垂直定向螺旋碳纳米管阵列的大量合成（英文）

以二甲苯作为碳源、二茂铁作为催化剂前驱体,采用催化裂解法大规模合成了具有不同螺距和螺旋直径、垂直于基底生长的碳纳米管阵列。通过拉曼光谱和高分辨透射电镜测试分析,结果表明,所制备的碳纳米管阵列分布均匀、石墨化程度高,且沿其长度方向具有不同的螺距和螺旋直径。由于在碳纳米管的生长过程中,会伴随着碳五环、碳七环与碳六环的生成,而碳六环是形成石墨晶格的基本结构单元。当碳六环网络结构中出现碳五环和碳七环时,螺旋形的碳纳米管就会形成。实验中螺旋形碳纳米管的产率约为4.5 mg/cm~2·h。螺旋形碳纳米管在高性能传感器、谐振器、纳米机械弹簧、电感等纳米电子器件中具有潜在的应用价值。     

气相生长纳米碳纤维的形态控制

报道了在浮动催化系统中,催化剂、促进剂以及苯/氢气比例等因素对气相生长纳米碳纤维形态的决定性作用和不同结构形态纳米碳纤维的选择生长.利用控制催化剂前体和促进剂的含量以及苯与氢气的比例等因素,制备了平直碳纳米管、弯曲碳纳米管、碳珠/纳米碳纤维、纳米碳纤维等不同结构的气相生长纳米碳纤维.实验结果表明,在浮动催化系统中,调节催化剂和促进剂的含量以及苯与氢气的摩尔比等关键性因素可以实现对气相生长纳米碳纤维形态结构的控制.     

含碳纳米管微波吸收材料的制备及其微波吸收性能研究

用竖式炉流动法,以二茂铁为催化剂,噻吩为助催化剂,苯为碳源通过催化裂解反应制备了碳纳米管,碳纳米管的外径为20-50nm,内径10-30nm,长度50-1000μm.分别以碳纳米管、羰基铁粉、碳纳米管与羰基铁粉的混合物为吸收剂制备了微波吸收材料,研究了上述三种微波吸收材料在2-18GHz的吸波性能,与纯碳纳米管和纯羰基铁粉微波吸收材料相比, 碳纳米管与羰基铁粉复合微波吸收材料在2-18GHz的吸收峰明显向低频移动.在含碳纳米管的微波吸收材料中,碳纳米管作为偶极子在交变电场的作用下,产生极化电流,电磁波的能量转换为其他形式的能量,瑞利散射效应和界面极化也是含碳纳米管微波吸收材料的主要吸波机理.     

等离子体射流辅助双催化剂原位催化法合成碳纳米管

以甲烷为碳源，Fe2O3／Ni为固定相催化剂，在常压条件下利用等离子体射流的高温将甲烷裂解生成碳自由基和氢气。同时联合原位催化法将碳自由基在Fe2O3／Ni双催化剂的共同作用下生长出碳纳米管。运用TEM和元素分析等测试手段对所得碳纳米管进行形貌、含量、结构的表征分析。结果表明，在一定反应条件下，可获得外径为10nm-30nm，管长约数百纳米、产率为75％左右的碳纳米管。与单催化剂相比，双催化剂的联合催化作用更有利于碳管的生长。     

浮游催化法半连续制取碳纳米管的研究

研究了浮浮催化法半连续制取碳纳米管的过程,根据透射电子显微镜等检测方法的结果,结合碳纳米管浮游催化的生长过程,论述了裂解温度、催化剂浓度,噻吩浓度等工艺参数对产物形态、产率及管径分布的影响,给出了正己烷为碳源情况下的最佳工艺参数。浮游催化法制的碳纳米管直径在３０ｎｍ－６０ｎｍ之间。     

浮动催化法制备碳管若干影响因素的研究

采用浮动催化法,利用卧式单一高温电阻炉,在以无水乙醇为碳源的反应体系中通过改变催化剂、反应气氛及流量、添加剂等实验参数合成了形貌不一的碳微纳米材料;采用SEM和Raman对产物进行了形貌观察和表征;比较了这些实验参数对浮动催化法制备碳纳米管的影响,并对其作用机理进行了简单分析.     

