高纯度单壁碳纳米管的制备与表征

采用Co/Mo二元金属催化剂,以甲烷为碳源,通过热化学气相沉积法制备出高质量的单壁碳纳米管.分别用FE-SEM、HR-TEM和Ram an光谱对产物进行了表征.通过控制沉积条件,研究了沉积温度、碳源流量和氢气预还原对产物的影响,确定了最佳的制备工艺参数.     

Hydrogen production by reforming methane in a corona inducing dielectric barrier discharge and catalyst hybrid reactor

A novel corona inducing dielectric barrier discharge(CIDBD) and catalyst hybrid reactor was developed for reforming methane. This corona inducing technique allows dielectric barrier discharge(DBD) to occur uniformly in a large gap at relatively low applied voltage.Hydrogen production by reforming methane with steam and air was investigated with the hybrid reactor under atmospheric pressure and temperatures below 600°C.The effects of input power,O2/C molar ratio and preheat temperature on methane conversion and hydrogen selectivity were investigated experimentally.It was found that higher methane conversions were obtained at higher discharge power,and methane conversion increased significantly with input power less than 50 W;the optimized molar ratio of O2/C was 0.6 to obtain the highest hydrogen selectivity(112%);under the synergy of dielectric barrier discharge and catalyst,methane conversion was close to the thermodynamic equilibrium conversion rate.     

Well-aligned carbon nanotube array membrane synthesized in porous alumina template by chemical vapor deposition

A new simple approach was devetoped for preparing wetl-aligned and monodispersed carbon nanotube (CNT) array membrane within the cylindrical pores of anodic aluminum oxide (AAO) template by chemical vapor deposition (CVD). Acetylene and hydrogen were used in the CVD process with Fe-catalyzer at 700°C under 250 Pa. Scanning etectron microscope (SEM) and transmission etectron microscope (TEM) were employed to characterize the resulting highly-oriented uniform hollow tube array which had a diameter of about 250 nm, a tube density of 5.3x10⁸ cm² and a length of about 60 μm. The length and diameter of the tubes depend on the thickness and pore diameter of the template. The growth properties of the CNT array film can be achieved by controlling the structure of the template, the particle size of Fe-catalyzer, the temperature in the reactor, the flow ratio and the deposition time. The highly-oriented and uniform CNT array membrane fabricated by this simple method is very much useful in a variety of applications.     

Topography,structure, and formation kinetic mechanism of carbon deposited onto nickel in the temperature range from 400 to 850℃

The carbon deposition behavior on nickel particles was observed within the temperature range from 400 to 800℃ in a pure methane atmosphere. The topography, properties, and molecular structure of the deposited carbon were investigated using field-emission scanning electron microscopy (FESEM), temperature-programmed oxidation (TPO) technology, X-ray diffraction (XRD), and Raman spectroscopy. The deposited carbon is present in the form of a film at 400-450℃, as fibers at 500-600℃, and as particles at 650-800℃. In addition, the structure of the deposited carbon becomes more ordered at higher temperatures because both the TPO peak temperature of deposited carbon and the Raman shift of the G band increase with the increase in experimental temperature, whereas the intensity ratio between the D bands and the G band decreases. An interesting observation is that the carbon deposition rate is suppressed in the medium-temperature range (M-T range) and the corresponding kinetic mechanism changes. Correspondingly, the FWHM of the G and D1 bands in the Raman spectrum reaches a maximum and the intensities of the D2, D3, and D4 bands decrease to low limits in the M-T range. These results indicate that carbon structure parameters exhibit two different tendencies with respect to varying temperature. Both of the two group parameters change dramatically as a peak function with increasing reaction temperature within the M-T range.     

Gas and pressure effects on the synthesis of amorphous carbon nanotubes

The effects nf gas. pressure and temperature on the production of amorphous carbon nanotubes were investigated using an are discharging furnace at controlled temperature. Co/Ni alloy powder was used as catalyst. The discharge current was 80 A and voltage was 32 V The optimal parameters were obtained: 600℃ temperature, hydrogen gas and 500 torr pressure. The productivity and purity of amorphous carbon nanotubes are 6.5 gram per hour and 80%, respectively. The diameter of the amorphous carbon nanotubes is about 7—20 nm.     

