Carbon nanotube growth from alkali metal salt nanoparticles

We demonstrate that alkali metal salts, including KCl, NaCl, K₂SO₄, Na₂SO₄, K₂CO₃, and Na₂CO₃, can act as catalysts for carbon nanotube (CNT) growth in chemical vapor deposition (CVD). The solution of alkali metal salt, water and ethanol was nebulized and was introduced into the CVD reactor, producing CNT with a multi-walled structure. Individual CNT are terminated with an onion-shaped carbon tip even when different alkali metal salt catalysts are used. Through observation and analysis of the catalyst particles and the resulting product, we elucidate the mechanism by which the alkali metal salt nanoparticles are served as “seeds” and provide nucleation sites for CNT growth. The ethanol decomposes to release carbon atoms into the catalyst particles, and the carbon nucleates and then begins to assemble on the surface of the catalyst particles, resulting in the CNT growth. By altering growth conditions, branched CNT and single-walled CNT also can be grown on alkali metal salt nanoparticles.     

Carbon nanotube ropes proposed as particle pipes

Classical molecular dynamics studies of carbon ion-irradiation on ropes made of (10, 10) carbon nanotubes have been made. The carbon ions were fired into the rope on the outside of the nanotubes in a direction almost parallel to the longitudinal axis. Channeling takes place when the incidence angle is smaller than a critical angle. The dependence of the critical angle on the energy follows an inverse square root function. Our calculations show that the dependence of the critical angle on the energy is very similar for intra- and inter-tube channeling. Wave creation during the collision process is discussed.     

Correlation between catalyst particle and single-walled carbon nanotube diameters

Single-walled carbon nanotubes (CNTs) were synthesised at different conditions by a novel aerosol method based on the introduction of pre-formed iron catalyst particles into conditions leading to CNT formation. The results of statistical measurements of individual CNT dimensions based on high-resolution TEM images showed the effects of the residence time and temperature in the reactor. The ratio between catalyst particle and CNT diameters was close to 1.6 and independent of the experimental conditions, thus revealing an astonishing “universality” in the growth process. A proposed geometric model of heptagon defect formation, which initiates and maintains the CNT growth, allowed us to theoretically explain the phenomenon.     

Carbon nanotube growth on conductors: Influence of the support structure and catalyst thickness

We investigate the formation and stability of Fe nanoparticles on TiN and poly-crystalline PtSi films, and their ability to grow carbon nanotubes forests. Using different-microstructure films, coated with or without their native oxides, we show that, upon purely-thermal catalyst pretreatment, PtSi favours the formation of homogenously sized nanoparticles and forest growth, partly due to its low surface energy. TiN, in contrast, leads to much less controllable processes and only when coated with its native oxide, or with thick catalyst films, yields large diameter nanotube forests. The microstructure of the material can dramatically limit catalyst diffusion into the bulk of the support during nanotube growth. These results allow us to establish the general behaviour expected for nanotube growth on any conductive materials.     

Optimizing catalyst nanoparticle distribution to produce densely-packed carbon nanotube growth

The experimental parameters involved in the formation of the Ni catalytic nanoparticles on Si/SiO₂ substrates that seed carbon nanotube growth were investigated. It was found that after deposition of a nickel film on the substrate, the temperature and time of the thermal and reduction catalyst pre-treatment steps are crucial variables for optimized nanoparticle distribution with different average diameters, depending on the initial film thickness. Densely-packed carbon nanotube forests with interesting potential applications have been grown from this nanoparticle distribution.     

Dynamics of catalyst particle formation and multi-walled carbon nanotube growth in aerosol-assisted catalytic chemical vapor deposition

In aerosol-assisted catalytic chemical vapor deposition (CCVD), the catalyst and carbon precursors are introduced simultaneously in the reactor. Catalyst particles are formed in situ and aligned multi-walled CNTs grow at a high rate. To scale-up the process, it is crucial to understand the chemical transformation of the precursors along the thermal gradient of the reactor, and to correlate nanotube growth with catalyst nanoparticle formation. The products synthesized along a cylindrical CVD reactor from an aerosol composed of ferrocene and toluene, as catalyst and carbon precursor, respectively, were studied. The product surface density and iron content are determined as a function of the location and the iron vapor pressure in the reactor. Samples are analyzed by electron microscopy, X-ray diffraction and Raman spectroscopy. We show the strong influence of the thermal gradient on location and rate of formation of both iron particles and CNTs, and demonstrate that catalyst particles are formed by gas phase homogeneous nucleation with a size which correlates with iron vapor pressure. They are gradually deposited on the reactor walls where nanotubes grow with an efficiency which is varying linearly with catalyst particle density. CNT crystallinity appears very high for a large range of temperature and iron content.     

