碳氢化合物催化裂解法制备碳纳米管所用催化剂的研究进展

目前,制备碳纳米管的方法甚多,碳氢化合物催化裂解法是最有希望实现大规模生产的合成方法.该方法中催化剂的选择又是成功制备碳纳米管的关键,因此对当前使用的各种催化剂进行了分类讨论和总结.     

碳纳米管的催化裂解聚苯乙烯法的制备及其表征研究

利用流动催化裂解法以聚苯乙烯为碳源,二茂铁为催化剂前躯体制备出了碳纳米管.用扫描电子显微镜,透射电子显微镜,拉曼光谱和X射线衍射对碳纳米管的结构进行了表征.再者,通过导入噻吩,合成了一种有很多细碳纳米管分支的碳纳米管.该制备过程工艺简单,碳源价格低廉.利用这个方法,通过控制条件,可得到不同结构的碳纳米管.     

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。     

多壁碳纳米管的合成及应用

介绍了批量制备高纯度多壁碳纳米管的方法.通过将金属M分散在MgO上形成催化剂,在680℃催化裂解石油液化气批量合成碳纳米管,考察了工艺条件的影响.最后研究了碳纳米管在高分子材料中应用.     

13X分子筛为载体制备单壁碳纳米管研究

采用流化床法,以Fe/13X分子筛作为催化剂载体,催化裂解正己烷制备出定向排列的、较纯的单壁碳纳米管.利用TEM、HRTEM、TG和Raman对产物进行了表征,对不同浸泡时间Fe/13X分子筛制成的单壁碳管的含量和分子筛的负载量进行了分析,研究了催化剂铁负载量对单壁碳纳米管的产量和直径的影响.结果表明,单壁碳纳米管产量受催化剂含量和活性的共同影响,且在一个特定催化剂负载量下碳管产量可以达到最高,而其直径变化不大,且不受催化剂负载量的影响.     

碳纳米管沉积铂和钌对PEMFC抗CO中毒能力的影响

通过催化裂解法制备了碳纳米管,对其进行氧化处理后,在其表面沉积了分布均匀、尺寸呈纳米级的铂和铂/钌颗粒.实验结果表明,当采用碳纳米管沉积铂为催化剂时,质子交换膜燃料电池的催化剂铂很容易受CO的毒化而失去活性,从而使电池的电压随电流密度的降低而迅速降低;当采用碳纳米管沉积铂/钌为催化剂时,钌能够使铂表面吸附的CO被氧化为CO₂,增加催化剂对CO的抵抗能力,使燃料电池的性能提高.     

甲烷催化裂解技术研究进展

甲烷催化裂解技术因在适当的吸热过程中裂解只生成碳和氢气而在制备高纯氢气和性能优异的碳纳米管以及ITER(国际热核聚变实验堆)废气处理系统中裂解氚、氘代甲烷以回收其中的氚和氘等方面具有十分重要的意义。介绍了甲烷催化裂解反应机理,阐述了甲烷裂解催化剂的制备方法、催化剂性能的影响因素以及催化剂的失活与再生,指出焙烧温度、活性金属、载体和反应温度对催化剂性能有重要影响,讨论了甲烷催化裂解反应中存在的问题。     

一种制备碳纳米管的新方法

以化学改性的膨润土为催化剂，利用化学气相沉积法催化裂解CH4，在高温条件下成功地制备了碳纳米管，并用透射电镜对其形貌与结构特征进行了表征。结果表明，所得产物形状弯曲，管径为15-20nm，长度达微米级的均匀碳纳米管；膨润土释放的金属铁起到了催化CH4的作用，在800℃条件下生长的碳纳米管质量最好、产率最高，若催化反应温度过高则会降低产品的质量，催化温度低于700℃时不能用来制备碳纳米管，与传统的过渡金属催化剂相比，这种矿物催化剂原料成本低廉，制备工艺简单，有利于碳纳米管的工业化生产。     

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.     

大内径碳纳米管的制备研究

采用化学气相沉积法（chemical vapor deposition）制备碳纳米管．在高温裂解甲烷制备碳纳米管的反应体系中，比较研究了碳酸钠、碳酸钾、碳酸钙和碳酸钡等碳酸盐作为毒物对镍基催化剂和碳纳米管的影响；另外，还考察了裂解温度对碳纳米管的产率和管型的影响。实验中采用气相色谱（gas chromatography）在线检测甲烷的转化率，从而比较镍基催化荆的催化活性；采用透射电子显微镜（transmission electron microscopy）对合成的碳纳米管的外部形貌进行观察。结果发现，无论是从碳纳米管的产率还是形貌，碳酸钠均优于其它几种碳酸盐，内管径可达到70-80nm，另外还发现，750℃为此法制备碳纳米管的最佳裂解温度。     

