Covalent functionalization of multi-walled carbon nanotubes by lipase

Lipase from Candida rugosa was covalently anchored onto acid-treated multi-walled carbon nanotubes (MWNTs) through a self-catalytic mechanism. A variety of characterization techniques including FTIR, Raman spectroscopy, and XPS were employed to demonstrate the formation of the ester linkage between lipase and MWNTs. The MWNTs-lipase biocomposites showed significantly increased solubility in some common-used organic solvents, such as THF, DMF and chloroform. This study may offer a novel and facile route for covalent modification of carbon nanotubes, and expand the potential utilization of both lipases and MWNTs in the fields of biocatalyst and biosensor.     

Synthesis and characterization of water-soluble carbon nanotubes from mustard soot

Carbon nanotubes (CNT) has been synthesized by pyrolysing mustard oil using an oil lamp. It was made water-soluble (wsCNT) through oxidative treatment by dilute nitric acid and was characterized by SEM, AFM, XRD, Raman and FTIR spectroscopy. The synthesized wsCNT showed the presence of several junctions and defects in it. The presence of curved graphene structure (sp²) with frequent sp³ hybridized carbon is found to be responsible for the observed defects. These defects along with the presence of di- and tri-podal junctions showed interesting magnetic properties of carbon radicals formed by spin frustration. This trapped carbon radical showed ESR signal in aqueous solution and was very stable even under drastic treatment by strong oxidizing or reducing agents. Oxidative acid treatment of CNT introduced several carboxylic acid group functionalities in wsCNT along with the nicking of the CNT at different lengths with varied molecular weight. To evaluate molecular weights of these wsCNTs, an innovative method like gel electrophoresis using high molecular weight DNA as marker was introduced.     

不同氮掺杂浓度碳纳米管的制备及其成键特性分析

采用化学气相沉积法,以吡啶为氮源,乙炔为碳源,制备出了不同氮掺杂含量的碳纳米管.使用透射电子显微镜(TEM)和X射线荧光光谱(XPS)对样品的形貌和成键特性进行了观察和分析.TEM测试发现随着掺杂量的增大,氮掺杂碳纳米管的竹节长度从120 nm减小为40 nm左右,同时管身变得更加弯曲,管壁变得粗糙.XPS测试发现氮元素在碳纳米管中以“吡啶”、“吡咯”和“石墨”三种C—N键合方式存在.结合三种价键的形成原因,分析了氮掺杂浓度对键合形式的影响,并根据价键的存在形式解释了碳纳米管形貌变化的原因. 关键词： 碳纳米管 氮掺杂 XPS     

Functionalization of vertically aligned carbon nanotubes with polystyrene via surface initiated reversible addition fragmentation chain transfer polymerization

Here we demonstrate the covalent attachment of vertically aligned (VA) acid treated single-walled carbon nanotubes (SWCNTs) onto a silicon substrate via dicyclohexylcarbodiimide (DCC) coupling chemistry. Subsequently, the pendant carboxyl moieties on the sidewalls of the VA-SWCNTs were derivatized to acyl chlorides, and then finally to bis(dithioester) moieties using a magnesium chloride dithiobenzoate salt. The bis(dithioester) moieties were then successfully shown to act as a chain transfer agent (CTA) in the reversible addition fragmentation chain transfer (RAFT) polymerization of styrene in a surface initiated “grafting-from” process from the VA-SWCNT surface. Atomic force microscopy (AFM) verified vertical alignment of the SWCNTs and the maintenance thereof throughout the synthesis process. Finally, Raman scattering spectroscopy and AFM confirmed polystyrene functionalization.     

Synthesis of anatase titania-carbon nanotubes nanocomposites with enhanced photocatalytic activity through a nanocoating-hydrothermal process

Anatase TiO₂ nanoparticles were covalently anchored onto acid-treated multi-walled carbon nanotubes (MWNTs) through a nanocoating-hydrothermal process to obtain TiO₂-MWNTs nanocomposites. The composition and structural properties of the nanocomposites were characterized by XRD, BET, TG, TEM, HRTEM, EDX, XPS, and FTIR, and the formation of ester-bond linkage between TiO₂ nanoparticles and MWNTs was demonstrated. The enhanced photocatalytic activity of TiO₂-MWNTs nanocomposites was probed by photodegradation reaction of methylene blue under visible-light irradiation.     

