催化剂结构与形态对碳纳米管生长的影响

采用溶胶-凝胶超临界流体干燥技术制备了含铁、钴的纳米SiO2复合气凝胶催化剂,用于碳纳米管和纳米碳包覆磁性纳米粒子的合成。利用N2物理吸附、XRD、TEM、HRTEM、EDS、SAED等手段对催化剂在不同温度下处理后晶型的转变、形态的变化进行了分析,并考察了催化剂对碳纳米管形貌、结构和碳增重率的变化。结果表明:随着处理温度从600℃升高到1000℃,催化剂比表面积从312.4m2 g降低到79.6m2 g,催化剂粒子从非晶态向晶态转变,粒径从5nm增大至60nm左右,碳的增重率从254.8%下降41.5%。采用低温处理的催化剂,碳产物中以碳纳米管为主,而采用较高温度处理后的催化剂,碳产物中则以碳包覆粒子为主,且随处理温度的升高碳包覆粒子的含量逐渐增加。     

铁催化分解二甲硫醚制备碳纳米管的研究

以二甲硫醚为碳源,Fe/MgO为催化剂,采用化学气相沉积法制备了碳纳米管。通过SEM、Raman、XRD、TEM表征方法研究了实验合成条件对碳纳米管产物的形貌和微结构的影响。结果表明,二甲硫醚的蒸汽浓度对碳纳米管的形貌和产量有重要影响。较高的二甲硫醚浓度会使催化剂的活性降低,制备出的碳纳米管较短且石墨化程度也较差。生长碳纳米管的最佳二甲硫醚浓度范围为2.69%～3.86%,且碳纳米管产物中有Y型碳纳米管的生成,并对其生长机理进行了初步讨论。     

温度对CVD法制备多壁碳纳米管的影响

以Fe／SiO2粉状物作催化剂用化学沉积法裂解乙炔制备出无序多壁碳纳米管,用TEM、XRD和DSC-TGA分析了反应温度对碳纳米管的影响。实验结果表明,反应温度分别为600、700和800℃时,制备出碳纳米管的直径相应为12～20、15～25和33～66nm,即碳纳米管的直径随着反应温度的升高而增大。同时随着反应温度的提高碳纳米管的石墨化程度也有明显的提高。因此碳纳米管的直径、石墨化程度等结构特性可以用反应温度来加以控制。     

衬底温度对碳纳米管生长和结构的影响

用CH4、NH3和H2为反应气体,利用等离子体增强热丝化学气相沉积在沉积有Ta缓冲层和Ni催化剂层的Si衬底上制备了准直碳纳米管,并用扫描电子显微镜和透射电子显微镜研究了它们的生长和结构随温度的变化.结果表明生长的准直碳纳米管是竹节型结构,其直径随衬底温度的降低而减小,生长速率随衬底温度的升高有一极值.从催化剂在衬底温度作用下的变化开始,分析了衬底温度对碳纳米管生长和结构的影响.     

反应温度对碳纳米管的影响

本文利用化学气相沉积( CVD)法,以乙烯为碳源气体,二茂铁为催化剂,在二氧化硅上制备出一系列碳纳米管,并通过拉曼光谱和扫描电子显微镜( SEM)对其形貌、结构和组分进行表征,分析反应温度对碳纳米管的影响.研究发现:当反应温度为860℃时,有均匀的碳纳米管薄膜生成,其管径和长度分别达到104 nm和95 μm,同时结构缺陷少,非碳管杂质较少,纯度较高.     

CO-Mo/MgO催化剂上甲烷化学气相沉积制备高纯度多壁碳纳米管

以甲烷为碳源,co-Mo/MgO为催化剂,通过气相化学沉积制备了直径均匀的多壁碳纳米管(MWC-NTs).采用溶胶-凝胶法所制双金属催化剂的组成为Co∶Mo∶MgO=5∶20∶75(质量比).热重分析表明多壁碳纳米管产率高达313.67%.催化剂对于多壁碳纳米管生长的选择性是91.17%(其余为无定形碳).透射电子显微镜分析显示:催化剂七生长的MWCNTs平均直径为6.2±0.5nm(平均±标准偏差).通过稀酸的简单纯化处理,纯化样品的催化剂残存率降至0.72%.     

热等离子射流法CO_2O_3/FeS催化裂解甲烷制备碳纳米管的研究

以CO_2O_3和FeS的混和物做催化剂前驱物,利用热等离子射流法制得包含碳纳米管的固相物,通过扫描电镜、透射电镜对产物进行表征并与高纯单质金属催化碳纳米管生长的类似文献报道做对比,证实其中碳纳米管密度大、纯度高、管径分布小、大部分为50～90nm的直线型多壁管且相互独立、管壁平滑、厚度约为10nm,在数量和质量上均可与已报道文献相比.结果表明,催化剂中微量氧的存在不仅不会影响催化效果,还有助于提高产物中碳纳米管纯度.     

