Influence of the catalyst type on the growth of carbon nanotubes via methane chemical vapor deposition

The preparation of the catalyst is one of the key parameters which governs the quality of carbon nanotubes (CNTs) grown by catalyzed chemical vapor deposition (CVD). We investigated the influence of three different procedures of catalyst preparation on the type and diameter of CNTs formed under identical growth conditions via methane CVD. In the first one, chemically synthesized colloidal iron oxide or iron molybdenum alloy nanoparticles were used, which were homogeneously deposited on silicon substrates by spin coating to prevent them from coalescence under CVD growth conditions. The obtained multiwall CNTs (MWNTs) exhibited diameters corresponding to the catalyst particle size, whereas no formation of single-wall CNTs (SWNTs) was observed. In the second method, commercial porous alumina nanoparticles were used in association with iron and molybdenum salts and the Fe/Mo catalyst was formed in situ. We determined that the alumina concentration significantly influenced the morphology of the catalyst and that below a critical value of the range of 1 g/L no CNTs were formed. While yielding nearly defect-free SWNTs, their diameter could not be controlled using this procedure, resulting in a large distribution of tube sizes. In a third, new preparation method, associating alumina and iron-based nanoparticles, SWNTs of a different size and narrower diameter distribution as compared to the second method were obtained. Our results are evidence of the essential role of alumina particles in the formation of SWNTs, and the newly developed method opens up a way to the synthesis of diameter-controlled SWNTs via catalyzed CVD.     

Electronic structure and field emission of multiwalled carbon nanotubes depending on growth temperature

The electronic structure of multiwalled carbon nanotubes (CNTs) has been investigated, depending on the growth temperature, using synchrotron X-ray photoelectron spectroscopy (XPS) and field emission measurements. The vertically aligned CNTs are grown via pyrolysis of ferrocene and acetylene in a broad temperature range 600-1000 degrees C. The CNTs have a cylindrical structure with a uniform diameter of 20 nm. As growth temperature increases, due to an improved crystallinity of the graphitic sheets, the width of the XPS C 1s peak becomes narrower and the intensity of the valence band increases. Field emission from the as-grown CNTs exhibits a large enhancement of current density with growth temperature, strongly correlated with the electronic structure revealed by XPS.     

含Fe、Co、Ni的LDHs为催化剂前体生长碳纳米管

分别以具有相似Fe、Co、Ni含量的层状双金属氢氧化物（LDHs）为催化剂前体,用化学气相沉积的方法生长碳纳米管（CNTs）。 催化剂由LDHs焙烧还原得到。 通过X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）及拉曼光谱（Raman）测试技术对LDHs及其焙烧产物的结构、CNTs的形貌和结构进行了研究。 结果表明,3种催化剂生长的CNTs均为多壁结构;其中Co催化剂活性较低,生长CNTs的管径较细、石墨化程度较高;Ni催化剂的活性较高,生长CNTs的密度较大、管壁较厚、石墨化程度较差;Fe催化剂的活性介于Co和Ni之间。 催化剂活性及CNTs的密度可以由生长CNTs的结构来解释。     

含Fe、Co、Ni的层状双金属氢氧化物为催化剂前体生长碳纳米管

分别以具有相似Fe、Co、Ni含量的层状双金属氢氧化物(LDHs)为催化剂前体,用化学气相沉积的方法生长碳纳米管(CNTs).催化剂由LDHs焙烧还原得到.通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)及拉曼光谱(Raman)测试技术对LDHs及其焙烧产物的结构、CNTs的形貌和结构进行了研究.结果表明,3种催化剂生长的CNTs均为多壁结构;其中Co催化剂活性较低,生长CNTs的管径较细、石墨化程度较高;Ni催化剂的活性较高,生长CNTs的密度较大、管壁较厚、石墨化程度较差;Fe催化剂的活性介于Co和Ni之间.催化剂活性及CNTs的密度可以由生长CNTs的结构来解释.     

