氨气氛中镍催化剂和纳米碳管的制备

用X射线衍射仪、扫描电子显微镜和透射电子显微镜,研究了以瓷舟为载体、硝酸镍为原料、乙炔为碳源,在氨气中制备镍催化剂和纳米碳管时温度的影响,并讨论了氨气的作用.结果表明,以氨气还原硝酸镍获得镍催化剂时,最佳温度范围是700～800℃,此时催化剂的颗粒较细小且均匀,有利于纳米碳管的生长;此外,选用孔径比较细小均匀多孔的载体材料,有助于获得颗粒均匀细小的镍催化剂;在制备纳米碳管时,热分解氨得到的活性氢原子有利于维持催化剂的活性,抑制无定型碳的生成,从而促进纳米碳管生长.实验中纳米碳管的最佳制备温度为700～800℃,管径为10～25nm.     

化学气相沉积法快速生长定向纳米碳管

利用化学气相沉积法，采用二甲苯为碳源，二茂铁为催化剂，氮气作保护气，在石英基底上催化裂解生长定向纳米碳管，试验结果表明：在775℃，120min的条件下，可生长出长达200μm厚的定向纳米碳管薄膜；在775℃，反应时间为60min～120min时，纳米碳管的长度为100μm～200μm，而纳米碳管的直径变化不明显。而无氢气，较高的反应温度和连续的催化剂供给对快速生长定向纳米碳管有重要的影响。     

气相催化热解法制备纳米碳管的研究

以二茂铁为催化剂、苯为碳源、噻吩为生长促进剂,采用气相催化热解法制备了纳米碳管,并运用TEM、Raman、XRD等对纳米碳管的外观形貌、结构、晶化程度等进行了观察研究.结果表明:在1155℃下能制备出管径20～100nm的纳米碳管,其最大产量是催化剂用量的350%.     

定向纳米碳管微观结构的观察和生长机制探讨

SiO2表面溅射铁膜后用CVD法制备了定向纳米碳管。用扫描电镜、透射电镜和高分辨透射电镜对顶部催化剂及包裹于管内的催化剂、纳米碳管的结构和所形成的竹节状形貌进行了观察。以液态生长纳米碳管为基础提出了一种纳米碳管生长机制。     

镁-镍合金催化剂制备及纳米碳管生长模式研究

采用多元醇法制备镁-镍合金纳米粉末,并以此为催化剂制备纳米碳管,利用比表面和孔径分布测定仪、X射线衍射仪和透射电镜,研究镁-镍合金催化剂的性能和纳米碳管的生长模式。结果表明:Mg∶Ni值对镁-镍合金催化剂特性影响较大,其中Mg∶Ni为1的催化剂颗粒比表面积较大且平均粒径较小;聚乙烯吡咯烷酮(PVP)用量增大,有利于提高催化剂颗粒的比表面积、减小平均粒径,但用量过大不利于Mg2Ni合成。在以镁-镍合金为催化剂制备碳纳米管的过程中,首先在催化剂表面形成碳膜,随后形成的碳膜将前期形成的碳膜及催化剂颗粒向外推挤,催化剂颗粒移动后遗留下中空隧道,最终形成碳管,由于纳米碳管尖端的催化剂颗粒反应后失去催化活性,碳管的生长动力主要来自碳管根部。     

纳米碳管/氧化锌异质结构的合成及发光性质

以纳米碳管（CNTs）为基体、铜为催化剂,采用催化碳热还原方法直接合成出具有异质结构的纳米碳管/氧化锌（CNT/ZnO）复合材料。利用扫描电镜、透射电镜及X射线衍射等手段研究了异质结构CNT/ZnO复合材料的形态和结构。发现氧化锌纳米线在纳米碳管表面的生长过程遵循催化剂诱导的汽-液-固（VLS）机制;氧化锌纳米线与铜催化剂和纳米碳管之间分别存在明显的界面,并且氧化锌纳米线与纳米碳管均保持了规整的晶体结构。同时也发现在大直径纳米碳管上易于形成高密的氧化锌纳米线;随沉积温度的升高ZnO的形态由线到棒最后形成颗粒。异质结构CNT/ZnO复合材料的诱导发光性能不同于氧化锌纳米线和纳米碳管,在蓝光区域的发光强度远大于紫外发光强度。     

