raman and optical absorption spectra from isolated SWNTs. This study is performed by analyzing the polarization, laser energy, and diameter dependence of two Raman features, the tangential modes (G band) and a second-order mode (G' band), at the isolated SWNT level.     

n-SiC的电子拉曼散射及二级拉曼谱研究

研究了利用离子注入法得到的掺氮n-SiC拉曼光谱. 理论线形分析表明,与4H-SiC相比,6H-SiC中LO声子等离子体激元耦合模(LOPC模)拉曼位移随自由载流子浓度变化较小. 5145nm激发光下得到的电子拉曼散射光谱表明,k位处由1s(A₁)到1s(E)的能谷轨道跃迁带来的拉曼谱6H-SiC中有四条,4H-SiC中有二条;高频6303及635cm^-1处观察到的谱线被认为与深能级缺陷有关. 最后,利用纤锌矿型结构二级拉曼散射选择定则指认了6 关键词： 碳化硅 电子拉曼散射 轨道能谷分裂 倍频谱     

以Y/Ni为催化剂制备的单壁碳纳米管的拉曼光谱研究

采用电弧放电法以Y/Ni为催化制备了单壁碳纳米管（SWNTs），对样品进行了扫描电镜、透射电镜和拉曼光谱的研究。所制备的样品中单壁碳纳米管的含量较高。对单壁碳纳米管的共振拉曼散射增强效应进行了观察，随激光波长的不同，单壁碳纳米管的拉曼光谱也随之变化，尤其是低频区径向呼吸模的变化比较明显。利用布里渊区折叠法计算了单壁碳纳米管的电子态密度曲线，根据SWNTs电子态密度尖峰之间的能量差、管子的直径和呼吸模频率建立了一个图表，并对SWNTs的呼吸模进行了归属。分析结果表明：样品中单壁碳纳米管的直径分布在0.79-1.76nm范围，金属管和半导体管均存在，并且直径在1.45nm附近的碳管居多。     

A detailed Raman study on thin single-wall carbon nanotubes prepared by the HiPCO process

The Raman spectrum of single wall carbon nanotubes (SWNTs) prepared by high pressure CO decomposition (HiPCO process) has been recorded at nine excitation laser energies ranging from 1.83 eV to 2.71 eV. The characteristic nanotubes features: G band, D band and radial breathing mode (RBM) have been analyzed and compared to those of an arc discharge SWNT material of similar diameter. A strong Breit-Wigner-Fano type (metallic) contribution to the G band was found in the spectra measured with green lasers, while spectra measured with red lasers indicate resonances of semiconducting SWNTs. Analysis of the energy dependence of the position of the D band revealed sinusoid oscillations superimposed on a linear trend. The validity of full DOS calculations for HiPCO materials has been confirmed by a match found between the estimated spectral contribution of metallic SWNTs as calculated from the components of the measured G band and as predicted by the (n, m) indexes of the major scatterers of DOS simulations. The RBM region of the HiPCO spectrum is more complex than usually observed for SWNTs. The analysis performed with a Gaussian distribution and improved fitting parameters leads to a mean diameter and variance of 1.05 nm and 0.15 nm, respectively. A bimodal Gaussian distribution had little influence on the error sum but reduced the standard error slightly. The major spectral features of the RBM could be interpreted using available resonance Raman theory. Received 5 February 2002 / Received in final form 3 April 2002 Published online 19 July 2002     

Structural transformations in single-wall carbon nanotubes under high pressure

Single-wall carbon nanotubes (SWNTs) under high pressure exhibit high structural stability and a series of structural transitions up to 35 GPa. As theoretically predicted, the irreversible transformation of SWNTs in the pressure range of 10–30 GPa can be attributed to the polymerization of nanotubes. The electrical conductivity of SWNTs is studied at high pressures up to 35 GPa using a diamond anvil cell (DAC) with electrically conductive anvils of the “rounded cone-plane” type made of synthetic carbonado-type diamonds. SWNTs are studied before and after the application of high pressure using the Raman confocal microscopy technique. Analysis of Raman spectra and pressure dependences of the SWNT resistance shows that the observed structural changes in SWNTs are reversible and no polymerization or collapse are observed.     

Multiphonon Raman scattering from individual single-walled carbon nanotubes

Combinations of up to 6 zone-edge and zone-center optical phonons are observed in the Raman spectra of individual single-walled carbon nanotubes (SWNTs). These multiphonon Raman modes exhibit distinct signatures of the one-dimensional nature of SWNTs and provide information on the phonon structure, exciton-phonon coupling, and excitonic transitions in nanotubes.     

THE RAMAN SCATTERING OF CARBON NANOTUBES PRODUCED IN DIFFERENT INERT GASES AND THEIR PRESSURES BY ARC DISCHARGE

First- and second-order Raman spectra of carbon nanotubes produced in helium and argon atmospheres at a pressure ranging from 11 to 92 kPa by arc discharge have been measured and compared with each other. The position and bandwidth of the spectral lines depend on the kind of inert gases and their pressure. The Raman spectra of the nanotubes produced in argon gas atmosphere are much more similar to that of polycrystalline graphite than those of the nanotubes produced in helium gas atmosphere. The position and bandwidth of nanotube Raman peaks change with gas pressure in arc discharge because different diameter distribution of nanotubes is produced at different inert gas pressure. The Raman spectra of nanotubes produced at high pressure is much more like that of graphite than those produced in lower pressure     

Raman spectroscopy of carbon nanotubes

The use of Raman spectroscopy to reveal the remarkable structure and the unusual electronic and phonon properties of single wall carbon nanotubes (SWNTs) is reviewed comprehensively. The various types of Raman scattering processes relevant to carbon nanotubes are reviewed, and the theoretical foundations for these topics are presented. The most common experimental techniques used to probe carbon nanotubes are summarized, followed by a review of the novel experimental findings for each of the features in the first order and second order Raman spectra for single wall carbon nanotubes. These results are presented and discussed in connection with theoretical considerations. Raman spectra for bundles of SWNTs, for SWNTs surrounded by various common wrapping agents, and for isolated SWNTs at the single nanotube level are reviewed. Some of the current research challenges facing the field are briefly summarized.