碳纳米管/聚四氟乙烯复合材料场发射特性研究

通过催化热解法制备了碳纳米管,采用机械共混法制作了碳纳米管/聚四氟乙烯复合材料场发射阴极,研究了不同碳纳米管质量分数对复合材料阴极场发射特性的影响,通过制作的封装结构,对比研究了真空环境下碳纳米管/聚四氟乙烯与碳纳米管/环氧树脂复合材料的场发射特性,证明碳纳米管/聚四氟乙烯复合材料更适用于场发射阴极的真空环境中,可以满足场发射显示器件的要求.     

Synthesis of multiwalled carbon nanotubes from polyethylene waste to enhance the rheological behavior of lubricating grease

Abstract

Carbon nanotubes (CNTs) are attracting great interest in enhancing rheological behavior and thermal performance of lubricating grease. In this study, CNTs were synthesized by catalytic chemical vapor deposition (CCVD) method using low-density polyethylene (LDPE) waste as a cheap carbon source and Co/MgO as an effective catalyst. The effect of temperature on the catalytic pyrolysis of LDPE to produce CNTs has been studied. Catalytic pyrolysis of LDPE waste was conducted in a temperature range of 350–600?°C using the H-ZSM-5 catalyst. The structure and quality of CNTs were fully characterized using HR-TEM, XRD, and Raman spectroscopy. On the other hand, various concentrations of CNTs (0.2, 0.4, 0.6, 0.8, and 1.0?wt%) were mixed with pure lithium grease to determine the optimum percentage that improves the properties of nano-grease. The results showed that a high yield of multiwalled carbon nanotubes (MWCNTs) was obtained with high quality at temperatures ranging from 400 to 550?°C. Also, the addition of CNTs enhanced the rheological behavior of lithium grease, and the optimum percentage of CNTs was 0.8?wt%. Furthermore, the apparent viscosity and shear stress of lithium nano-grease increased by increasing the concentration of CNTs up to 0.8%. At this concentration, the penetration value of lithium nano-grease was greater than pure grease, and the dropping point increased by 12.5%. These results suggested that CNTs prepared from LDPE waste were an excellent additive to enhance the physicochemical properties of lithium grease.     

One-pot synthesis of carbon nanotubes from renewable resource: cellulose acetate

In the present work, we report for the first time one-pot synthesis of carbon nanotubes (CNTs) by pyrolysis of cellulose acetate (CA) cross-linked with polyisocyanate in the fumed silica template. NiCl₂ was chosen as precatalyst for CNT growth. The diameter of CNTs is 24–38 nm and their wall thickness is 9–11 nm. The main role in the formation of CNTs by the pyrolysis of CA may be attributed to combination of closed macropores in the template formed by evolved CO₂ during cross-linking reaction and mesopores formed by silica particles. The macropores acted as microreactors while the mesopores templated catalytic nanoparticles. The importance of this method for CNT synthesis reported here consists of the utilization of readily available renewable resource—CA. Moreover the method does not require preliminary synthesis of catalyst, it is technologically simple (can be performed in the conventional tube furnace), and hence it is energetically efficient.     

Chemical vapor deposition of carbon nanotube layers on aluminum foil

A novel technique has been demonstrated for direct chemical vapor deposition of carbon nanotubes (CNTs) on aluminum foil. It has been shown that the foil surface acquires catalytic properties after being held in an aqueous nickel nitrate solution for a certain time. CNTs were deposited by the catalytic pyrolysis of ethanol vapor. The hybrid materials thus prepared have the form of aluminum foil coated with “carbon wool” from CNTs on both sides. The layers have good adhesion to the aluminum substrate, which allows it to be deformed without causing the CNT layer to peel off. Such material is potentially attractive, in particular, for the fabrication of supercapacitors.     

A simple method of producing single-walled carbon nanotubes from a natural precursor: Eucalyptus oil

Single-walled carbon nanotubes (SWNTs) have been synthesized by catalytic decomposition of eucalyptus oil, on a high silica-zeolite support impregnated with Fe/Co catalyst at 850 °C by the spray pyrolysis method. Catalyst with 5 wt.% (molar ratio of Co:Fe = 1:1), impregnated in zeolite was suitable for effective formation of carbon nanotubes (CNTs). As-grown CNTs were characterized by SEM, TEM and Raman spectroscopy. Raman spectroscopy reveals that as-grown CNTs are well graphitized. Raman spectroscopy also reveals that the as-prepared SWNTs have a diameter of about 0.79-1.71 nm.     

