催化剂、基底对ECR-CVD法制备碳纳米管的影响

采用电子回旋共振微波等离子体化学气相沉积技术(ECR CVD),CH4和H2为气源,分别以Fe3O4,Co纳米粒子及Fe(NO)3溶胶为催化剂在多孔硅基底上制备了碳纳米管;在Si(111)和石英基底上以Fe3O4纳米粒子为催化剂实现了碳纳米管的生长·使用扫描电子显微镜(SEM)、透射电子显微镜(TEM)对样品的形貌、尺寸及结构进行表征·讨论了催化剂和基底对碳纳米管形貌、密度和取向性的影响·结果表明:催化剂影响碳纳米管的成核密度和生长速度,基底通过影响催化剂的特性和分布均匀性,对碳纳米管的形貌和生长模式产生重要影响,以Fe3O4为催化剂在多孔硅上实现了碳纳米管的最优定向生长·     

硼掺杂对碳纳米管形貌和结构的影响

以Fe3O4纳米粒子为催化剂,CH4,B2H6和H2为气源,采用电子回旋共振微波等离子体化学气相沉积技术(ECR CVD)在多孔硅基底上制备出了掺硼碳纳米管薄膜·使用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、能量色散X射线谱(EDX)和X射线光电子谱(XPS)对样品的形貌、结构及组分进行表征·结果表明:通入B2H6后,纳米管的形貌和结构均发生了变化·生长气氛中硼的存在使得高取向性密集碳纳米管转变为较为分散且取向性很差的纳米管·从中空结构转变为类竹节结构,同时多壁管外径增大,管壁增厚,表面变得粗糙,并导致纳米管的生长速度降低,长度减小·     

硫辅助填充高压Fe5C2/Fe7C3单晶相的碳纳米管研究

硫可以用作生长促进剂制备具有不同形态的碳纳米结构, 例如: Y型和海胆状结构, 单壁碳纳米管(SWCNTs), 双壁碳纳米管薄膜等. 此外, 研究表明低浓度的硫和低气体流量可实现碳纳米管中高压Fe7C3和Fe5C2相晶体的填充. 然而, 碳纳米管中高压相的填充条件以及连续垂直取向的碳纳米管薄膜的合成和形貌控制的条件尚需进一步研究. 本文采用化学气相沉积(CVD),使用硫和二茂铁的混合物作为生长促进剂和碳源, 在氩(Ar)气环境中将Si/SiO2基底作为局部生长区域, 实现了在碳纳米管内填充碳化铁相, 并通过对所得碳结构进行详细表征, 揭示填充的碳化物相(Fe5C2和Fe7C3)之间可能存在结合, 这些结果在磁数据存储方面将有潜在应用.     

气流控制的碳纳米管的定向生长研究

通过严格控制气流的方向和催化剂颗粒的密度,加以利用材料自身的重力作用,用热化学气相沉积（T-CVD）的方法在硅衬底上制备了长度可控且与衬底平行的碳纳米管（CNTs）。并研究了催化剂的厚度,生长时间和重力等因素对碳纳米管定向生长的影响。利用扫描电镜对制备的碳纳米管进行了表征。     

Solvothermal synthesis and ferromagnetic property of bamboo-shoot-like oriented carbon micromaterials

Bamboo-shoot-like oriented carbon micromaterials (BOCMs) were synthesized by a solvothermal method at 450°C for 4 h using deoiled asphalt (DOA) as carbon source, toluene as solvent, ferrocene as catalyst precursor and amphiphilic triblock copolymer P123 as surfactant. The morphology and structure of the products were characterized by X-ray diffraction, field emission scanning electron microscopy, high resolution transmission electron microscopy and Fourier transform infrared spectroscopy. The results reveal that the obtained products have good distribution with uniform diameters of about 0.5 μm and the lengths of 1–1.5μm, and hydrogen-carbon bonds are observed on the surface of BOCMs. The growth mechanism of BOCMs is discussed, in which that the catalysis of ferrocene and the dispersion and assembly of the aromatic molecules of DOA directed by P123 are critical to the formation of the BOCMs. The coercivity value (231.91 Oe) from the measurement of a vibrating sample magnetometer shows that the BOCMs have an obvious ferromagnetic behavior.     