镁钼氧化物催化剂制备多壁纳米碳管的初步研究

采用溶胶-凝胶法合成了可用来催化裂解甲烷大量制备高质量和较高纯度的多壁纳米碳管的镁钼氧化物催化剂. 实验表明该催化剂具有较高的活性和催化效率, 反应2h后, 制备的多壁纳米碳管的量接近原始催化剂量的30倍. 并用透射电镜、高分辨透射电镜、激光拉曼和热重分析对制得的粗产品进行了表征, 结果表明: 碳管的直径在10～22nm之间, 且随着反应时间的延长, 制备的纳米碳管石墨化程度增加, 反应1h后, 粗产品中碳管含量达95%, 同时, 对催化剂的特殊催化生长机理作了讨论, 生长过程中多层Mo颗粒析出在MgO载体表面是碳管成束的主要原因.     

膨胀石墨的孔隙内生长纳米碳管

膨胀石墨具有丰富的网络状微孔结构和石墨微晶的活性表面,因此有较大的比表面积和较高的表面活性.膨胀石墨的孔隙结构可以负载催化剂粒子,是生长纳米碳管的物理基础.以硝酸铁为催化剂前驱体,乙炔为碳源,采用化学气相沉积工艺,可以在膨胀石墨的孔隙结构中生长稠密的纳米碳管.     

以煤为碳源直流电弧法制备单壁纳米碳管绳

以太西无烟煤为碳源，以稀土氧化物La2O3和过渡金属Ni为催化剂制备复合的煤基炭棒，采用直流电弧放电技术，成功实现了单壁纳米碳管绳的批量制备。用TEM和Raman光谱技术对纳米碳管绳产品进行了分析表征。结果表明：太西煤是制备单壁纳米碳管的合适碳源；电弧放电得到的煤基单壁纳米碳管的直径分布在2．01nm-1．80nm之间；双金属催化剂Ni-La在单壁纳米碳管的形成过程中存在协同作用，其催化活性优于其中的单一组分。     

冷壁装置化学气相沉积制备纳米碳管

采用冷壁装置化学气相沉积(CVD)制备纳米碳管,以乙炔(C2H2)为碳源气体,研究了2种催化剂(镍、铁)、3种基底、3种稀释气体、3种稀释气体和碳源气体流量比以及温度对CVD法生长纳米碳管的影响,用SEM和TEM分析了产物的形貌.结果表明,镍催化活性高于铁的催化活性.与石墨和纯铁基底相比,以单晶硅基底生长的纳米碳管纯度更高,管壁更干净.3种稀释气体和碳源气体流量比(2/1、10/1、19/1)中,以流量比为10/1时生长纳米碳管效果最好.3种稀释气体(氨气、氢气、氮气)中,以氨气最好.随着生长温度的升高,催化剂的活性提高,有利于碳的有序排列,但生长的碳纳米管直径增大.当基底为单晶硅、催化剂镍膜厚度为20nm、氨气气氛、生长温度为850℃时,得到了近似定向生长的纳米碳管.     

催化剂加载对连续碳纤维表面生长碳纳米管的影响

通过化学气相沉积(CVD)在碳纤维表面还原得到均匀细小的催化剂颗粒并在碳纤维表面催化生长了均匀、规整的碳纳米管(CNTs)。系统研究了催化剂种类以及浓度对碳纳米管产量和微观组织结构的影响,探究了碳纤维的浸润性能和单丝强度的变化。结果表明,Ni的催化活性最高,Co的催化活性适中,产生的CNTs较为均匀、规整,当催化剂浓度为0.02mol/L时,碳纤维表面生长CNTs多尺度增强体的拉伸强度最大。碳纤维表面生长CNTs,促使碳纤维的表面粗糙度增加,与树脂之间的结合变强,从而提高了碳纤维与环氧树脂之间的浸润性。     

Synthesis of vertically aligned carbon nanotube arrays by injection method in CVD