以生物质为催化剂化学气相沉积制备碳纳米管

以富含过渡金属元素铁的天然生物质黑木耳、紫菜、香菇、黑芝麻的炭化粉末作为催化剂前驱体,天然气为碳源,采用化学气相沉积工艺制备了碳纳米管(CNTs)。所制CNTs阵列的管径较窄,排列整齐,归因于蘑菇、紫菜和黑芝蔴的碳含量高及铁基纳米颗粒分散均匀。采用黑木耳为催化剂所制CNTs的直径也较窄,但杂乱生长,可能是由于黑木耳的碳含量低及铁基纳米颗粒分布不均匀所致。     

介孔材料对纳米碳管制备及结构的影响

本文报道了制备含Fe的硅介孔材料以及利用该介孔材料生长纳米碳管的工艺条件.利用化学气相沉积法,以含有Fe的介孔材料为催化剂,在800%条件下催化分解乙炔气体制备纳米碳管,同时利用扫描电子显微镜（SEM）及透射电子显微镜（TEM）对制备的纳米碳管的形貌及结构进行观察表征.实验结果表明该介孔材料可以在一定程度上控制纳米碳管的结构及形貌,得到直径均一、笔直开口的纳米碳管.     

Fe-Ni双活性金属催化剂制备碳纳米管的研究

利用催化化学气相沉积法,以Fe-Ni双活性金属为催化剂来制备碳纳米管.其中,Fe-Ni双活性金属催化剂由柠檬酸络合法制得.催化剂的组成和碳纳米管的形貌分别用XRD和TEM来进行了表征.实验结果表明,由于催化剂中的活性成分Fe-Ni形成了固溶体,相互之间产生了协同作用,使得其催化性能大大提高,因而由其制备的碳纳米管的产率明显高于由单一活性金属Fe或Ni催化剂所制备碳纳米管的产率.特别当双活性金属催化剂中的Fe的摩尔百分含量为75%时,产率为最高,达到2000%(gCNTs/gcatalyst precursor·h),这约是相同制备条件下,由单一活性金属Fe或Ni所得到碳纳米管产率的6或4倍.     

Influence of catalyst particles on multi-walled carbon nanotubes morphology and structure

Multi-walled carbon nanotubes (MWCNTs) have been successfully grown by Chemical Vapor Deposition (CVD) method. Elucidating the key characteristics of catalyst sources that affect carbon nanotubes growth is of great importance for improving and control MWCNTs morphology and structure. In this work we present a systematically study of CVD parameters, such as catalyst source, substrate morphology and temperature and how it affects carbon nanotubes synthesis. The novelty of this work lies on the catalyst composition. Two specific catalyst sources were analyzed: (i) Fe₂Co and (ii) Fe₂Co with ferrocene. Cyclic Voltammetry results confirmed the presence of Fe²⁺ in the Fe₂Co with ferrocene solution. X-Ray Diffraction analysis confirmed the presence of iron particles on the substrate surface after its submission to growth conditions. Raman results suggested an improvement in carbon nanotubes crystalline quality catalyzed by Fe₂Co with ferrocene. For tridimensional substrates such as fibers, the Fe₂Co with ferrocene provided aligned CNTs with lower defects density noticed in Raman spectra and SEM micrographs. Finally, we corroborated the Fe²⁺ encapsulation relation with the growth mechanism and MWCNTs formation.     

Effect of temperature for synthesizing single-walled carbon nanotubes by catalytic chemical vapor deposition over Mo-Co-MgO catalyst

The influence of temperature on synthesizing single-walled carbon nanotubes (SWCNTs) by catalytic chemical vapor deposition of methane over Mo-Co-MgO catalyst was studied by Transmission Electron Microscope (TEM) and Raman scattering. The Mo-Co-MgO bimetallic catalyst was prepared by decomposing the mixture of magnesium nitrate, ammonium molybdate, citric acid, and cobalt nitrate. The results show that Mo-Co-MgO bimetallic catalyst is effective to synthesize SWCNTs. By using Mo-Co-MgO bimetallic catalyst, generation of SWCNTs even at 940 K was demonstrated. The optimum temperature of synthesizing SWCNTs over Mo-Co-MgO bimetallic catalyst may be about 1123 K. At 1123 K, the diameters of SWCNTs are in the range of 0.75–1.65 nm. The content of SWCNTs is increased with the increase of temperature below 1123 K and the carbon yield rate is also increased with the increase of synthesis temperature. Therefore, the amount of SWCNTs increases with the increase of temperature below 1123 K. However, above 1123 K, the content of SWCNTs is decreased with the increase of temperature; therefore, it is not effective to increase the amount of SWCNTs through increasing synthesis temperature above 1123 K.     