不同碳源制备碳基固体酸及其在水解纤维素中的应用

采用磁性碳纳米管(CNTs)、葡萄糖、炼焦酚渣为碳源,制得碳基固体酸催化剂.通过XRD、FTIR、13C NMR和SEM/TEM对其结构和活性基团进行表征,并且以经过预处理的微晶纤维素为纤维素模型物,以总还原糖得率为考察指标,利用制备的碳基固体酸非均相催化水解纤维素,比较了3种碳源制得的碳基固体酸在水解纤维素中的水解效率.研究结果表明,与传统原料葡萄糖制得的碳基固体酸相比,酚渣基固体酸碳环上除了含有酚羟基、羧基和磺酸基外,还含有其它碳基固体酸不具备的烷基侧链,这一结构优势对碳基固体酸催化剂的催化活性具有促进作用,能够提高碳基固体酸催化剂的水解效率;碳纳米管固体酸尽管具有致密的碳层结构、磺化后磺酸密度低,但高比表面积使其在非均相催化水解纤维素中表现出较高的活性.     

铁-硫协同作用对甲苯热解产物的影响

以甲苯为碳源，二茂铁为催化剂前躯体，噻吩为生长促进剂，在不同条件下通过甲苯催化热解反应得到不同的炭产物。借助TEM和XRD考察了催化剂和促进剂对热解产物形貌和结构的影响。研究发现，不使用任何催化剂和促进剂时，甲苯热解产物为纳米级球状炭颗粒，且部分颗粒之间会发生各向异性排列，形成链状物。单独使用二茂铁时，产物为球状炭包裹铁纳米颗粒。而二茂铁和噻吩同时使用时，产物的形貌随噻吩浓度的不同而变化。结果表明，铁和硫的协同作用对甲苯热解的反应过程和产物形貌影响很大。     

Cu/CNTs复合粉末制备工艺研究

采用原位合成和化学共沉积相结合的方法制备了Cr/Cu复合粉体催化剂,并将其用于碳纳米管的制备。利用XRD、SEM和TEM手段分别对其晶相、微观结构形态进行表征。研究表明,Cr含量对最终产物CNTs的结构有明显影响,10%(质量分数)Cr复合催化剂催化效果最好;不同煅烧温度下所得催化剂存在差异,其中700℃煅烧条件下可制备出结晶良好的Cr/Cu纳米复合催化剂。不同生长温度下所得复合粉体催化合成的碳纳米管品质形貌不一,其中800℃条件下可得到纯度高、表面光滑的碳纳米管。     

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.     

Crystallographic order in multi-walled carbon nanotubes synthesized in the presence of nitrogen

Multi-walled carbon nanotubes were synthesized by chemical vapor deposition from pure toluene and toluene/diazine mixtures using ferrocene as a catalyst precursor at 760 degrees C. As recently announced, characterization of the resulting nanotube films showed that, unlike pure carbon nanotubes, those grown in the presence of nitrogen have an extremely high degree of internal order, both in terms of the uniform chirality in the nanotube walls and of the crystallographic register between them. Here, the structure, defects, and morphology of the nanotubes were analyzed in depth using advanced electron microscopy techniques, and compared with existing models and observations. Nitrogen, which seems to be responsible for the dramatic structural order, was found to segregate preferentially within the core of the nanotubes.     

催化化学气相沉积过程中硫元素引发的炭形貌衍变

以甲苯为碳源,二茂铁为催化剂,噻吩为生长促进剂,通过化学气相沉积方法得到了多分叉结构的炭.借助SEM、XRD和EDX考察了硫元素对产物的形貌和微观结构的影响.结果表明,当甲苯中的噻吩体积分数在0.01%～1%变化时,产物形貌由树状逐渐衍变为分支状.树状炭南较长而笔直的多分叉炭纤维构成,而分支状炭则由较短且弯曲的炭纤维构成.XRD结果表明硫元素对产物的微观结构没有明显的影响.     

