Synthesis of sulfur-doped carbon nanotubes from sulfur powder using chemical vapor deposition

Sulfur-doped carbon nanotubes (SCNT) with high sulfur contents have been prepared using chemical vapor deposition (CVD) from sulfur powder, acetylene gas and Fe/CaCO₃ (as catalyst). In this regard, various growth's temperatures were examined to investigate its effects on the structure and the sulfur content of prepared SCNT. The best condition was obtained at 700°C and using 4 g of sulfur powder. The product was characterized using FE-SEM and EDS, which showed rode-like SCNT with about 40 nm diameter and 10.75% sulfur content. Moreover, TEM, Raman and XPS analyses were employed to obtain more details related to the product. The XPS results confirmed the presence of sulfur atoms, which covalently incorporated in the carbon framework. Finally, the catalytic ability of the product in oxygen evolution reaction was examined and the results showed high stability and low oxygen production rate for this product.     

Synthesis of carbon nanotubes

Carbon nanotubes play a fundamental role in the rapidly developing field of nanoscience and nanotechnology because of their unique properties and high potential for applications. In this article, the different synthesis methods of carbon nanotubes (both multi-walled and single-walled) are reviewed. From the industrial point of view, the chemical vapor deposition method has shown advantages over laser vaporization and electric arc discharge methods. This article also presents recent work in the controlled synthesis of carbon nanotubes with ordered architectures. Special carbon nanotube configurations, such as nanocoils, nanohorns, bamboo-shaped and carbon cylinder made up from carbon nanotubes are also discussed.     

碳纳米管与铝合金基体材料的混合工艺研究

为改善碳纳米管在铝合金基体中的分散性和发挥其增强作用,分别采用湿混、球磨以及湿混后球磨的方式将碳纳米管与铝合金粉末进行混合,再经真空烧结制备出碳纳米管增强铝合金复合材料.不同混合工艺的对比试验结果表明:碳纳米管于液相环境下被均匀分散并吸附于铝合金颗粒表面,但在烧结过程中易再次发生团聚;而较长时间的机械球磨会对碳纳米管结构造成一定程度的破坏.相比下,液相分散与机械球磨结合的方式提高了碳纳米管的分散程度和缩短了球磨时间,碳纳米管增强铝合金材料(3%CNTs/5083Al)的抗拉强度达620 MPa.     

Alumina powder assisted carbon nanotubes reinforced Mg matrix composites

Mg matrix composites reinforced by carbon nanotubes (CNTs)-Al₂O₃ mixture, which was synthesized by in situ growing CNTs over Al₂O₃ particles through chemical vapor deposition (CVD) using Ni catalyst, were fabricated by means of powder metallurgy process, followed by hot-extrusion. By controlling synthesis conditions, the as-grown CNTs over Al₂O₃ particles possessed high degree of graphitization, ideal morphology, higher purity and homogeneous dispersion. Due to the ‘vehicle’ carrying effect of micrometer-level A₂O₃, CNTs were easy to be homogeneously dispersed in Mg matrix under moderate ball milling. Meanwhile, Al₂O₃ particles as catalyst carriers, together with CNTs, play the roles of synergistic reinforcements in Mg matrix. Consequently, the Mg matrix composites reinforced by CNTs-Al₂O₃ mixture exhibited remarkable mechanical properties.     

A facile route to sea urchin-like NiO architectures

Sea urchin-like NiO architectures were successfully synthesized by thermal decomposition of the as-prepared precursors deposited from NiCl₂·6H₂O aqueous solution with urea via hydrothermal route, without using any templates or surfactants. The precursors and ultimate products were characterized by XRD, FESEM, TEM and SAED. Results showed that the obtained samples were of high purity and the phase was polycrystalline cubic NiO; the NiO architectures composing numerous nanowires had a uniform diameter of about 1 μm and the diameter of the nanowires on the architectures was in the range of 10–30 nm. The possible formation mechanism was discussed. The presented method is facile and inexpensive, so it may be suitable for bulk production.     

