乙醇火焰中的一维碳纳米材料及其生长机理研究

文章利用扫描电镜（SEM）、透射电镜（TEM）系统观察和研究了乙醇燃烧火焰中合成的具有各种不同形貌特征的一维碳纳米材料。观察发现燃烧产物中除了“空心”碳纳米管和平直“实心”碳纳米纤维以外,还包括锥状、单螺旋型、双螺旋型、带状、节状、疏松状、节状-螺旋混合型、平直-螺旋混合型等形貌特殊的一维碳纳米材料。研究认为影响它们生长的主要因素有：Fe和Ni元素与碳的亲和力的差异、基板预处理、火焰的宽区域和不稳定性等。对火焰中各种形貌一维碳纳米材料的生成机理和过程进行了分析和讨论。     

电场磁场控制一维碳纳米材料生长研究进展

施加电场或磁场是一种能够有效控制一维碳纳米材料（包括碳纳米管、碳纳米纤维）生长的方法。文章评述了近年来电场磁场控制一维碳纳米材料生长的研究进展,介绍了电场磁场施加于各种不同的碳纳米材料制备方法,并提出了该方法在未来的发展方向。     

纳米孔"炭"和纳米孔"碳"——对碳质多孔材料的几点思考

对碳质纳米孔隙材料提出一种新的分类方法——基于孔壁结构分类。根据这种方法，碳质多孔材料分为：纳米孔“碳”（石墨烯纳米孔材料）和纳米孔“炭”（类石墨微晶纳米孔材料）。具有相近比表面积的两种碳质材料由于具有不同的孔壁结构而可能具有完全不同的物理化学性质（比如：电化学性质）。文中简要介绍了两种新型的纳米孔“碳”——单壁微孔“碳”和碳纳米管-DNA杂化物以及区分纳米孔“碳”和纳米孔“炭”的重要判据：拉曼光谱。     

纳米材料产业化发展中的若干问题

纳米是一种长度单位，1nm等于10^-9m。按照实空间三维坐标体系，任何一种材料只要有其中一维的尺寸是纳米级的（1～100nm之间），即可称为纳米材料；而按照材料的外形又可划分为零维（颗粒）、一维（晶须、纤维、管）、二维（膜或薄膜）、三维（块体）纳米材料，其中三维（块体）纳米材料是一个例外，因为尽管其外形尺寸不是纳米级的，     

北京纳米材料产业发展分析简

一．概述1．纳米材料定义纳米材料广义上讲是指在三维空间中至少有一维处于纳米尺度范围或者由该尺度范围的物质为基本结构单元所构成的超精细颗粒材料的总称。一般纳米材料包括的基本条件是材料的特征尺寸在1～100nm之间及材料具有区别于常规尺寸材料的一些特殊物理化学性质。2．纳米材料分类根据不同的分类依据,纳米材料主要分为如下几类：按材质,可分为纳米金属材料、纳米非金属材料、纳米高分子材料和纳米复合材料,其中纳米非金属材料又可分为纳米氧化物材料、纳米陶瓷材料和其他非金属纳米材料;按照材料的形态,可分为零维纳米材料（纳米颗粒材料）、一维纳米材料（如纳米线、棒、丝、管和纤维等）、二维纳米材料（如纳米膜、纳米盘、超晶格等）、纳米结构材料即纳米空间材料（如介孔材料等）;按材料功能,可分为纳米生物材料、纳米磁性材料、纳米药物材料、纳米催化材料、纳米吸波材料、纳米智能材料、纳米环保材料、纳米热敏材料等。     

乙醇催化燃烧法制备竹节形碳纳米管

乙醇催化燃烧法可以方便的制备出碳纳米管和碳纳米纤维。介绍采用该方法制备出一种独特的竹节形的碳纳米管，利用乙醇作为碳源和燃料，提供材料生长所需的能量；利用Cu薄片作为基底；利用FeCl3或Fe（NO3）3作为催化剂先体。通过扫描电子显微镜（SEM），透射电子显微镜（TEM），对黑色絮状的沉积产物进行表征。实验结果表明，产物中的碳纳米管具有较好的竹节形结构。实验也表明制备的竹节形碳纳米管的形貌和微结构与其独特的制备条件有关，如：火焰的抖动，催化剂先体溶液的浓度，制备时间等。并对竹节形碳纳米管的形貌和生长机制进行了详细的讨论。     