硅掺杂氮化硼纳米管的制备及其光学性质

通过高温热解聚合物前驱体方法制备Si掺杂BN纳米管. 采用扫描电子显微镜（SEM）和透射电子显微镜（TEM）对样品的结构与形貌进行表征, 结果表明, 样品属于一端开口的竹节状BN纳米管, 通过变温光致发光谱及喇曼光谱研究了Si掺杂BN纳米管的光学性质.      

催化剂厚度对碳纳米管直径的影响

由于碳纳米管具有独特的结构和性能，因而自从被发现以来一直受到人们的关注。近年来，已利用各种方法成功地合成出碳纳米管，特别是利用化学气相沉积方法制备高度准直的碳纳米管。分析了该方法中催化剂厚度对碳纳米管直径的影响，利用负衬底偏压热灯丝CVD系统和不同厚度的NiFe催化剂在Si衬底上直接生长，并用扫描电子显微镜来研究碳纳米管的生长过程。结果表明催化剂颗粒封闭了碳纳米管的顶端，催化剂厚度对碳纳米管的直径有较大的影响，碳纳米管的平均直径随催化剂厚度的增大而增大。     

Synthesis of carbon nanotube arrays using ethanol in porous anodic aluminum oxide template

Carbon nanotube (CNT) arrays confined by porous anodic aluminum oxide (AAO) template were synthesized using ethanol as reactant carbon source at low pressure. Images by scanning electron microscope (SEM) and low magnification transmission electron microscopy (TEM) show that these CNTs have highly uniform outer diameter and length, absolutely controlled by the diameter and depth of nano-channel arrays of the AAO. High resolution transmission electron microscopy (HRTEM) imaging indicates that the graphitization of the CNT walls is better than the results reported on this kind of template-based CNT arrays, although it is not so good as that of multiwalled carbon nanotubes (MWCNTs) synthesized by catalysis. CNTs synthesized using acetylene as reactant gas show much less graphitization than those prepared using ethanol by comparing the results of HRTEM and Raman spectroscopy. The etchingeffects of decomposed OH radicals on the amorphous carbon and the roughness of AAO nano-channel arrays on the CNTs growth were employed to explain the graphitization and growth of the CNTs.     

碳纳米管的催化合成、结构表征及应用研究

概述近10年来国内外在碳纳米管催化合成及其应用研究领域的发展动态,着重介绍本研究组在管径小而均匀碳纳米管的催化合成、结构性能表征、及其在作为新型催化剂载体材料及储氢等应用领域的研究进展。     

碳纳米管负载Mo-Co-S催化剂的能谱研究

碳纳米管负载的Mo-Co-S加氢脱硫催化剂,其对噻吩的HDS在一定的反应条件下显示出比常规载体γ-Al2O3或SiO2负载催化剂更高的催化活性;从能谱(XPS)表征的角度研究探讨了该类催化剂反应活性高的原因,并结合H2-TPR,H2-TPD等谱学表征的结果,讨论了CNTs载体的促进作用本质.     

Flexible supercapacitor electrodes with vertically aligned carbon nanotubes grown on aluminum foils

In this work, vertically aligned carbon nanotubes (VACNTs) grown on aluminum foils were used as flexible supercapacitor electrodes. Aluminum foils were used as readily available, cheap and conductive substrates, and VACNTs were grown directly on these foils through chemical vapor deposition (CVD) method. Solution based ultrasonic spray pyrolysis (USP) method was used for the deposition of the CNT catalyst. Direct growth of VACNTs on aluminum foils ruled out both the internal resistance of the supercapacitor electrodes and the charge transfer resistance between the electrode and electrolyte. A specific capacitance of 2.61 mF/cm2 at a scan rate of 800 mV/s was obtained from the fabricated electrodes, which is further improved through the bending cycles.     