Dispersion of carbon nanotubes (CNTs) in aluminum powder

In the present work, we use mechanical alloying (MA) for the first time to generate a homogenous distribution of 2 wt% CNT within Al powders. The effect of milling time (up to 48 h) on the morphological development of the powders and dispersion of CNTs was investigated. The results show that the technique is effective in dispersing the nanotubes within the soft Al matrix which simultaneously protects the nanotubes from damage under the impact of the milling balls. The results can have important implications for the processing of CNT-reinforced metal-matrix composites in general.     

碳纳米管管径的可控性研究

为了合理有效控制碳纳米管(CNTs)的管径,比较研究了化学气相沉积(CVD)-模板法与CVD-中毒法.通过透射电镜(TEM)观察碳纳米管形貌及其管径尺寸,分析了不同条件下,碳纳米管的形貌差异,讨论了制备阳极氧化铝(AAO)膜的氧化电压对碳纳米管的管径、管的有序度的影响和碳酸钠毒物对碳纳米管的管径、管形、产率的影响,并且分析了两种制备方法的生长机理.结果表明,在CVD-模板法中,在一定范围内,电压升高可以使AAO膜孔增大,从而控制碳纳米管的外径;在CVD-中毒法中,微量的碳酸钠粉末能增大碳纳米管的内径.     

改进化学气相沉积法在炭纤维表面生长碳纳米管(英文)

采用一种改进的化学气相沉积法在炭纤维表面制备碳纳米管。为了提高炭纤维表面的润湿性能,炭纤维在浸渍之前先在CVD设备中在真空下973 K的高温处理,然后在硝酸和浓硫酸体积比为3∶1的混合酸中酸处理30 min。而改进的化学气相沉积法关键在于让催化剂的还原步骤和碳纳米管的生长步骤同时进行。这样通过减小过渡金属元素与炭纤维之间的接触时间从而降低了它们之间的相互扩散,在确保了炭纤维本身的力学性能下降程度明显小于用普通化学气相法制备的情况下生长出长且茂密的碳纳米管阵列。另外,经过对工艺参数的优化发现当用乙醇作溶剂,Fe(NO3)3.9H2O溶度为100 mmol/L,氢气和碳源气体比值为4/1,而生长时间为30 min时得到最好的碳纳米管阵列。     

不同基底上碳纳米管的制备及生长机理

以二茂铁为催化前驱物,C2H2为碳源,N2为载气,采用浮动催化法,在蓝宝石、单晶硅、石英、玻璃以及碳纤维基底上制备了不同形貌和结构的碳纳米管.利用扫描电子显微镜和Raman光谱对碳纳米管的形貌和微结构进行了表征.结果表明在蓝宝石和石英基底上所生长的碳纳米管薄膜具有较好的定向性和较高的石墨化程度;单晶硅基底上碳纳米管薄膜呈"底疏顶密"分布;而玻璃和碳纤维基底上所生长的碳纳米管不具有定向性.最后,对不同基底对碳纳米管生长的影响进行了分析和讨论.     

Synthesis and characterization of phospholipid-modified multiwalled carbon nanotubes

A simple three-step strategy to functionalize multiwalled carbon nanotubes using 1,2-distearoyl-sn-glycero-3-phosphoethanolamine phospholipids has been described. The resulting phospholipid-modified multiwalled carbon nanotubes were analyzed by TEM, AFM, NMR, IR, UV-vis and TGA techniques. The experimental results show that the use of amine-terminated phospholipids not only improves the dispersity of multiwalled carbon nanotubes in both aqueous and organic solvents greatly, but also results in the significant enhancement of biocompatibility. These findings will serve as a future biological platform for new devices ranging from biosensors to nano-detectors.     