碳纳米管及相关的一维纳米材料

简要介绍碳纳米管及其制备技术,以及利用碳纳米管的填充,包数和空间限制反应等方法合成其它材料的一维纳米结构,这此具有独特性质的一维纳米材料在纳米电子学,纳米光电子学、超高密度存储和扫描探针显微镜等领域有着潜在的应用前景。     

由煤或焦炭制备纳米碳质材料的新进展

评述了以煤为碳源制备富勒烯、纳米碳管、竹节形碳管、铁嵌入的纳米碳棒和由碳包覆的金属纳米粒子等各种纳米材料。认为：等离子体电孤放电法是由煤制备各种纳米碳质材料最常用的方法，随电弧条件及电极性质的不同，所制备的纳米碳质材料可有各种不同形态及结构、由于煤是分子固体而石墨是晶格固体，两种碳源的反应机理有明显不同。在等离子体电弧加热时，煤分解并产生许多具有简单芳烃结构的分子，在纳米碳质材料的形成过程中，这些分子可能作为纳米碳质材料的结构单元，同时原煤中的矿物质在合成过程中也起着重要作用，因此煤本身的性质对纳米材料的制备极为重要。煤是成本低廉且储量最丰富的碳源，将是大规模工业化生产纳米碳质材料最好的碳源之一。     

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。     

准一维纳米材料

准一维纳米材料是指在二维方向上为纳米尺度、长度为宏观尺度的新型纳米材料。这种材料研究历史接近30年,早在 1970年法国科学家就首次研制出直径为7纳米的碳纤维。1991年日本首次用高分辩电镜发现了碳纳米管。我国科学家解思深等人实现了碳纳米的定向生长,并成功合成了世界上最长的碳纳米管。     

低碳钢基体表面氧乙炔碳化焰法沉积纳米炭纤维

低碳钢经浓硝酸浸蚀预处理后,调节氧乙炔火焰成碳化焰,预处理过的低碳钢基体表面火焰沉积获得纳米炭纤维涂层。采用扫描电镜、X射线衍射和显微激光拉曼光谱等先进分析手段对其形态和结构进行了表征。研究发现纳米炭纤维相互缠绕弯曲,石墨化程度高,直径为80nm~100nm、长度为4μm~5μm,形态短而粗。纳米炭纤维相互排列紧密但与基体结合力弱易从低碳钢表面脱落,浓硝酸浸蚀预处理的低碳钢表面在火焰中形成大量氧化铁颗粒,催化纳米炭纤维成核生长。     

一维纳米材料的ECR-CVD方法制备

应用电子回旋共振微波等离子体化学气相沉积方法(ECR-CVD)进行了一维纳米材料的制备.以Fe3O4纳米粒子为催化剂,采用不同的气源,在多孔硅基底上制备出了碳纳米管、掺硼碳纳米管以及异质结构的纳米管.利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和 X射线光电子谱(XPS)对样品的形貌、结构及组分进行表征.     

Catalytic synthesis of carbon nanofibers and nanotubes by the pyrolysis of acetylene with iron nanoparticles prepared using a hydrogen-arc plasma method

Carbon nanofibers (CNFs) and carbon nanotubes (CNTs) were synthesized at different temperatures by the catalytic pyrolysis of acetylene with iron nanoparticles prepared using a hydrogen-arc plasma method. The obtained carbon nanomaterials were characterized by transmission electron microscopy and field-emission scanning electron microscopy. An iron nanoparticle was always located at the tip of CNFs or CNTs, whose diameter was approximately identical with the diameter of the iron nanoparticle. The structures of the products were closely related to the reaction temperature, and could be changed from fibers to tubes by simply increasing the temperature. CNFs were obtained at the reaction temperature of 550-650 °C. When the reaction temperature was increased to 710-800 °C, CNTs were obtained.     