A catalytic gas diffusion layer for improving the efficiency of a direct methanol fuel cell

The efficiency of a single direct methanol fuel cell (DMFC) with Pt–Ru decorated carbon nanotubes directly grown on carbon cloth (Pt–Ru/CNTs/CC) as a catalytic gas diffusion layer (GDL) at the anode was evaluated by polarization analysis. Pt–Ru nanoparticles were electrodeposited on dense carbon nanotubes directly grown on carbon cloth in ethylene glycol containing sulfuric acid solutions. The presence of relatively well dispersed Pt–Ru nanoparticles (4–6 nm) on the surfaces of CNTs was confirmed by transmission electron microscopy. Two more GDLs, one with dense CNTs but without the presence of Pt–Ru nanoparticles and the other with neither CNTs nor catalysts, were also prepared for comparison purpose. For quantitatively evaluating the performance of the catalytic GDL, three identical membrane–electrode-assemblies were prepared and laminated with different GDLs before they were used to construct DMFCs for performance test. It was found via polarization analyses the catalytic GDL was able to promote the peak specific power density of the DMFC by 27% at ambient temperature.     

Two types of carbon nanocomposites: Graphite encapsulated iron nanoparticles and thin carbon nanotubes supported on thick carbon nanotubes, synthesized using PECVD

In this work, graphite encapsulated Fe nanoparticles and thin carbon nanotubes (CNTs) supported on the pristine CNTs, respectively, were synthesized using plasma enhanced chemical vapor deposition via efficiently controlling the flow rate of discharging CH₄ and H₂ gas. The properties of the obtained hybrid materials were characterized with superconducting quantum interference and field emission measurements. The results showed that the encapsulated Fe nanoparticles had diameters ranging from 1 to 30 nm, and this hybrid nanocomposite exhibited a ferromagnetic behavior at room temperature. Thin CNTs with an average diameter of 6 nm were attached to the surface of the prepared CNTs, which exhibited a lower turn-on field and higher emission current density than the pristine CNTs. The Fe nanoparticles either encapsulated with graphite or used as catalyst for thin CNTs growth were all originated from the pyrolysis of ferrocene.     

High-density growth of carbon nanotubes with catalytic sites activated on nickel substrate

We describe the growth of carbon nanotubes (CNTs) from catalytic nanoparticles formed on a nickel surface. For the growth of CNTs, a chemical vapor deposition (CVD) furnace was set up and ethanol was used as carbon source. Observation of SEM images shows that CNTs grew densely on the nickel surface and that nanoparticles play a key role in the growth of the CNTs. XRD and Raman analyses reveal that the obtained products have graphitic pattern of multi-walled carbon nanotubes (MWCNTs). Also HRTEM images confirm clearly that the product was a MWCNT and their diameter was in the range of 20–50 nm.     

Tuning of redox properties of iron and iron oxides via encapsulation within carbon nanotubes

We report the tuning of the redox properties of iron and iron oxide nanoparticles by encapsulation within carbon nanotubes (CNTs) with varying inner diameters. Raman spectroscopy was employed to investigate the interaction of the encapsulated nanoparticles with the CNTs. A red shift of the Fe-O mode is observed in the nanoparticles deposited on the outer CNT surfaces with respect to bulk Fe2O3. However, this mode is found to be stepwise blue-shifted with decreasing inner diameter in the CNT-encapsulated Fe2O3 nanoparticles, suggesting an enhanced interaction of Fe2O3 with the inner CNT surface as its curvature increases. The autoreduction of the encapsulated Fe2O3 is significantly facilitated inside CNTs with respect to the outside nanoparticles. Interestingly, it becomes more facile with decreasing CNT channel diameter as evidenced by temperature programmed reaction, in situ XRD, and Raman spectroscopy. The oxidation of encapsulated metallic Fe nanoparticles on the other hand is retarded in comparison to that of the outside Fe particles as shown by in situ XRD and gravimetrical measurements with an online microbalance. We attribute this tunable redox behavior of transition metal nanoparticles inside CNTs to a particular electronic interaction of the encapsulates with the interior CNT surface, which stabilizes the metallic state of Fe.     

