硼碳氮纳米管的拉曼光谱研究

对不同温度和不同催化条件下用高温热解法制备的硼碳氮(BCN)纳米管的拉曼光谱进行了分析。随着制备温度的升高,拉曼光谱中D带和G带的强度比I_D/I_G由小变大,而后又变小,说明存在一个最佳温度,在该温度下生成的BCN纳米管中B、N元素掺杂浓度最大。不同催化剂对BCN纳米管的拉曼光谱也有影响,当以钴/二茂铁和镍/二茂铁为催化剂时的I_D/I_G值比以钴、镍和钴/镍为催化剂时大,说明这时的B、N的掺杂浓度较高,纳米管的质量较好,这与透射电子显微镜观察结果一致。     

不同催化剂热解法制备硼碳氮纳米管过程中的影响

对以钴、镍、钴/镍、钴/二茂铁、镍/二茂铁和二茂铁为催化剂高温热解法制备的硼碳氮（BCN）纳米管的结构、产率等的影响进行了分析.实验中发现催化剂在BCN纳米管的生长过程中有重要作用.高分辨率透射电子显微镜图像显示在860℃时，以镍/二茂铁、钴/二茂铁为催化剂生成的BCN纳米管具有“竹节状”结构，且管壁较薄，镍、钴或镍/钴作催化剂生成的BCN纳米管不具有明显的“竹节状”结构，管壁较厚，且粗细不均匀，而以二茂铁作催化剂没有BCN纳米管生成.在所有生成的BCN纳米管中含有催化剂颗粒.通过对生成的BCN纳米管的结 关键词： BCN纳米管 热解 催化剂 拉曼光谱     

不同催化剂对热解法制备CNx纳米管的影响

利用铁、钴、镍以及二茂铁为催化剂在高温下热解乙二胺制备CNx纳米管,研究了不同催化剂对CNx纳米管的形貌、结构及产量的影响,并对其催化机理进行了初步讨论.二茂铁和铁催化都能制备出“竹节状”结构的CNx纳米管,但产量较低.钴催化生成CNx纳米管多弯曲,管壁多褶皱,产量较高.镍催化只生成了直径500nm左右的螺旋管.拉曼光谱研究进一步表明,二茂铁催化生成“竹节状”结构CNx纳米管由于氮的掺杂程度相对较高而结晶有序度较低.     

乙炔/空气预混火焰法合成多壁碳纳米管的实验研究

本文利用乙炔-空气预混火焰研究了多壁碳纳米管(MWCNTs)的合成,采用涂覆有二茂铁或硝酸镍催化剂的探针在预混火焰中采样,用扫描电镜(SEM)和透射电镜(TEM)对碳纳米材料(CNTs)的形貌和结构进行了表征.结果表明在乙炔-空气预混火焰中,二茂铁和硝酸镍均能够成功合成竹节状多壁碳纳米管,严物中处发现了碳纤维(CNF)、巴基葱(bucky onion)和碳黑等物质.二茂铁催化生成的碳纳米管管径大于硝酸镍催化生成的碳纳米管的管径;在乙炔-空 气散火焰和甲烷-空气扩散火焰中硝酸镍所催化合成的碳纳米管管径相近,说明碳纳米管的管径受催化剂颗粒尺寸的影响较大.研究表明探针在火焰中停留的时间和保护气体也会影响碳纳米管的合成.     

金镍复合膜上碳纳米管的定向生长及生长过程中金的作用

以金镍复合膜作催化剂，在96%的高氢气浓度下实现了碳纳米管的定向生长，并对其生长过 程进行了深入探讨.结果表明，高氢气浓度下碳纳米管生长的实现与本实验所选用的催化剂 ——金镍复合膜有密切关系.催化剂中金的参与，促进了碳在催化剂中的扩散，提高了碳在 催化剂中的活度.与催化剂中没有金的情况相比较，金的参与有利于镍吸收气氛中的碳，从 而使镍更容易达到碳饱和，有利于在高的氢气浓度下实现碳纳米管的定向生长. 关键词： 金镍复合膜 高氢气浓度 原子氢 碳活度     