The well aligned multiwalled carbon nanotube arrays were synthesized by injecting the acetonitrile-ferrocene solution at regular intervals of time. The carbon nanotube arrays were deposited on quartz substrate which is placed at the centre of the CVD reactor in quartz tube. The injection method in chemical vapor deposition allows-excellent control of the catalyst to carbon ratio which facilitates the better growth of aligned carbon nanotubes. The effect of various reaction parameters such as growth temperature, catalyst concentration, gas flow rate, growth time and substrate surface on growth of carbon nanotubes have been studied. It was observed that the diameter of carbon nanotubes increases with increase in catalyst concentration and temperature of the synthesis. The SEM analysis reveals that the average growth rate of carbon nanotube film synthesis was about 1.1 microm/min when the synthesis time was one hour.     

Catalytic action of gold and copper crystals in the growth of carbon nanotubes

Multi-wall carbon nanotubes are grown in a chemical vapor deposition process by using bulk gold and copper substrates as catalysts. Nanotube growth starts from a nanometer-sized roughness on the metal surfaces and occurs in a mechanism where the catalyst particle is either at the tip (Au) or root (Cu) of the growing nanotube. Whereas Au leads to nanotubes with good structural perfection, nanotubes grown from Cu show a higher density of defects. High-resolution transmission electron microscopy shows the bonding between Au and carbon at the metal-nanotube interface whereas no bonds between Cu and carbon occur. Highly mobile Au or Cu atoms adsorb at the growing edge of a carbon nanotube from where diffusion along the nanotube wall can lead to the formation of Au or Cu nanowires inside the central hollow of carbon nanotubes.     

辅助气体对RF-PECVD制备碳纳米管薄膜形貌的影响

采用射频等离子体增强化学气相沉积(RF-PECVD)技术,以Ni为催化剂,经600℃裂解C2H2在Si基底上制备出定向碳纳米管薄膜。采用扫描电子显微镜(SEM)表征了刻蚀后Ni颗粒与沉积的碳纳米管薄膜的形貌。研究了辅助气体对等离子体预处理催化剂与碳纳米管生长的影响。结果表明:辅助气体(H2与N2)流量比对催化剂颗粒尺寸、分布以及碳纳米管生长有显著影响;合适的气体流量比有利于减少碳纳米管薄膜的杂质颗粒,促进其定向生长。预处理过程中气体流量比H2:N2=20:5时,预处理后催化剂Ni颗粒分布密度大、粒径小且分布范围窄,适合碳纳米管均匀着床;沉积生长碳纳米管薄膜时,H2:N2=20:15可得到纯度高、定向性好的碳纳米管。     

The preparation of carbon nanotubes by dc arc discharge using a carbon cathode coated with catalyst

Carbon nanotubes (CNTs) were grown using a dc arc discharge process and relevant process parameters were investigated. Unlike the usual process in which a carbon anode is filled with metal catalyst powder, CNTs were prepared using a carbon cathode on which the metal catalyst had been deposited using an electroplating system. Various transition metals were investigated. The results show that multi walled carbon nanotubes (MWNTs) and single walled carbon nanotubes (SWNTs) can both be synthesized using this technique. SWNTs are detected in the soot sample collected around the cathode, whereas the MWNTs are detected mainly in the deposit sample collected from the central area of the cathode. The CNT yield varies depending on the catalyst used and the properties of a good catalyst are discussed.     

Growth control of carbon nanotubes by plasma-enhanced chemical vapor deposition and reactive ion etching

A novel process for growth of carbon nanotubes using plasma processes is reported. This process consists of formation of nanotips on substrate and growth of carbon nanotubes on it. The formation of the nanotips, which were formed under an intention to control formation of catalyst nanoparticles, was carried out on substrates by reactive ion etching. After the nanotips formation, the carbon nanotubes were grown on the substrate by plasma-enhanced chemical vapor deposition. Our results showed that the introduction of the nanotips on surface gave lower density and smaller diameter growth of carbon nanotubes than those without the structure.     