The effect of catalyst evolution at various temperatures on carbon nanostructures formed by chemical vapor deposition

Solid carbon nanofibers (CNFs), hollow CNFs, metal-filled carbon nanotubes (CNTs), and carbon onions were synthesized by chemical vapor deposition (CVD) using a novel Ni/Y catalyst supported on Cu at different reaction temperatures. XRD, TEM, and EDS analyses reveal that the structure of the catalyst changes with increasing reaction temperature. The evolution of Y doped in Ni directly influences the morphologies of the products. At relatively low temperature, Y is doped in Ni and causes CNF formation, and when the temperature is increased to above 650 °C, Y separates from Ni as yttria nanoparticles and carbon onions are synthesized. The catalyst evolution and carbon nanostructure growth mechanism are discussed in detail.     

Hydrothermal synthesis of β-nickel hydroxide nanocrystalline thin film and growth of oriented carbon nanofibers

Novel well-crystallized β-nickel hydroxide nanocrystalline thin films were successfully synthesized at low temperature on the quartz substrates by hydrothermal method, and the oriented carbon nanofibers (CNFs) were prepared by acetylene cracking at 750 °C on thin film as the catalyst precursor. High resolution transmission electron microscopy (HR-TEM) measurement shows that thin films were constructed mainly with hexagonal β-nickel hydroxide nanosheets. The average diameter of the nanosheets was about 80 nm and thickness about 15 nm. Hydrothermal temperature played an important role in the film growth process, influencing the morphologies and catalytic activity of the Ni catalysts. Ni thin films with high catalytic activity were obtained by reduction of these Ni(OH)₂ nanocrystalline thin films synthesized at 170 °C for 2 h in hydrothermal condition. The highest carbon yield was 1182%, and was significantly higher than the value of the catalyst precursor which was previously reported as the carbon yield (398%) for Ni catalysts. The morphology and growth mechanism of oriented CNFs were also studied finally.     

Evaluation of the role of Au in improving catalytic activity of Ni nanoparticles for the formation of one-dimensional carbon nanostructures

In situ dynamic imaging, using an environmental transmission electron microscope, was employed to evaluate the catalytic activity of Au/SiO(2), Ni/SiO(2), and Au-Ni/SiO(2) nanoparticles for the formation of one-dimensional (1-D) carbon nanostructures such as carbon nanofibers (CNFs) and nanotubes (CNTs). While pure-Au thin-film samples were inactive for carbon deposition at 520 °C in 0.4 Pa of C(2)H(2), multiwalled CNTs formed from Ni thin films samples under these conditions. The number of nanoparticles active for CNF and CNT formation increased for thin films containing 0.1 mol fraction and 0.2 mol fraction of Au but decreased as the overall Au content in thin films was increased above 0.5 mol fraction. Multiwalled CNTs formed with a root growth mechanism for pure Ni samples, while with the addition of 0.1 mol fraction or 0.2 mol fraction of Au, CNFs were formed via a tip growth mechanism at 520 °C. Single-walled CNTs formed at temperatures above 600 °C in samples doped with less than 0.2 mol fraction of Au. Ex situ analysis via high-resolution scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDS) revealed that catalytically active particles exhibit a heterogeneous distribution of Au and Ni, where only a small fraction of the overall Au content was found in the portion of each particle actively involved in the nucleation of graphitic layers. Instead, the majority of the Au was found to be segregated to an inactive capping structure at one the end of the particles. Using density-functional theory calculations, we show that the activation energy for bulk diffusion of carbon in Ni reduces from ≈1.62 eV for pure Ni to 0.07 eV with the addition of small amounts (≈0.06 mol fraction) of Au. This suggests that the enhancement of C diffusion through the bulk of the particles may be responsible for improving the number of particles active for nucleating the 1-D carbon nanostructures and thereby the yield.     