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.     

Simple method for synthesis of carbon nanotubes over Ni-Mo/Al2O3 catalyst via pyrolysis of polyethylene waste using a two-stage process

Synthesis of valuable multi-walled carbon nanotubes (MWCNTs) by thermal pyrolysis of low-density polyethylene (LDPE) waste was investigated via a two-stage process. The first stage was the thermal pyrolysis of LDPE to gaseous hydrocarbons, and the second stage was the catalytic decomposition of the pyrolysis gases over Ni-Mo/Al₂O₃ catalysts. Two catalysts with the compositions of 5.2%Ni-10.96%Mo/Al₂O₃ and 10%Ni-9.5%Mo/Al₂O₃ were tested for carbon nanotubes (CNTs) formation. The catalyst containing 10%Ni showed better activity in terms of CNTs production. Accordingly, the impact of either pyrolysis or decomposition temperatures was investigated using the 10%Ni-9.5%Mo/Al₂O₃ catalyst. TEM, XRD, Raman spectroscopy, TGA, TPR, and BET analysis tools were used to characterize the fresh catalysts as well as the obtained carbon nanomaterials. TEM images proved that MWCNTs with various morphological structures were obtained at all pyrolysis and decomposition temperatures. Moreover, cup-stacked carbon nanotubes (CS-CNTs) were observed at the decomposition temperature of 600°C. MWCNTs with the best quality were produced at decomposition temperature of 750°C. The optimum pyrolysis and decomposition temperatures in terms of CNTs production were at 700 and 650°C, respectively.     

碳纳米管改性海泡石多孔陶瓷及其高效油水分离性能研究

为了有效地从油/水混合液体中回收油, 本工作以纤维状海泡石为原料, 硝酸镍为催化剂前驱体, 聚乙烯粉体为造孔剂和碳源, 采用冷冻干燥结合催化裂解法制备了超疏水/超亲油碳纳米管(CNTs)改性海泡石多孔陶瓷, 研究了固含量和催化热解温度对改性多孔陶瓷形貌的影响, 并表征了其在pH=1的强酸、pH=14的强碱、373 K高温和77 K低温等极端环境中的表面润湿性能及水油分离性能。结果表明: 催化剂前驱体溶液浓度为0.5 mol/L、海泡石的固含量为15wt%、催化热解温度为973 K且保温时间为2 h时所制备的CNTs改性多孔陶瓷具有最好的超疏水/超亲油性能, 其对柴油、白油、植物油和真空泵油的最高吸附量分别是其自身质量的15.7、20.8、23和25倍; 其连续油水分离时油通量高达250 kg·s ^-1·m ^-2, 且在5 h内分离效率及选择性不发生明显降低。     

Synthesis of carbon nanotubes by swirled floating catalyst chemical vapour deposition method

A series of developments have been made in synthesizing Carbon Nanotubes (CNTs) by Catalytic Vapour Deposition (CVD) methods since its discovery as a possible route to the large scale and high quality production of CNTs. In this study, CNTs were synthesized continuously in a swirled floating catalytic chemical vapour deposition reactor using acetylene as carbon source, ferrocene as catalyst, with argon and hydrogen as carrier gases within the temperature range of 900-1050 degrees C. The effects of pyrolysis temperature, acetylene flow rate, hydrogen flow rate, and ratio of flow of acetylene to hydrogen on the rate of production of CNTs were investigated. The CNTs produced were purified with dilute nitric acid and the nature and quality of the CNTs were analysed by TEM, Raman spectrometer, EDX, and TGA. Results obtained revealed that a mixture of single and multi wall carbon nanotubes were produced continuously with a maximum yield rate of 0.31 g/min at 1000 degrees C and a flow ratio of acetylene to hydrogen of one to five.     

铜/碳纳米管复合粒子的制备及其对高氯酸铵热分解性能研究

以碳纳米管为载体, 用化学沉积法制备了Cu/CNTs复合粒子, 并用TEM、SEM、FT-IR、XRD、XPS和DTA对其表观形貌、结构及催化性能进行了表征. 结果表明, CNTs和Cu之间无论是简单混合还是复合, 对高氯酸铵(AP)的热分解均有催化作用. 与纯AP相比, Cu/CNTs复合粒子中的AP高温分解峰温降低126.3℃, 低温分解峰几乎消失, 表观分解热由309.92J/g提高到711.13J/g; 与简单混合物相比, 复合粒子中的AP高温分解峰温降低11.4℃, 表观分解热由494.06J/g提高到711.13J/g. 表明CNTs与Cu的复合处理可显著提高其对AP热分解反应的催化作用.