Diameter-controlled growth of aligned single-walled carbon nanotubes on quartz using molecular nanoclusters as catalyst precursors

Molecular nanoclusters containing Fe and Mo atoms have been used as catalyst precursors for the growth of single-walled carbon nanotubes (SWNTs) on stable temperature (ST)-cut quartz substrates by chemical vapor deposition. Attribute to the uniform catalyst nanoparticles and the confinement effect of the crystalline substrates, well-aligned SWNTs with narrow diameter distribution have been synthesized. Atomic force microscopy measurements show that the mean diameter of the nanotubes obtained by thermal decomposition of ethanol at 900°C is 0.76 ± 0.16 nm, which is the smallest among all reported results for aligned SWNTs. The mean diameter of the nanotubes increases with growth temperature. In addition to using identical nanoclusters as the catalyst precursors, the avoidance of annealing treatment of catalyst precursors is also a key point for obtaining SWNTs with controlled diameters. Using these identical nanoclusters as catalyst precursors and carefully tuning the growth parameters make us closer to the ultimate goal of controlling the chirality of SWNTs.     

Synthesis of carbon nanotube array using corona discharge plasma-enhanced chemical vapor deposition

A corona discharge phasma-enhanced chemical vapor deposition with the features of atmospheric pressure and low temperature has been developed to synthesize the carbon nanotube array ,The array was synthesized from methane and hydrogen mixture in anodic aluminum oxide template channels in that cobalt was electrodeposited at the bottom.The characterization results by the scanning electron microscopy,transmission electron microscopy,energy dispersive X-ray spectroscopy and Raman spectroscopy indicate that the array consists of carbon nanotubes with the diameter of about 40 nm and the length of more than 4 μm, and the carbon anotubes are mainly restrained within the channels of templates.     

单壁纳米碳管制备的新进展

综述了成熟的且能大量合成纯度较好的单壁纳米碳管(SWCNTS)的制备方法,分析不同的制备方法的特点以及关键的工艺参数,并在同一制备方法中讨论工艺条件的改变对合成SWCNTS产物的影响.催化剂及碳源种类以及它们的配比在制备SWCNTS中起决定重要作用.此外,电弧电流及电压、惰性气体种类及压力、电极的冷却速度等因素是电弧法制备SWCNTS的重要参数.激光束的强度、环境温度、惰性气体的种类及流速、脉冲的频率及间隔时间等工艺参数决定激光蒸发法制备SWCNTS的产物.而碳源的流量,催化剂粒度大小、反应温度,气体压强以及基体材料等在有机气体催化热解法合成SWCNTS中发挥重要作用.     

不同载体负载的钴基费-托合成催化剂性能研究

考察了碳纳米管与传统氧化物作为载体负载的钴基催化剂用于费-托合成反应的性能.采用等体积浸渍法制备了钴基催化剂,并对催化剂进行了TPR、TEM、H2-化学吸附等表征分析.结果表明,Co/SiO2和Co/CNTs催化剂具有较低的还原温度且Co/SiO2催化剂还原峰较狭窄.TEM的结果显示Co/γ-Al2O3催化剂和Co/CNTs催化剂中的钴颗粒粒径分布范围较宽,而Co/SiO2催化剂的钴颗粒粒径分布较为均匀,这是导致其还原峰温范围不同的原因之一.费-托合成反应结果显示Co/CNTs催化剂和Co/γ-Al2O3催化剂具有比Co/SiO2催化剂更高的一氧化碳转化率,而Co/γ-Al2O3和Co/SiO2催化剂具有比Co/CNTs催化剂更高的C5＋选择性和较高的α值.     

低渗透性煤层注液态CO2置换驱替CH4试验

针对低渗透性煤层瓦斯难以抽采的问题,结合液态CO_2低温、低黏、渗流阻力小、相变增压等特性,提出低渗透性煤层注液态CO_2置换驱替CH_4技术。在韩城矿区桑树坪二号井开展煤层注液态CO_2置换驱替CH_4工业性试验,开发了压注工艺系统,确定了压注关键性参数,判定了CO_2置换驱替CH_4技术效果。试验结果表明:液态CO_2压注时压力呈现波动特性,起始升压速率较快,达到2.5MPa左右时趋于稳定;压注管路瞬时流量为0.6~1.4m~3/h,累计压注液态CO_2为6.0m~3;以压注过程中检验孔内CO_2体积分数为指标,判定试验有效影响半径达到18m。试验区域瓦斯抽采体积分数是原始体积分数的2.5倍,抽采纯量是原始纯量的3.5倍,相比瓦斯抽采效率提高。     