Synthesis of binary and triple carbon nanotubes over Ni/Cu/Al2O3 catalyst by chemical vapor deposition

Novel binary and triple carbon nanotubes (CNTs) with one common catalytic particle encapsulated have been synthesized using Ni/Cu/Al₂O₃ catalyst, which was produced by a sol-gel method. But when using Ni/Al₂O₃ as catalyst, a mass of common CNTs, that is, one CNT with one catalytic particle encapsulated, was obtained. The results showed that copper-element doping to the Ni/Al₂O₃ catalyst played a key role in the synthesis of CNTs, signifying a novel approach to modify the Ni/Al₂O₃ catalyst. Based on the transmission electron microscopy observations, a simple growth mechanism was developed to describe the growth of the binary or triple CNTs, which could be well explained by a diffusion segregation process.     

Growth of carbon nanotubes directly on a nickel surface by thermal CVD

A simple method of growing carbon nanotubes directly on nickel substrate without chemical pretreatment is reported. It is demonstrated that carbon nanotubes growth is directly affected by the roughness on the surface. Carbon nanotubes density is large in each growth zone observed on the surface; these zones being spread sparsely for coarse roughness of the surface. The density of carbon nanotubes decreases and the number of growth zones increases as the roughness on the surface is reduced. The above trend was not affected with C₂H₂ flow time changing from 10 to 2 min. A similar result was obtained using a Ni alloy as substrate, but the effect of surface roughness on the growth of CNTs was less pronounced. The CNTs grown on the Ni alloy were free of amorphous carbon and uniformly distributed.     

洁净单壁碳纳米管在Fe2O3／Al2O3二元气凝胶催化剂上的水辅助合成

分别以甲烷-氧气和甲烷-氢气-水的混合气作为反应气源,利用Fe2O3/Al2O3二元气凝胶作为催化剂于900℃反应30min合成了单壁碳纳米管.并采用SEM、XRD、TEM,高分辨透射电子显微镜(HRTEM)以及Raman光谱等分析技术对所制得的碳产物的结构和形貌进行了表征,以研究反应气氛中水蒸气的引入对单壁碳纳米管生长的影响.结果表明:反应气氛的组成对最终所形成的碳产物的产率和结构有着密切的关联.通过控制氢气载入甲烷-氢气-水的混合气氛中水蒸气的量可以合成低无定形碳的沽净单壁碳纳米管.     

调变Ni／Mo／MgO催化剂中Ni／Mo比例可控合成薄壁碳纳米管

采用摩尔分数1%Ni及负载少量Mo的Ni/MO/MgO催化剂裂解甲烷合成薄壁碳纳米管.通过SEM、TEM、XRD和Raman光谱表征方法研究了碳纳米管直径和催化剂中Ni/Mo比例关系.实验发现:通过控制Ni/Mo比例可以调变催化剂颗粒大小以及活性相.TEM及XRD表征发现,随着Ni/Mo比例的降低,金属Mo相逐渐从NiMo合金相中析出.NiMo合金相对应的活性组分颗粒很小,容易催化裂解甲烷形成薄壁碳纳米管;而后析出的Mo相则主要形成了大管径厚壁的碳纳米管.当Ni/Mo比例为6时可以高选择性地获得窄分布,内径为1.3nm,外径为3.0nm的溥壁碳纳米管.Raman光谱进一步验证了碳纳米管含有较少的缺陷.薄壁碳纳米管形成的关键因素主要体现为碳在其表而的快速扩散以及小颗粒的碳纳米管催化剂活性相控制.     

Scalable preparation of carbon nanotubes by thermal decomposition of phenol with high carbon utilizing rate

Practical application of carbon nanotube would have to be determined by a matter of its economical and large-scale preparation. In this study, phenol was used as carbon resource to fabricate carbon nanotubes with large scale in home-made chemical vapor deposition setup. The as-prepared carbon nanotubes are of multi-walls with bamboo compartments, and of having a limited distribution in diameter of 10-15 nm and length of several decades μm. In particular, in this preparation the carbon transformation rate from the carbon content in used phenol to carbon nanotubes is 75%, much higher than the previous reports. Hence this work would be of significance for the industrial preparation of carbon nanotubes even their practical applications.     

The effect of temperature on the growth of carbon nanotubes on copper foil using a nickel thin film as catalyst

Growth of carbon nanotubes (CNTs) on bulk copper foil substrates has been achieved by sputtering a nickel thin film on Cu substrates followed by thermal chemical vapor deposition. The characteristics of the nanotubes are strongly dependent on the Ni film thickness and reaction temperature. Specifically, a correlation between the thin film nickel catalyst thickness and the CNT diameter was found. Two hydrocarbon sources investigated were methane and acetylene to determine the best conditions for growth of CNTs on copper. These results demonstrate the effectiveness of this simple method of directly integrating CNTs with highly conductive substrates for use in applications where a conductive CNT network is desirable.