State of the catalyst during carbon nanotube growth

We review our in-situ X-ray photoemission (XPS) and in-situ transmission electron microscopy studies which determined that the catalyst is in the metallic state for Fe, Co and Ni catalysts. We show that the existence of surface carbide phases in related catalytic reactions could account for the observation of carbide peaks in XPS. The observed catalytic activity of gold is discussed in terms of carbon solubility, reaction rates, and surface coordination numbers.     

Carbon nanotube supported Pd catalyst for liquid-phase hydrodehalogenation of bromobenzene

A multi-walled carbon nanotube (MWCNT) supported Pd catalyst has been prepared by conventional impregnation for the liquid-phase hydrodehalogenation of bromobenzene under mild reaction conditions. Compared with conventional supports such as activated carbon, Al₂O₃, SiO₂ and MgO, MWCNTs as a catalyst support offer not only better performance but also a substantial reduction in the amount of Pd required.     

Carbon nanotube growth by rapid thermal processing

A new method for carbon nanotube (CNT) growth by rapid thermal processing (RTP) of amorphous carbon film is reported. This is a two-step method, involving an ion-beam sputtering process followed by an RTP treatment. Amorphous carbon film containing iron was first deposited by ion-beam sputtering. The as-deposited films were then annealed by RTP under an inert environment. High-density multi-wall carbon nanotubes with a length of 1 μm and a diameter of approximately 30 nm were observed on the surface of amorphous carbon film after RTP at 1200°C for 30 s in nitrogen (N₂). Detailed morphology and structure analyses of carbon nanotubes thus obtained using SEM and HR-TEM indicated that the number density and growth rate of the CNT were dependent on the process temperature and ambient gas. The use of RTP provides a straightforward, convenient and cost-effective method to grow carbon nanotubes with controllable length and density.     

Effect of catalyst particle interspacing on the growth of millimeter-scale carbon nanotube arrays by catalytic chemical vapor deposition

Vertically aligned millimeter-scale carbon nanotube (CNT) arrays have been successfully deposited on both Fe(3 nm)/Al₂O₃ and Fe(1 nm)/Al₂O₃ catalyst films under different optimum pretreatment conditions by catalytic chemical vapor deposition. By investigating the catalyst particles before CNT array growth, it has been found that inter-particle spacing plays a significant role in influencing CNT array height, CNT diameter and wall number in the present study. The growth kinetics of CNT arrays grown from the two catalyst films with different pretreatment conditions demonstrates a competitive lengthening-thickening process. Based on the kinetics studies, it has been proved that inter-particle spacing affects the CNT array height by affecting their lengthening time, and accordingly affects the diameter and wall number of CNTs because of the concurrent change in the thickening time.     

How to switch from a tip to base growth mechanism in carbon nanotube growth by catalytic chemical vapour deposition

The catalytic growth of carbon nanotubes is performed at 580 °C with iron catalyst using a hot-wall CVD technique. It is shown that the growth mode can be switched from ‘tip’ to ‘base’ growth mode by an insertion of plasma pre-treatment of catalyst at room temperature before growth. To understand this phenomenon, the oxidation state of catalyst is compared using XPS before and after the pre-treatment. Growth mechanisms induced by different oxidation states of catalyst are proposed to explain the switching of the growth mode. A thermodynamic calculation shows the relation between induced growth mode and resulting CNT diameter.     

Relating carbon nanotube growth parameters to the size and composition of nanocatalysts

A gas-phase approach to studying carbon nanotube (CNT) nucleation and growth from nanoparticle catalysts has been developed. Dimensionally- and compositionally-tuned metal particles with mean diameters between 2 and 5 nm and standard deviations less than 15% are initially synthesized from metallocene vapors in an atmospheric-pressure microplasma. The nanocatalysts are continuously fed with acetylene and hydrogen into a flow furnace reactor to grow CNTs. Kinetic studies are performed by in situ aerosol size classification of the nanotubes to relate the CNT length and thus, the growth rate in our thermal process to the catalyst size and composition. We find that reducing the catalyst size results in an increase in the growth rate while varying the catalyst composition affects the growth rate, activation energy, and the onset temperature for CNT growth.     

High density carbon nanotube growth using a plasma pretreated catalyst

We have developed a direct current plasma pretreatment of the Fe catalyst to increase the area density of vertically-aligned carbon nanotube forests. The carbon wall density of the double- and multi-walled nanotubes reaches 4.8 × 10¹² cm⁻², with a 40% volume occupancy and a mass density of ∼0.4 g cm⁻³. The plasma pretreatment works by reducing the sintering of the catalyst nanoparticles during growth. This treatment increases the forest density by 8 times compared to the standard growth conditions.     