Microst ructure andflexural properties of carbon/ca rbon composite with in-situ grown carbon nanotube as secondary reinforcement

Carbon nanotubes (CNTs) were in-situ grown in carbon felts using ferric chloride as catalyst and natural gas as carbon precursor via thermal gradient chemical vapor infiltration (TGCVI). Subsequently, the carbon felts were densified to obtain CNT reinforced carbon/carbon (C/C) composites in the same furnace. Effects of CNTs on the microstructure and flexural property of C/C composites were investigated by polarized light microscopy, Raman spectroscopy, scanning electron microscopy and universal mechanical testing machine. The results of PLM observation and Raman analysis showed that CNTs have two-sided effects on the microstructure of pyrocarbon: the pyrocarbons in the region without CNTs show medium texture; while, in the region full of CNTs, the microstructure was low-textured or even isotropic though the TGCVD conditions would lead to the deposition of pure low texture pyrocarbons. Analysis based on stress-strain curves demonstrated that the flexural strength increased first and then decreased with the CNT content increasing. When the CNT content was 5.23 wt%, the flexural strength was maximum and had a nearly 35% improvement compared with pure C/C composite. Besides, after adding CNTs, the flexural modulus of the composites decreased and the ductility increased obviously, indicating CNTs can toughen C/C composites.     

TiO2/Fe2O3/CNTs磁性光催化剂的制备及可见光下降解盐酸四环素

以碳纳米管为载体支架,利用简便的化学沉积和热处理方法,将Fe2O3纳米颗粒负载在碳纳米管表面,得到磁性碳纳米管(Fe2O3/CNTs)。再利用溶胶-凝胶法包覆Ti O2纳米颗粒,制得一种新型的磁性光催化剂(Ti O2/Fe2O3/CNTs),通过SEM、TEM、XRD、VSM和UV-Vis等方法,对样品进行了一系列的表征。将其用于水体中盐酸四环素的降解,探究了p H条件、原始浓度以及光催化剂用量对降解作用的影响。结果表明,样品具有紧凑的交错多孔结构,Ti O2/Fe2O3纳米颗粒包覆在其表面。样品能对紫外-可见光产生较强吸收,光能利用率及光催化性能显著提高。在25 mg/L盐酸四环素偏酸性体系中,在1.5 mg/L催化剂用量下,光催化反应降解率可达95.1%,光催化反应符合一级反应动力学模型。此外,催化剂还具备良好的超顺磁性,易于分离回收,重复使用,有望成为一种经济,环保,高效,可循环的四环素降解材料。     

CCVD法制碳纳米管用Ni-Mg-O催化剂的制备研究

用草酸盐共沉淀法制备一类固溶体型NixMg1-xO纳米催化剂.该类催化剂用于甲烷催化分解合成碳纳米管(CNTs)显示出优良的性能.催化剂的制备优化研究揭示,催化剂的金属元素组成、氧化前驱物的焙烧和还原的温度对催化剂的性能有强烈的影响.在经优化的制备条件(n(Ni)∶n(Mg)=0.5:0.5,焙烧温度873 K,H2-还原温度973 K)下制备的Ni0.5Mg0.5O催化剂上,在经优化的制管反应条件(873 K,甲烷原料气GHSV=5×104mL/(h.g))下,反应2 h的CNTs产物的产率达到14.5 g/g.     