Effect of Co and Ni nanoparticles formation on carbon nanotubes growth via PECVD

The effect of cobalt (Co) and nickel (Ni) nanoparticle catalysts on the growth of carbon nanotubes (CNTs) were studied, where the CNTs were vertically grown by plasma enhanced chemical vapour deposition (PECVD) method. The growth conditions were fixed at a temperature of 700 °C with a pressure of 1000 mTorr for 40 minutes with various thicknesses of sputtered metal catalysts. Only multi-walled carbon nanotubes are present from the growth as large average diameter of outer tube (～10–30 nm) were measured for both of the catalysts used. Experimental results show that high density of CNTs was observed especially towards thicker catalysts layers where larger and thicker nanotubes were formed. The nucleation of the catalyst with various thicknesses was also studied as the absorption of the carbon feedstock is dependent on the initial size of the catalyst island. The average diameter of particle size increases from 4 to 10 nm for Co and Ni catalysts. A linear relationship is shown between the nanoparticle size and the diameter of tubes with catalyst thicknesses for both catalysts. The average growth rate of Co catalyst is about 1.5 times higher than Ni catalyst, which indicates that Co catalyst has a better role in growing CNTs with thinner catalyst layer. It is found that Co yields higher growth rate, bigger diameter of nanotube and thicker wall as compared to Ni catalyst. However, variation in Co and Ni catalysts thicknesses did not influence the quality of CNTs grown, as only minor variation in I_G/I_D ratio from Raman spectra analysis. The study reveals that the catalysts thickness strongly affects not only nanotube diameter and growth rate but also morphology of the nanoparticles formed during the process without influencing the quality of CNTs.     

包覆纳米镍粒子的碳纳米管磁性研究(英文)

通过溶胶 -凝胶超临界干燥技术制备出NiO SiO2 比为 1.2的二元气凝胶纳米催化剂 ,并以气凝胶为催化剂通过化学气相热解法合成了碳纳米管 ;碳纳米管的合成是在石英管式炉中完成。将催化剂置于石英舟中 ,在流动氮气中将管式炉加热至所需的温度 ,然后通入甲烷、氢气混合气体 ,热解反应 30min～ 6 0min后形成碳纳米管。反应结束后 ,生成的碳纳米管在氮气氛中冷却至室温。采用XRD、SEM、TEM、HRTEM、Raman分析手段对制得的碳纳米管进行了表征 ,并测定其磁化系数。结果表明 :裂解产物主要由碳纳米管和纳米镍粒子组成 ,且纳米镍粒子包覆于碳纳米管的顶端。这种包覆纳米镍粒子的碳纳米管的比饱和磁化强度和矫顽力分别为 0 .6 6A·m2 ·kg- 1 和2 0 15 7A·m- 1 。     

The growth of aligned carbon nanotubes on quartz substrate by spray pyrolysis of hexane

Vertically aligned multiwall carbon nanotubes were grown by spray pyrolysis of hexane as the carbon source in the presence of ferrocene as catalyst precursor on a quartz substrate. In recent work we used optimal experimental parameters for the feeding method, reactor conditions, reaction temperature and time, concentration of catalyst and flow rate of feed and gas. The process parameters were chosen so as to obtain multiwall carbon nanotubes and aligned multiwall carbon nanotubes. The tubes are around 15-80?nm in diameter. The morphology and structure of the samples were characterized by x-ray diffraction, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy analyses.     

用ECR-CVD方法制备定向碳纳米管

以FeaO4纳米粒子为催化剂,CH4和H2为气源,采用电子回旋共振微波等离子体化学气相沉积技术(ECR-CVD)在多孔硅基底上制备出定向生长的碳纳米管.研究了气氛组成、气压、温度和反应时间对碳纳米管生长特性的影响.使用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和拉曼光谱(Raman spectrum)表征了样品的形貌和结构.结果表明:气氛组成和气压影响了反应腔内离解碳的浓度,从而影响碳纳米管的成核、生长速度及定向生长;温度的变化改变催化剂的尺寸从而改变碳纳米管的直径,在过低的温度下碳纳米管不能实现定向生长;碳纳米管随着反应时间的延长而不断增长,但超过一定时间后催化剂颗粒被碳包覆而失去催化作用,生长停止.