Conversion of toluene into carbon nanotubes using arc discharge plasmas in solution

In order to form nanocarbon materials, an arc discharge plasma method in hydrocarbon solvent is developed. In the case that the arc discharge is performed in toluene with nickel electrodes, tube-like nanocarbons were formed from toluene. The catalysis of the metal electrodes is found to be an important factor for the formation of the nanocarbons by the arc discharge in toluene. This method has a possibility of forming carbon nanotubes from liquid state solvents as a new carbon source by using catalyst ingredient as discharge electrodes.     

工业级原料制备碳纳米管的研究

为降低碳纳米管批量制备的原料成本,以焦化苯和二茂铁为主要原料(工业级),采用浮游催化热解法制备碳纳米管,用TEM、SEM、Raman、XRD等对产物的形貌和结构进行观察和表征,着重讨论了二茂铁的分解温度和苯的挥发温度对碳纳米管的制备及其形貌的影响,并对其影响机理进行了分析.研究表明:在噻吩体积分数为0.55 mL/100 mL苯、炉膛反应温度为1170℃的前提下,当二茂铁的分解温度为150℃、苯的挥发温度为50℃时,用工业级原料完全可以制备出碳纳米管,此时,碳纳米管的内径分布在0.88~1.15 nm.     

A one-step technique to prepare aligned arrays of carbon nanotubes

A simple effective pyrolysis technique has been developed to synthesize aligned arrays of multi-walled carbon nanotubes (MWCNTs) without using any carrier gas in a single-stage furnace at 700?°C. This technique eliminates nearly the entire complex and expensive machinery associated with other extensively used methods for preparation of CNTs such as chemical vapour deposition (CVD) and pyrolysis. Carbon source materials such as xylene, cyclohexane, camphor, hexane, toluene, pyridine and benzene have been pyrolyzed separately with the catalyst source material ferrocene to obtain aligned arrays of MWCNTs. The synthesized CNTs have been characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Raman spectroscopy. In this technique, the need for the tedious and time-consuming preparation of metal catalysts and continuously fed carbon source material containing carrier gas can be avoided. This method is a single-step process where not many parameters are required to be monitored in order to prepare aligned MWCNTs. For the production of CNTs, the technique has great advantages such as low cost and easy operation.     

Carbon dioxide as a carbon source for synthesis of carbon nanotubes by chemical vapor deposition

Carbon dioxide was successfully used as carbon source in the synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD) over Fe/CaO catalyst. The product was evaluated using both transmission electron microscopy (TEM) and Raman spectroscopy. Crooked and branching structures of multi-walled carbon nanotubes (MCNTs) with diameters of around 50 nm were observed on the TEM micrographs. Raman spectrum results show that the nanotubes have small defects, which is in agreement with the results of TEM. The influence of reaction variable such as furnace temperature and types of support media was also studied and the reaction mechanism was then discussed in this paper.     

Activated carbon catalyzing the formation of carbon nanotubes

Activated carbon (AC), a common carbon material, is employed as catalyst to synthesize carbon nanotubes (CNTs) through chemical vapor deposition (CVD) and detonation-assisted CVD methods. The results show AC can effectively catalyze CNT formation. From the microscopic observations on morphologies and structures of the formed intermediates, it is found that carbon-catalyzed CNT formation follows particle-wire-tube stepwise evolution mechanism, in which carbon nanoparticles first assemble into wire-like nanostructures, then evolve into nanotubes via particle-particle coalescence and structural crystallization.     

Synthesis of carbon nanotubes via toluene-thermal reduction process at moderate temperature

Carbon nanotubes were synthesized with toluene as carbon source and solvent at 350^∘C under stiring situation. In this process, La/Ni were used as catalyst, which were reduced via LaCl₃ and NiCl₂ with sodium as reductant. The products were characterized with X-ray powder diffractometer (XRD), transmission electronic microscopy (TEM) and Raman spectroscopy. The carbon nanotubes had diameters ranging from 100–200 nm and lengths ranging from hundreds of nanometers to several micrometers. The yield of carbon nanotubes, in accordance with TEM observations was estimated to be about 70%.