Synthesis and thermoelectric power of nitrogen-doped carbon nanotubes

We have previously shown that high-purity multiwalled carbon nanotubes (pristine MWNTs) can be prepared from a mixture of xylene-ferrocene (99 at% C:1 at% Fe) inside a quartz tube reactor operating at approximately 700 degrees C. In a similar process, approximately 3 g of melamine (C3H6N6) was introduced during the growth of MWNTs to prepare nitrogen-doped nanotubes. The structural and electronic properties of nitrogen-doped MWNTs were determined by scanning electron microscopy, high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), and thermopower measurements. The individual nitrogen-doped nanotube exhibits a bamboo-like structure and comprises 6-16 tube walls, as evidenced by HRTEM studies. The EELS measurements yielded an average nitrogen content of approximately 5 at% in the doped tubes. The thermoelectric power data of nitrogen-doped MWNTs remained negative even after exposure to oxygen for an extended period of time, suggesting that nitrogen doping of MWNTs renders them n-type, consistent with scanning tunneling spectroscopic studies on similar nanotubes.     

Preparation and properties of powder styrene-butadiene rubber composites filled with carbon black and carbon nanotubes

Carbon nanotubes (CNTs) and carbon black (CB) filled powder styrene-butadiene rubber (SBR) composites were prepared by spray drying of the suspension of CNTs and CB in SBR latex. The powders were sphere like and fine with uniform diameters of 10-15 μm. Experimental results showed that the introduction of CNTs into the matrix was beneficial to improve the security of the vulcanization of the rubber composites, and the dynamic and basic mechanical properties of the CNTs/SBR composites were better than those of CB/SBR and neat SBR composites. Observations on the microstructure of the composites indicated that CNTs were well dispersed in the matrix. Morphology of the fracture confirmed that the bonding between CNTs and rubber matrix was strong and load can be transferred to CNTs efficiently during the mechanical property tests. Moreover, the powder SBR composites containing well-dispersed CNTs could be perfect candidate as additives for other polymers.     

Synthesis and characterization of aligned Fe-filled carbon nanotubes on silicon substrates

We describe the preparation and the properties of Fe-filled multi-walled carbon nanotubes on Co-coated oxidized silicon substrates. The material was grown by pyrolysis of ferrocene, using a chemical vapor deposition process. Scanning and transmission electron microscopy studies indicate that the material consists of filled and aligned MWNTs. They have outer diameters of 40–100 nm and diameters of the metal core of 20–40 nm. Energy dispersive X-ray analysis of individual tubes reveals that their filling consists of pure Fe. Alternating gradient magnetometry investigations demonstrate the ferromagnetic behavior of the filled tubes. We observe unique magnetic properties differing from those of bulk Fe.     

Synthesis and characterization of carbon nanotubes grown on montmorillonite clay catalysts

Multiwall carbon nanotubes have been grown on montmorillonite clay catalysts through anchoring on FeCo nanoparticles. The starting clay is a commercial sodium-rich montmorillonite in which the intercalated sodium ion was exchanged for cobalt(II) and iron(III) ions via mechanical agitation or sonication, both with and without subsequent centrifugation. The cobalt-iron intercalate clay was used as a catalyst for the synthesis of carbon nanotubes via decomposition of ethylene at 700 °C. The largest carbon deposit was obtained for catalysts prepared with 3 or 4 cation exchange equivalents. X-ray diffraction indicates both that the basal spacing of the clay increases from 12.43 Å to 16.4 Å upon intercalation of cobalt and iron. Atomic absorption analysis of the catalysts indicates that virtually all of the sodium ions originally present in the clay have been replaced by iron(III) and cobalt(II). Transmission electron micrographs show the presence of multiwall carbon nanotubes with inner and outer diameters of ca. 10 nm and 20 nm grown on metal particles present on the plates of catalysts. The iron-57 Mössbauer spectra indicate that the intercalated clay contains iron(III) in octahedral and tetrahedral sites and iron(II) in octahedral sites, the catalysts contain an extensive amount of small superparamagnetic particles of α-Fe₂O₃ and that the carbon-nanotube catalyst composites show the presence of iron(II) and iron(III) paramagnetic doublets, characteristic of a reduced montmorillonite, and of sextets that are characteristic of an FeCo alloy and of Fe₃C cementite. The Mössbauer spectra indicate that the carbon nanotubes grow on FeCo metallic nanoparticles and bond to these particles through the formation of cementite.     