E?ect of Growth Parameters on Morphology of Vertically Aligned Carbon Nanotubes

Vertically aligned carbon nanotubes (CNTs) were synthesized on Fe-deposited silicon substrates using chemical vapor deposition. Scanning electron microscope investigations reveal that the morphology of the CNTs depends on several growth parameters including the reaction temperature, the size of catalyst nanoparticles, and the partial pressure of the reaction gas. When the reaction temperature rises or the concentration of carbon source gas increases, the diameter of CNTs gets larger, but the length becomes shorter. With decreasing thickness of the catalyst film, the diameter of the CNTs shrinks monotonically, but the length of the CNTs increases first, reaches a maximum and then decreases afterwards. These results indicate that the diameter and the length of the vertically aligned CNTs can be manipulated by selecting appropriate growth parameters.     

Preparation of airborne Ag/CNT hybrid nanoparticles using an aerosol process and their application to antimicrobial air filtration

Carbon nanotubes (CNTs) have been widely used in a variety of applications because of their unique structure and excellent mechanical and electrical properties. Additionally, silver (Ag) nanoparticles exhibit broad-spectrum biocidal activity toward many different bacteria, fungi, and viruses. In this study, we prepared Ag-coated CNT hybrid nanoparticles (Ag/CNTs) using aerosol nebulization and thermal evaporation/condensation processes and tested their usefulness for antimicrobial air filtration. Droplets were generated from a CNT suspension using a six-jet collison nebulizer, passed through a diffusion dryer to remove moisture, and entered a thermal tube furnace where silver nanoparticles were generated by thermal evaporation/condensation at ～980 °C in a nitrogen atmosphere. The CNT and Ag nanoparticle aerosols mixed together and attached to each other, forming Ag/CNTs. For physicochemical characterization, the Ag/CNTs were introduced into a scanning mobility particle sizer (SMPS) for size distribution measurements and were sampled by the nanoparticle sampler for morphological and elemental analyses. For antimicrobial air filtration applications, the airborne Ag/CNT particles generated were deposited continuously onto an air filter medium. Physical characteristics (fiber morphology, pressure drop, and filtration efficiency) and biological characteristics (antimicrobial tests against Staphylococcus epidermidis and Escherichia coli bioaerosols) were evaluated. Real-time SMPS and transmission electron microscopy (TEM) data showed that Ag nanoparticles that were <20 nm in diameter were homogeneously dispersed and adhered strongly to the CNT surfaces. Because of the attachment of Ag nanoparticles onto the CNT surfaces, the total particle surface area concentration measured by a nanoparticle surface area monitor (NSAM) was lower than the summation of each Ag nanoparticle and CNT generated. When Ag/CNTs were deposited on the surface of an air filter medium, the antimicrobial activity against test bacterial bioaerosols was enhanced, compared with the deposition of CNTs or Ag nanoparticles alone, whereas the filter pressure drop and bioaerosol filtration efficiency were similar to those of CNT deposition only. At a residence time of 2 h, the relative microbial viabilities of gram-positive S. epidermidis were ～32, 13, 5, and 0.9% on the control, CNT-, Ag nanoparticle-, and Ag/CNT-deposited filters, respectively, and those of gram-negative E. coli were 13, 2.1, 0.4, and 0.1% on the control, CNTs, Ag nanoparticles, and Ag/CNTs, respectively. These Ag/CNT hybrid nanoparticles may be useful for applications in biomedical devices and antibacterial control systems.     