Role of support in photothermal carbon dioxide hydrogenation catalysed by Ni/CexTiyO2

Nickel was supported on varied ratios of ceria-titania mixed oxides(Ni/Ce_xTi_yO_2) to evaluate the role the support plays in photothermal carbon dioxide hydrogenation to produce methane. In a batch photothermal reactor system, Ni/CeO_2 achieved the highest conversion rate, reaching a conversion of 93% in approximately60–90 min. To decouple the influence of light and heat, the CO_2 hydrogenation was examined in an in-house designed photothermal reactor, whereby heat can be applied externally. Decoupling experiments revealed that heat from the thermalisation by light was the main driving force for the reaction. In addition, the conversion and temperature profile of the different catalysts revealed that the catalyst performance was governed by catalyst reducibility. H_2-TPR analyses showed that the Ni became more readily reducible with increasing Ce O_2 content,suggesting that the oxide plays a role in activating the Ni. The reduction temperature of the nickel catalyst(following a reduction and passivation process) was below 200 °C, which meant that the inherent heating temperature of the photothermal reactor was sufficient to initiate Ni/CexTiyO_2 catalyst activity. The exothermic methanation reaction was then able to heat the system further, ultimately reaching a temperature of 285 °C. The ancillary rise in temperature promotes further nickel reduction and methane formation, leading to a "snow-ball"effect. The findings demonstrate that, to achieve a "snow-ball" effect in a photothermal system, designing a catalyst which is easy to reduce, active for CO_2 hydrogenation, and capable of converting light to heat for its initial activation is critical.     

Synthesis of carbon nanotube array using corona discharge plasma-enhanced chemical vapor deposition

Carbon nanotube array plays an important role in the area of nanomaterials due to its potential applications, e.g. as field emitter in flat panel display[1,2] and as template for synthesizing arrays of other important nanomaterials[3]. Anodic aluminum oxide (AAO) template possesses an ordered porous structure that is formed through self-or- ganization during anodization[4,5], and is widely used to synthesize one-dimensional nanomaterial arrays[6]. Carbon nanotubes are usually assembled into t…     

镍基催化剂上催化裂解甲烷生长碳纳米管

以共沉淀法制备的 Ni-Al、Ni-Cu-Al和 Ni-L a-Al为催化剂 ,甲烷为碳源 ,在 773～ 10 2 3 K制备碳纳米管 ( CNTs) ,并通过 TEM和 XRD表征了 CNTs的部分性质 ,讨论了催化剂、反应时间和反应温度对 CNTs形貌、结构和产率的影响。结果表明 ,不同催化剂在相同温度下制备的 CNTs的形貌和结构有很大差异。Ni-Al催化剂上生长的 CNTs倾向于碳纤维结构。Ni-Cu-Al催化剂上生长的 CNTs具有节状结构。Ni-La-Al催化剂上生长的 CNTs管腔较大、管径较均匀且石墨化程度最高。在 10 2 3 K下 ,各种催化剂的活性都是在反应初期较高 ,然后随反应时间降低。Ni-Al催化剂在 2 h后活性降低很快 ,在 5 h后完全失活。Ni-Cu-Al和 Ni-La-Al催化剂活性随时间降低较缓慢 ,最后分别在 10 h和 15 h后完全失活。各种催化剂上生长的CNTs的产率随反应温度变化而变化。Ni-Al、Ni-Cu-Al和 Ni-La-Al催化剂上制备的 CNTs分别在 92 3 K、973 K和高于 10 2 3K左右达到最高产率     

低温催化裂解烷烃法制备碳纳米管

实验发现，甲烷可在较低温度（７２３Ｋ）下，在一种Ｎｉ催化剂上分解生成碳纳米管．透射电镜测试结果显示，通过此法制得的碳纤维几乎都具有管状结构．碳纳米管的外径，管长及产率明显地受催化剂的结构、性能，反应温度和原料气流速所支配．将所制得的产物浸泡在稀硝酸溶液中，溶去催化剂颗粒，经水洗，并于４７３Ｋ温度下烘干，可达到将碳纳米管产物与催化剂分离、纯化的目的．     