A Novel Process for High-efficient Synthesis of One-dimensional Carbon Nanoraaterials from Flames

The substrate pre-treatment plays a key role in obtaining hollow-cored carbon nanotubes (CNTs) and solidcored carbon nanofibers (CNFs) from flames. This paper introduces a simply and high-efficient process by coating a NiSO4 or FeSO4 layer on the substrate as catalyst precursors. Comparing with the regular pretreatment methods, the present experiments showed that the coating pre-treatment provided the following advantages: 1) greatly shortening the synthesis time; 2) available variant substrates and carbon sources; 3) narrowing the diameters distribution. The sulfate is considered to be a crucial factor at the growth of CNTs and CNFs, because it increases the surface energy of catalyst particles and the surface specificity of sulfurs action in metallic grains. This novel process provides a possibility for high quality and mass production of CNTs and CNFs from flames.     

A Novel Process for High-efficient Synthesis of One-dimensional Carbon Nanomaterials from Flames

The substrate pre-treatment plays a key role in obtaining hollow-cored carbon nanotubes （CNTs） and solid-cored carbon nanofibers （CNFs） from flames. This paper introduces a simply and high-efficient process by coating a NiSO4 or FeSO4 layer on the substrate as catalyst precursors. Comparing with the regular pre-treatment methods, the present experiments showed that the coating pre-treatment provided the following advantages： 1） greatly shortening the synthesis time; 2） available variant substrates and carbon sources; 3） narrowing the diameters distribution. The sulfate is considered to be a crucial factor at the growth of CNTs and CNFs, because it increases the surface energy of catalyst particles and the surface specificity of sulfurs action in metallic grains. This novel process provides a possibility for high quality and mass production of CNTs and CNFs from flames.     

纳米纤维素/碳纤维-聚苯胺/碳纳米管电极的制备

目的以纳米纤维素/碳纤维复合膜为导电基底,制备纳米纤维素/碳纤维-聚苯胺/碳纳米管超级电容器电极。方法利用超声处理和真空抽滤制备纳米纤维素/碳纤维复合膜;利用原位聚合法制备聚苯胺和聚苯胺/碳纳米管复合材料;通过真空抽滤法制备纳米纤维素/碳纤维-聚苯胺电极和纳米纤维素/碳纤维-聚苯胺/碳纳米管电极。结果在纳米纤维素/碳纤维复合膜中,碳纤维形成了互穿导电网络结构,是良好的超级电容器电极导电基体;纳米纤维素/碳纤维-聚苯胺/碳纳米管电极具有良好的电化学性能,在扫描速率为5 mV/s的条件下,质量比电容为380.74 F/g,且在1000次循环测试后,电容保留率为88.05%。结论以纳米纤维素/碳纤维导电复合膜作为基体制备的纳米纤维素/碳纤维-聚苯胺/碳纳米管电极具有良好的电化学性能,可以作为超级电容器电极。     

Electrochemical characterization of carbon nanotube forests grown on copper foil using transition metal catalysts

Growth of vertical, multiwalled carbon nanotubes (CNTs) on bulk copper foil substrates can be achieved by sputtering either Ni or Inconel thin films on Cu substrates followed by thermal chemical vapor deposition using a xylene and ferrocene mixture. During CVD growth, Fe nanoparticles from the ferrocene act as a vapor phase delivered catalyst in addition to the transition metal thin film, which breaks up into islands. Both the thin film and iron are needed for dense and uniform growth of CNTs on the copper substrates. The benefits of this relatively simple and cost effective method of directly integrating CNTs with highly conductive copper substrates are the resulting high density of nanotubes that do not require the use of additional binders and the potential for low contact resistance between the nanotubes and the substrate. This method is therefore of interest for charge storage applications such as double layer capacitors. Inconel thin films in conjunction with Fe from ferrocene appear to work better in comparison to Ni thin films in terms of CNT density and charge storage capability. We report here the power density and specific capacitance values of the double layer capacitors developed from the CNTs grown directly on copper substrates.