氢氧化钠对多壁碳纳米管结构的影响

以苯和乙醇的混合溶液为碳源，二茂铁、噻吩和氢氧化钠为催化剂体系，采用催化裂解法制备出多壁碳纳米管，并研究了氢氧化钠的添加对多壁碳纳米管结构的影响。结果表明：随着反应体系中氢氧化钠质量浓度的增加，多壁碳纳米管的外径显著减小，内径略有增大。     

Si@CNT纳米结构与MOF衍生多孔碳的链状化合物作为锂离子电池负极材料的研究

Silicon anodes are considered to have great prospects for use in batteries; however, many of their defects still need to be improved. The preparation of hybrid materials based on porous carbon is one of the effective ways to alleviate the adverse impact resulting from the volume change and the inferior electronic conductivity of a silicon electrode. Herein, a chain-like carbon cluster structure is prepared, in which MOF-derived porous carbon acts as a shell structure to integrally encapsulate Si nanoparticles, and CNTs play a role in connecting carbon shells. Based on the exclusive structure, the carbon shell can accommodate the volume expansion more effectively, and CNTs can improve the overall stability and conductivity. The resulting composite reveals excellent rate capacity and enhanced cycling stability; in particular, a capacity of 732 mA·h·g?1 at 2 A·g?1 is achieved with a reservation rate of 72.3% after cycling 100 times at 1 A·g?1.     

Preparation of double-walled carbon nanotubes

Double-walled carbon nanotubes were prepared using the floating chemical vapor deposition with methane as carbon source and adding small amount of sulfur into the ferrocene catalyst. The optimized technological parameters are: the reaction temperature is 1200℃; the catalyst vapor temperature is 80℃; the flow rate of argon is 2000 SCCM; the flow rate of methane is 5 SCCM. The purified DWNTs under these optimized technological parameters have high purity above 90 wt%.     

铁硫化物／石墨烯纳米复合材料溶剂热法一步合成

以二茂铁和硫磺粉作为铁源和硫源,乙醇或邻二氯苯为溶剂,利用溶剂热法一步合成了FeS2／石墨烯和Fe2S8／石墨烯纳米复合材料;采用X射线衍射（XRD）法、扫描电子显微镜（SEM）和透射电子显微镜（TEM）对产物的晶相结构和形貌进行了分析与表征;并研究了原料的配比及溶剂对产物的组成和形貌的影响．当二茂铁与硫磺粉的摩尔比为1：2．5时,所得产物为Fe7S8／石墨烯纳米复合材料;而当它们的摩尔比为1：2时,所得产物为FeS2／石墨烯纳米复合材料,使用乙醇或邻二氯苯为溶剂合成所得FeS2／石墨烯纳米复合材料的形貌有较大的差异．     

定向生长碳纳米管的研究进展

由于碳纳米管具有独特的结构和性能，因而自从被发现以来一直受到人们的关注，近年来，已利用各种方法成合成出碳纳米管，特别是利用化学气相沉积（CVD）方法制备了高度准直的碳纳米管，实现了碳纳米管的定向生长，使得碳纳米管具有更加广泛的应用价值和研究价值。本文综述了近几年CVD定向生长碳纳米管的方法和生长机制，分析和讨论了不同制备方法对碳纳米管生长过程的影响，同时还着重分析了催化剂颗粒在碳纳米管的生长过程中对定向生长碳纳米管的作用。     

催化裂解法制备大孔径碳纳米管

Ni-Cu-Al催化剂中加入少量碳酸钠,催化裂解甲烷制备了大孔径碳纳米管,碳纳米管的产量为2.4g/g.cat。用这种方法制备的碳纳米管的内径约为20 nm~60 nm,外径约为40 nm~80nm。用扫描电镜(TEM)和X射线衍射(XRD)研究了碳纳米管的形貌和微结构。分析结果表明:用这种方法制备的碳纳米管不仅内径较大而且石墨化程度较高。碳酸钠的加入引起了甲烷转化率和碳产率的轻微下降。实验结果表明:碳酸钠是一种温和的毒物,它能影响Ni-Cu-Al催化剂的催化活性,导致大孔径碳纳米管的生成。文中还讨论了大孔径碳纳米管的生长机理。