二茂铁质量对气相爆轰法合成碳纳米管的影响

以甲烷和氧气作为爆源,二茂铁为前驱体,探究了不同前驱体质量对所合成的碳纳米管的影响。利用X射线衍射(XRD)、透射电子显微镜(TEM)、高分辨透射电子显微镜(HRTEM)等手段对碳纳米管的形貌和结构进行表征,结果发现:当二茂铁量较少时,只有碳包覆铁纳米颗粒存在;随着二茂铁质量的增加,逐渐有碳纳米管生成,其管径大多分布在10~50nm之间,为多壁碳纳米短管。随着前驱体质量的增加,碳纳米管的石墨化程度提高,结构缺陷也变少。通过对合成产物的热重分析可得,气相爆轰法所制备的碳纳米管具有强烈吸氧性,所得样品中碳纳米管的质量分数为26%左右。     

二茂铁在高温热解乙二胺制备CN_x纳米管过程中的催化性能研究

采用高温热解法 ,以二茂铁 乙二胺有机溶剂为前驱液制备CNx 纳米管过程中 ,改变前驱液配比 ,对 86 0℃ ,不同二茂铁含量条件下制备出的CNx 纳米管进行了产量统计、形貌结构观察和拉曼光谱研究。结果显示 :随着前躯液中二茂铁含量的相对增大 ,不但CNx 纳米管产量随之增加 ,而且产物中“竹节状”结构纳米管相对“中空”结构纳米管的比重也增大 ;拉曼光谱结果进一步证实了由于“竹节状”结构CNx 纳米管的含量或比重增加所带来的纳米管样品整体或平均含氮量的升高而导致的样品结晶有序程度的降低。对单独钴粉和二茂铁催化条件下生成CNx 纳米管的形貌观察进一步证实 :二茂铁在热解法制备“竹节状”结构CNx 纳米管过程中的浮动催化作用显著 ,有利于实现含氮量较高、结构均匀的CNx 纳米管的可控制生长。     

化学气相沉积法制备定向碳纳米管阵列

以二茂铁和二甲苯分别作为催化剂和碳源，采用一种无模板的化学气相沉积法，使用单温炉设备，成功地制备了高度定向的碳纳米管阵列.分别用扫描电子显微镜、透射电子显微镜和电子能量散射谱、拉曼光谱对碳纳米管阵列进行形貌观察和表征, 并研究了不同工艺参数对碳纳米管阵列形貌的影响.结果表明：在生长温度为800℃，催化剂浓度为0.02g/mL，抛光硅片上容易获得高质量的定向碳纳米管阵列，在此优化条件下生长的定向碳纳米管的平均生长速率可达25μm/min.     

氮掺杂碳纳米管负载铂催化剂的简易制备及催化性能

以氮掺杂碳纳米管为载体,在温和条件下采用简单的浸渍法制备得到铂催化剂,铂的粒径分布在4～7 nm,且氮掺杂碳纳米管无需进行预处理. 采用X射线衍射仪、扫描电子显微镜、透射电镜和能量色散X射线仪等对Pt/CN_x催化剂进行了详细的表征. 结果表明,氮掺杂碳纳米管中高含量的氮原子能够有效俘获Pt(IV) 离子,且表面的含氮官能团及亲水性能的提高都有利于铂纳米粒子的分散. Pt/CN_x催化剂在烯丙醇加氢反应中表现出高的催化性能及循环使用性能,这是由于铂纳米粒子的高分散性及铂与载体间强的连接性阻止了Pt的流失及聚积,从而避免生成Pt黑导致失活等.     