Growth, new growth, and amplification of carbon nanotubes as a function of catalyst composition

Carbon nanotubes (CNTs) have been grown using Fe, Co, Ni, and Co/Fe spin-on-catalyst (SOC) systems, involving the metal salt dispersed with a spin-on-glass precursor. During initial growth runs (CH4/H2/900 degrees C), the CNT yield followed the order Co-SOC > Fe-SOC > Ni-SOC. The Fe catalysts produced the longest nanotubes at the expense of a larger average CNT diameter and broader diameter distribution than the Co-SOC system. A series of Co/Fe-SOCs were prepared where as the atomic percentage of Co is increased nucleation of CNT increases but the CNT length decreases. The linear relationship between the diameter and length of CNTs grown from the Co/Fe-SOC suggests that slow growth is beneficial with respect to control over CNT diameter. After initial CNT growth, the original samples were subjected to additional growth runs. Four individual reactions were observed in the Fe-SOC and binary Co/Fe-SOC: regrowth (amplification), double growth (a second CNT growing from a previously active catalyst), CNT etching, and nucleation from initially inactive catalysts (new growth). CNT etching was observed for the mixed catalyst systems (Co/Fe-SOC) but not for either Fe-SOC or Co-SOC. During the regrowth experiments, CNTs were observed that were not present after the initial growth run (and were not as a result of amplification or double growth). Thus, catalysts, which were initially inactive toward nucleation of CNTs in the original growth run, are capable of becoming activated when placed back into the furnace and submitted to regrowth under identical conditions.     

多壁碳纳米管结构与其电化学容量之间关系的研究

采用化学气相沉积法,通过改变催化剂的成分、碳源、反应和后处理条件来制 备不同管径、管长、石墨化程度的多壁碳纳米管。经电化学容量性能测试、透射电 子显微镜观察和N_2吸附等结构表征,发现管径分布为30.0～40.0 nm、管长越短、 石墨化程度越低、比表面积越大、孔容越大的多壁碳纳米管具有更好的电化学容量 。     

Electrochemically-assisted deposition of oxidases on platinum nanoparticle/multi-walled carbon nanotube-modified electrodes

Platinum nanoparticles were electrodeposited by a multi-potential step technique onto a multi-walled carbon nanotube (MWCNT) film pre-casted on a glassy carbon (GC) or boron-doped diamond (BDD) electrode. The MWCNT network consisted of Pt nanoparticles with an average diameter of 120 nm after an optimization of 36 deposition cycles. The resulting electrochemical sensors were capable of detecting hydrogen peroxide as low as 25 nM. Five different enzymes: glucose, lactate, glutamate, amino acid and xanthine oxidases, respectively, were deposited by a constant current technique for 5-10 min to form a stable and active biolayer for the analysis of their corresponding analytes. The glucose oxidase-based biosensor was linear up to 10 mM glucose with a detection limit of 250 nM and a response time of 5 s. Similar response times and detection limits were observed with glutamate, lactate, and amino acid oxidase despite the fact that the linear ranges were noticeably narrower. The mechanism of deposition was attributed to the decrease of local pH, created by oxygen evolution and effected enzyme precipitation.     

多元醇法制备Cu2O/CNTs复合材料的研究

以Cu(CH₃COO)₂•H₂O和经硝酸处理的CNTs作为原料, 采用多元醇法成功合成了纳米氧化亚铜均布于碳纳米管表面的复合光催化剂. 用透射电镜(TEM), 高分辨透射电镜(HRTEM), X射线粉末衍射(XRD)对样品进行了表征, 测试结果表明大小为2～5 nm的氧化亚铜纳米颗粒均匀分散于碳纳米管的表面. 讨论了反应条件对Cu₂O在CNTs上负载效果的影响并就多元醇法合成Cu₂O/CNTs复合材料的反应机理作了初步探讨.     

Alignment of carbon nanotubes under low magnetic fields through attachment of magnetic nanoparticles

The alignment of multiwalled carbon nanotubes (MWNTs) has been accomplished through deposition of uniform layers of magnetite/maghemite nanoparticles (diameter = 6-10 nm) and use of an external magnetic field. The coating of CNTs with magnetic nanoparticles was performed by combining the polymer wrapping and layer-by-layer (LbL) assembly techniques. The particle-coated MWNTs are superparamagnetic and can be aligned at room temperature on any substrate by deposition from an aqueous solution in an external field B = 0.2 T. The volume magnetization of the particle coated MWNTs is found to be enhanced by 17% compared to the pure particles in a powder indicating that either the adsorption process onto the CNTs changes the particle magnetization, or the MWNTs carry an intrinsic magnetization due to remaining Ni used as a catalyst for the growth process.     