Effect of catalyst preparation on the carbon nanotube growth rate

A series of silica supported Fe catalysts were prepared by different methods in order to obtain varying Fe particle sizes. The catalysts were characterized by XRD, TPR, BET, and TEM. The CNT growth from CO disproportionation was studied in order to establish a relationship between the CNT growth rate and the particle size. We found that there is an optimum catalyst particle size at around 13–15 nm which will lead to the maximum growth rate. The influence of the metal loading on the growth rate was also investigated. A CNT growth model has been formulated to explain the experimental results.     

Mechanically activated catalyst mixing for high-yield boron nitride nanotube growth

ABSTRACT: Boron nitride nanotubes (BNNTs) have many fascinating properties and a wide range of applications. An improved ball milling method has been developed for high-yield BNNT synthesis, in which metal nitrate, such as Fe(NO3)3, and amorphous boron powder are milled together to prepare a more effective precursor. The heating of the precursor in nitrogen-containing gas produces a high density of BNNTs with controlled structures. The chemical bonding and structure of the synthesized BNNTs are precisely probed by near-edge X-ray absorption fine structure spectroscopy. The higher efficiency of the precursor containing milling-activated catalyst is revealed by thermogravimetric analyses. Detailed X-ray diffraction and X-ray photoelectron spectroscopy investigations disclose that during ball milling the Fe(NO3)3 decomposes to Fe which greatly accelerates the nitriding reaction and therefore increases the yield of BNNTs. This improved synthesis method brings the large-scale production and application of BNNTs one step closer.     

大粒径硅溶胶粒径增长及其控制工艺的研究

大粒径硅溶胶在涂料、化学机械抛光、催化剂载体等工业领域中都有着极其广泛的应用。在添加适量催化剂的条件下,采用单质硅粉氧化法制备了大粒径溶胶。重点介绍了大粒径硅溶胶的分类、性质及应用,通过研究不同条件下大粒径硅溶胶的粒径增长过程分析了大粒径硅溶胶制备过程中的粒径增长机理。在添加阴离子表面活性剂的条件下,采用浓缩蒸馏实验研究了大粒径硅溶胶粒径增长与其浓度的关系,结果表明：随着大粒径硅溶胶浓度的增大,大粒径硅溶胶的粒径呈先减小后增大的趋势。最后提出了制备大粒径硅溶胶的粒径控制工艺。     

Carbon nanofibers grown over graphite supported Ni catalyst: relationship between octopus-like growth mechanism and macro-shaping

Carbon nanofibers (CNFs) with a uniform diameter of ca. 30 nm have been grown via catalytic decomposition of C₂H₆/H₂ mixture over a nickel (1 wt.%) catalyst supported on graphite microfibers which constitutes the macroscopic shape of the final C/C composite. The productivity reached 50 g of CNFs / g of Ni / h on stream and is among the highest reported to date. The resulting composite consisting in a web-like network of CNFs covering the starting catalyst was characterized by SEM and TEM in order to get more insight on the relationship between the starting nickel catalyst particles and the as-grown CNFs. Apparently the CNFs growth proceeds from different mechanisms: base-growth mechanism involving especially the large nickel particles, tip-growth mechanism involving the smaller nickel particles and tip/octopus-growth mechanism, the most frequent involving all particles. The restructuration of the nickel particle from a globular to a more faceted structure seems to be the key step to produce an extremely large quantity of CNF with yields up to 100 wt.% after 2 h of synthesis.     

火柴棒状纳米碳管的制备及其生长机理

以钨酸钠为钨源,氯化钠为诱导剂,通过水热法制备了三氧化钨(WO₃)纳米棒,再以葡萄糖为碳源,经再次水热反应对WO₃表面进行碳包覆,然后在氢气和甲烷混合气氛中反应一段时间获得了具有火柴棒状结构的纳米碳管。采用X射线衍射分析、场发射扫描电子显微镜、透射电子显微镜和X射线能量散射谱等手段对样品的晶型、形貌、微结构和表面化学元素进行了表征与分析。结果表明,样品由纳米碳管和碳化钨(WC)构成。其中,纳米碳管为火柴棒状,长度0.5～1.0 μm,直径100 nm左右;WC颗粒位于纳米碳管内部,其大小决定了火柴棒状纳米碳管的内径。这充分说明WC在碳管的生长过程中充当催化剂的作用。