Synthesis of multiwalled carbon nanotubes by high-temperature vacuum annealing of amorphous carbon

Vacuum annealing of a mixture of amorphous carbon and cobalt nanoparticles supported on microporous zeolite at high-temperature results in the formation of multiwalled carbon nanotubes which are essentially filled with metal nanoparticles or nanowires as observed by transmission electron microscopy. The electronic properties of nanotubes by variable temperature ESR techniques shows that g values show little change with temperature from 77 to 327 K but the line width (ΔH_pp) of the ESR signal for nanotubes synthesized from amorphous carbon increases from 7.9 G at 77 K to 9.5 G at 327 K.     

Synthesis of single-walled carbon nanotubes by induction thermal plasma

The production of high quality single-walled carbon nanotubes (SWCNTs) on a bulk scale has been an issue of considerable interest. Recently, it has been demonstrated that high quality SWCNTs can be continuously synthesized on large scale by using induction thermal plasma technology. In this process, the high energy density of the thermal plasma is employed to generate dense vapor-phase precursors for the synthesis of SWCNTs. With the current reactor system, a carbon soot product which contains approximately 40 wt% of SWCNTs can be continuously synthesized at the high production rate of ∼100 g/h. In this article, our recent research efforts to achieve major advances in this technology are presented. Firstly, the processing parameters involved are examined systematically in order to evaluate their individual influences on the SWCNT synthesis. Based on these results, the appropriate operating conditions of the induction thermal plasma process for an effective synthesis of SWCNTs are discussed. A characterization study has also been performed on the SWCNTs produced under the optimum processing conditions. Finally, a mathematical model of the process currently under development is described. The model will help us to better understand the synthesis of SWCNTs in the induction plasma process.      

Synthesis of carbon nanotubes within Pt nanoparticles-decorated AAO template

Template-based synthesis of Pt-doped carbon nanotubes has been conducted with a corona discharge enhanced chemical vapor deposition. In this paper, nanoporous anodic alumina template was firstly decorated with Pt nanoparticles upon its interior walls. As the fabrication of carbon nanotubes within the nanopores, Pt nanoparticles were simultaneously embedded into the carbon nanotubes. HRTEM indicated that the grain size of these Pt nanoparticles is 5 nm and they are homogeneously exposed on the outer surface of carbon nanotubes.     

Synthesis of carbon nanotubes using mesoporous Fe-MCM-41 catalysts

MWNTs (multi-walled carbon nanotubes) were made by catalytic CVD process using iron-containing mesoporous silica, Fe-MCM-41, with 4 mol% Fe loading prepared by direct synthesis route. Uniform 5 nm size Fe2O3 nano-particles impregnated onto a mesoporous silica support, SBA-15 were also prepared for CNTs synthesis. The catalysts were characterized using XRD, SEM/TEM, N2 physisorption, UV-vis diffuse reflectance and FT-IR spectroscopies. Acetylene gas was introduced as a carbon source, and the gas mixture of Ar:H2:C2H2 = 14:5:1 pyrolyzed at 750 degrees C for 60 min was found to be the optimum synthesis condition. Fe-MCM-41 due to higher dispersion of nano-sized Fe-species was efficient as catalyst for MWNTs with more uniform size distribution. Cobalt-impregnated Fe-MCM-41 (Co/Fe = 1) produced a small fraction of SWNTs of ca. 2 nm diameter mixed with MWNTs.