超长定向含铁多壁碳纳米管阵列的制备

采用无模板化学气相沉积法,以二茂铁为催化剂,二甲苯为碳源,利用单温炉加热装置制备了定向碳纳米管阵列。运用扫描电子显微镜、透射电子显微镜、拉曼光谱和X射线衍射仪等对定向碳纳米管阵列的形貌、成分和物相进行细致的分析和表征。结果表明:制得的碳纳米管阵列具有良好的定向性和多壁管状结构,并且石墨化程度高;碳纳米管中除碳元素外,管中包含有少量以纳米颗粒和纳米线形式存在的铁及其化合物,主要成分是铁和碳化铁。结合碳纳米管的制备和透射电子显微镜分析表征结果,认为超长碳纳米管阵列的生长模式为底部生长方式,即经历催化剂分解、催化、成核、长大、中毒、凝聚成粒和连接成线的循环过程,正是由于碳源和催化剂的连续供应促成了碳纳米管阵列的快速定向生长。     

催化裂解CH4制备碳纳米管的影响因素

以柠檬酸法制备的Fe MgO、Co MgO和Ni MgO为催化剂 ,CH4 为碳源气 ,H2 为还原气 ,在 873、973和 10 73K制备出碳纳米管 ,通过TEM和拉曼光谱表征 ,讨论了催化剂、制备温度、反应时间等因素对碳纳米管形貌、产率和内部结构的影响 .结果表明 :不同的催化剂在相同的温度下制备的碳纳米管的形态和内部结构有很大的差异 .其中Fe MgO催化剂制备的碳纳米管管径粗 ,且大小不均匀 ,而Ni MgO催化剂制备的碳纳米管管径较细、较均匀 .碳纳米管的产率随着裂解温度的变化而改变 .Fe MgO催化剂制备碳纳米管的产率随制备温度的升高而提高 ,而Ni MgO催化剂制备碳纳米管的产率随制备温度的升高而降低 .Fe MgO催化剂制备碳纳米管 ,在10 73K甚至更高的制备温度才能达到其最高产率 .Co MgO催化剂制备碳纳米管的产率在 973K左右产率较高 ,而用Ni MgO催化剂制备碳纳米管 ,则在 873K甚至更低的制备温度就能达到最高产率 .反应时间与碳纳米管的产率不成正比 ,有一最佳反应时间 ,如Ni MgO催化剂的最佳反应时间为 2h .     

Functionalization of ultradispersed diamond for DNA detection

Carbon nanotubes have been synthesized by catalytic chemical vapour deposition of acetylene diluted with argon using three different catalysts, namely, nickel formate, cobalt formate and ferrocene. The synthesis was carried out at 700°C in a quartz reactor for 30 minutes. Thermal analysis was carried out in order to determine the yield of the nanotube. It was found that the deposit contains 86% nanotube, with nickel-based catalyst, which was the maximum. The yield of nanotube was 71 times that of the nickel loading. The TEM images reveal helical type of nanotubes with iron catalyst while cobalt and nickel catalysts yielded straight nanotubes. This technique can be explored for the bulk production of carbon nanotube in an economic way.     

Effect of nickel,iron and cobalt on growth of aligned carbon nanotubes

The effect of pure nickel, iron and cobalt on growth of aligned carbon nanotubes was systematically studied by plasma-enhanced hot-filament chemical vapor deposition. It is found that the catalyst has a strong effect on the nanotube diameter, growth rate, wall thickness, morphology and microstructure. Ni yields the highest growth rate, largest diameter and thickest wall, whereas Co results in the lowest growth rate, smallest diameter and thinnest wall. The carbon nanotubes catalyzed by Ni have the best alignment and the smoothest and cleanest wall surface, whereas those from Co are covered with amorphous carbon and nanoparticles on the outer surface. The carbon nanotubes produced from Ni catalyst also exhibit a reasonably good graphitization. Therefore, Ni is considered as the most suitable catalyst for growth of aligned carbon nanotubes. Received: 30 November 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Effects of catalysts on the internal structures of carbon nanotubes and corresponding electron field-emission properties