压强对PECVD制备碳纳米管的影响

采用等离子体增强化学气相沉积技术(PECVD),以C2H2、H2和N2为反应气体,在镀Ni催化剂的Si基底上成功制备出多壁碳纳米管薄膜.并通过扫描电镜拍摄其表征,系统、深入地研究了沉积压强对碳管形貌的影响.结果表明:沉积压强对催化剂的刻蚀和碳纳米管薄膜的形成起着重要作用,获得定向性良好、分布均匀、密度适中的碳纳米管的最佳沉积压强是300 Pa.     

催化裂解法制备螺旋状碳纳米管的实验研究

在硅片上用直流溅射镀铁的方法制备催化剂 ,通过乙炔在 70 0°C下催化裂解制备碳纳米管 .对热解产物进行了扫描电镜观察和 X射线衍射测试 .本文通过对有氢气预处理和没有氢气预处理两种情况下催化裂解法制备的碳纳米管的形貌、管径大小等性质的研究 ,来初步揭示螺旋状碳纳米管的生长机理 .     

用浮动催化裂解法制取单壁碳纳米管

为寻找一种可以批量制备高质量、高产率单壁碳纳米管的方法 ,对浮动催化裂解碳氢化合物法制取单壁碳纳米管进行了研究。实验采用苯为碳源 ,二茂铁为催化剂 ,氢气为载气 ,噻吩为添加剂。采用扫描电镜、透射电镜、高分辨透射电镜以及拉曼谱等方法对产物进行检测与评估 ,分析了参数对产物的影响。结果表明 ,裂解温度越高 ,越有利于单壁碳纳米管的生长 ;发现通过碳源和直接通入反应室的 H2 流量比为 1:2时 ,较利于单壁碳纳米管的生长。浮动催化裂解法制备出来的单壁碳纳米管直径约为 1nm,直径分布较均匀 ,并且可以半连续、低成本地生产     

Effects of Temperature and Catalyst Concentration on the Growth of Aligned Carbon Nanotubes

The effects of preheating and pyrolysis temperatures and catalyst concentration on the synthesis of aligned carbon nanotubes （CNTs） using ferrocene as the catalyst and xylene as the carbon source in chemical vapor deposition were experimentally studied. The as-grown aligned CNTs were characterized by field emission scanning electron microscopy, transmission electronic microscopy, high-resolution transmission electronic microscopy, and Raman spectroscopy. The growth rate, the diameters, and the degree of crystal structure of the aligned CNTs were all found to depend on the preheating and pyrolysis temperatures and the catalyst concentration. The optimized conditions for the growth of aligned CNTs resulted in a rapid growth rate of 20.4 um/min, with the CNTs having a good, uniform crystal structure, and clean surfaces with little amorphous carbon. The results also show that higher preheating temperatures and lower ferrocene concentrations favor the growth of single-walled CNTs.     

多壁碳纳米管及其对H_2吸附体系的Raman光谱

利用原位和非原位紫外 Raman谱法 ,对以 CH4 为碳源 ,由催化法制备的多壁碳纳米管( MWCNTs) ,K -修饰的该类 MWCNTs,以及它们对 H2 的吸附体系进行了 Raman谱表征 ,观测到可分别归属于类石墨结构的基频模 D和 G以及它们的三阶组合频 ,表面 C-H3基和 C-H2 基等的特征Raman峰 ;H2 在这类碳纳米管上的吸附态包括解离吸附生成表面 C-H3和非解离吸附分子氢 H2 ( a) ;在相同实验条件下 ,K -修饰体系上这两类氢吸附物种的表面浓度都比未经 K -修饰的相应体系高 .     

Spread of double-walled carbon nanotube membrane

A single-layer double-walled carbon nanotube (DWNT) membrane, with 100 cm2 in area, 50 nm in thickness, was spread by adding a few drops of ethanol (or acetone) on the purified DWNTs. Compared with acetone, ethanol is more efficient in spreading DWNT films. The spreading rate of DWNT mem-brane increases with the ethanol concentration, and it also first increases with temperature (below 60℃), then decreases as the temperature rises to above 60℃.