Microstructure control of MnO2/CNT hybrids under in-situ hydrothermal conditions

In this work, single-crystalline MnO₂ nanoparticles were directly grown on the surface of multi-walled carbon nanotubes (CNTs) homogeneously under in-situ hydrothermal conditions, during which the CNTs were well dispersed in aqueous solution with the aid of dodecyl benzene sulphonic acid sodium (SDBS). This stable suspension ensures the continuous deposition of the MnO₂ nanocrystals. It was found that the MnO₂/CNTs nanocomposites formed in the presence of CNTs, but the MnO₂ nanowires formed without CNTs under the same hydrothermal conditions. Moreover, the as-synthesized MnO₂/CNTs sample showed a high specific capacity and cycling stability, which was ascribed to its highly-homogeneous hybrid nanostructure. This homogeneous MnO₂/CNTs nanocomposite is shown to be able to take full advantages of both the high capacity of MnO₂ and the high electron conductivity of CNTs by integrating them homogeneously. This homogeneous hybrid nanostructure is a promising electrode material for energy storage/conversion devices with excellent performances.     

Obtaining chitosan nanoparticles from Bombyx mori

Russian Chemical Bulletin - Chitosan nanoparticles (CS NPs) with sizes of 100–700 nm were isolated from Bombyx mori. The NPs were obtained by fractional precipitation in the presence of a...     

Electrochemical modification of vertically aligned carbon nanotube arrays

Electrochemical oxidation and reduction were utilized to modify vertically aligned carbon nanotube (CNT) arrays grown on a porous network of conductive carbon microfibers. Ultrafast and complete CNT opening and purification were achieved through electrochemical oxidation. Highly dispersed platinum nanoparticles were then uniformly and densely deposited as electrocatalysts onto the surface of these CNTs through electrochemical reduction. Using supercritical drying techniques, we demonstrate that the unidirectionally aligned and laterally spaced geometry of the CNT arrays can be fully retained after being subjected to each step of electrochemical modification. The open-tipped CNTs can also be electrochemically detached in full lengths from the supporting substrates and harvested if needed.     

纳米三氧化钨复合催化剂的制备及对甲醇电催化性能

采用浸渍沉淀法制备出WO₃-碳纳米管(WO₃-CNTs)纳米复合材料, 微波辅助乙二醇法在其表面负载活性成分Pt, 得到纳米Pt/WO₃-CNTs 催化剂. 采用X射线衍射(XRD), 透射电子显微镜(TEM)和X射线光电子能谱(XPS)等测试手段对催化剂的结构和形貌进行表征, 结果表明Pt 纳米粒子为面心立方晶体结构, 粒径大小在3-5 nm之间, 均匀地分布在WO₃-CNTs 纳米复合材料表面, 同时发现催化剂中的Pt 主要以金属态的形式存在. 采用循环伏安和计时电流法研究了在酸性溶液中Pt/WO₃-CNTs 催化剂对甲醇的电催化氧化性能, 结果表明Pt/WO₃-CNTs 催化剂比用硝酸处理的碳纳米管载铂催化剂(Pt/CNTs)对甲醇呈现出更高的电催化氧化活性和抗CO中毒性能.     

Preparation and electrochemical property of Fe2O3 nanoparticles-filled carbon nanotubes

Fe(2)O(3) nanoparticles with a mean diameter of ~9 nm were homogeneously filled into the hollow core of high aspect ratio CNTs synthesized by the AAO template method with tunable filling ratios. These Fe(2)O(3)-filled CNTs were employed as the anode material of lithium-ion battery, and desirable electrochemical properties of high reversible lithium storage capacity and good rate capability were demonstrated.