Using a chemical vapor deposition (CVD) method, multi-walled carbon nanotubes with uniform diameters of approximately 10 nm were synthesized on silicon substrates by the decomposition of acetylene using Fe, Co and Ni as the catalysts. Catalyst effects on the internal structures of the carbon nanotubes were evident in the Fe, Co and Ni catalyzed nanotubes. Although these nanotubes demonstrated similar morphologies, due to the variety of internal structures, the nanotubes synthesized from different catalysts demonstrated various electron field-emission characteristics including turn-on field, threshold field and field enhancement factor. Compared with carbon nanotubes from Ni catalyst, nanotubes from Fe and Co with the same diameters have better field-emission properties. Graphite layers in nanotubes from Fe and Co are much straighter and more parallel to the tube axis with fewer defects. For instance, the turn-on field and threshold field for nanotubes from Ni are 5 V/m and 9 V/m, respectively. These electric fields are much higher than those for nanotubes from Fe, which are 0.35 V/m and 2.8 V/m, respectively. This could be due to the effect of catalysts on the work function of nanotubes, since the catalyst particle usually terminates the free end of the nanotube, and the influence of internal structure on electron transportation along the nanotube axis. Therefore, this study suggests that besides a small diameter, good graphitization (crystallization) is an important prerequisite for a good carbon nanotube emitter. PACS 79.70.+q; 68.37.Lp; 81.07.De     

STRUCTURE AND MORPHOLOGY OF CARBON NANOTUBES GROWN ON ZEOLITE-SUPPORTED CATALYSTS BY CHEMICAL VAPOR DEPOSITION

The zeolite-supported catalysts were prepared in nickel and cobalt nitrate aqueous solutions by ion exchange method. After reducing these substrates by hydrogen, we grew carbon nanotubes on them by chemical vapor deposition under different conditions. The results reveal that nickel/zeolite, cobalt/zeolite and nickel+cobalt/zeolite have different optimal conditions. When nickel+cobalt/zeolite was used as the catalyst, we can get straight carbon nanotubes. The Raman spectrum of the straight nanotubes shows they have fewer defects. We propose a growth mechanism for the growth of these nanotubes.     

Chemical vapor deposition of multi-walled carbon nanotubes from nickel/yttria-stabilized zirconia catalysts

Multi-walled carbon nanotubes (MWNT) were produced by chemical vapor deposition using yttria-stabilized zirconia/nickel (YSZ/Ni) catalysts. The catalysts were obtained by a liquid mixture technique that resulted in fine dispersed nanoparticles of NiO supported in the YSZ matrix. High quality MWNT having smooth walls, few defects, and low amounts of by-products such as amorphous carbon were obtained, even from catalysts with large Ni concentrations (>50 wt. %). By adjusting the experimental parameters, such as flux of the carbon precursor (ethylene) and Ni concentration, both the MWNT morphology and the process yield could be controlled. The resulting YSZ/Ni/MWNT composites can be interesting due to their mixed ionic-electronic transport properties, which could be useful in electrochemical applications. PACS 61.46.Fg; 81.15.Gh; 82.45.Jn     

Electronic state of nitrogen incorporated into CNx nanotubes

CN_x nanotubes have been prepared by acetonitrile decomposition over Ni, Co and Ni/Co catalysts. X-ray photoelectron spectroscopy study on the samples revealed a change of nitrogen concentration and shape of N 1s line with variation of the catalyst used. Quantum-chemical calculations on tube fragments showed the energy of N 1s level depends on the atomic structure of carbon tube and kind of incorporated nitrogen. The largest binding energies were found to be characteristic of three-coordinated nitrogen atoms doping the zigzag and chiral carbon nanotubes.     

Carbon nanofibers and multiwalled carbon nanotubes from camphor and their field electron emission

Vertically aligned carbon nanofibers (CNF) and multiwalled carbon nanotubes (MWCN) have been synthesized from camphor by catalytic thermal CVD method on Co and Co/Fe thin films (for CNF) and on silicon substrates using a mixture of camphor and ferrocene (for MWCN). CNF and MWCN are studied by field emission scanning electron microscopy, high-resolution transmission electron microscopy, visible Raman spectroscopy, X-ray diffraction in order to get insight into the microstructure and morphology of these materials. Field electron emission study indicates turn-on field of about 2.56, 3.0 and 6.5 V/μm for MWCN, Co/CNF and Co/Fe/CNF films, respectively. The best performance of MWCN in field electron emission among the materials studied can be due to the highest aspect ratio, good graphitization and good density.