碳纳米管的稳定性研究

石墨晶体结构遭到破坏时,总是碎化为微小尺寸的片状粉末.孤立的石墨烯片在其边缘存在大量的悬挂键,使得石墨烯片的能量较高,状态也不稳定.石墨烯片卷曲形成碳纳米管后,悬挂键减少,系统能量相应降低.另一方面,石墨烯片卷曲形成碳纳米管将产生相应的形变势能,形变势能的产生将抵消由于减少石墨烯片边缘上的悬挂键所带来的能量降低,使碳纳米管的能量可能高于石墨烯片的能量,导致碳纳米管结构的不稳定.在建立碳纳米管生成的力学模型并进行深入理论分析的基础上得出了碳纳米管可以稳定存在的最小直径约为0.32nm的结论. 关键词： 碳纳米管 稳定性 形变势能 键能     

单壁BN纳米管和碳纳米管物理吸附储氢性能的理论对比研究

采用巨正则蒙特卡罗方法(GCMC)研究了单壁氮化硼纳米管(SWBNNTs)和单壁碳纳米管(SWCNTs)的物理吸附储氢性能,主要对比研究了纳米管的管径、温度和手性对二者物理吸附储氢量的影响. 研究结果表明：在低温下,SWBNNTs的物理吸附储氢性能优于相应的SWCNTs;但是随着温度的升高,二者的物理吸附储氢性能差别越来越小,在常温下,SWBNNTs不具备有比SWCNTs更强的物理吸附储氢性能,而是和相同条件下的SWCNTs相差不大,只是在高压下的物理吸附储氢量稍稍大于SWCNTs,并给出了合理的理论解释 关键词： 巨正则蒙特卡罗方法(GCMC) 单壁氮化硼纳米管(SWBNNTs) 单壁碳纳米管(SWCNTs) 储氢     

Synthesis and characterization of carbon nanotubes on carbon microfibers by floating catalyst method

In this paper, carbon nanotubes were synthesized on carbon microfibers by floating catalyst method with the pretreatment of carbon microfibers at the temperature of 1023 K, using C₂H₂ as carbon source and N₂ as carrier gas. The morphology and microstructure of carbon nanotubes were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The composition of carbon nanotubes was determined by energy dispersive X-ray spectroscopy (EDX). The results showed that the surface of treated carbon microfibers was thickly covered by carbon nanotubes with diameters of about 50 nm. EDX image indicated that the composition of carbon nanotubes was carbon. In comparison with the sample grown on untreated carbon microfibers surface, it was found that after carbon microfibers were boiled in the solution of sulfur acid and nitric acid (VH₂SO₄:VHNO₃ = 1:3) and immersed in the solution of iron nitrate and xylene, carbon nanotubes with uniform density can be grown on carbon microfibers surface. Based on the results, we concluded that the pretreatment of carbon microfibers had great effect on the growth of carbon nanotubes by floating catalyst method.     

Off-axis Thermal Properties of Carbon Nanotube Films

Theoretical calculations have predicted that individual Single-Walled Carbon Nanotubes (SWNT) have extremely high thermal conductivity (around 6.6 × 10⁴ W/m-K). The feasibility of constructing practical devices using the above mentioned properties, is critically dependent on the ability to synthesize high-thermal-conducting films. Highly conducting films would be of great use as heat sinks for the next generation of integrated chips. Excessive heating is currently a very serious problem in the endeavor for achieving faster and smaller chips. Since it is still not possible to perfectly align SWNT in the macroscopic scale, the thermal properties of the nano-films are therefore expected to have a statistical effect and thus lower than the intrinsic thermal conductivity of a single nanotube. Also the thermal conductivity perpendicular to the tube direction is more significant from a practical point of view. Multi-Walled Carbon Nanotubes (MWNT) were synthesized by Chemical Vapor Deposition (CVD) technique and subsequently characterized. The thin MWNT films were deposited by a solution casting technique over a metallic substrate. The off-axis thermal properties of these nano-films were studied by AC-calorimetry studies. In this method, the sample is heated by an AC source and the measurement of the relaxation rate is used to determine the thermal properties. This technique is well established for studying the thermal properties of complex fluids. Our results are contrasted with other thermal conductivity measurements intrinsic and bulk carbon nanotube samples. We have also measured off-axis thermal properties of nano-films synthesized from more crystalline SWNT samples and have compared this result with that of the MWNT-film. A model to explain the thermal conduction for our system is proposed. George Muench: Presently at the Department of Physics, University of New Haven, West Haven, CT-06516, USA     

Synthesis,characterization, and electrochemical properties of imidazole derivatives functionalized single‐walled carbon nanotubes

The imidazole derivatives functionalized single‐walled carbon nanotubes (SWNTs) were synthesized by a diazonium‐based reaction. We have designed and synthesized two imidazole derivatives to modify SWNTs. The resulting products were characterized by Fourier transform infrared (FT‐IR) spectroscopy, Raman spectroscopy, ultraviolet visible (UV/Vis) spectroscopy, thermo gravimetric analysis (TGA), energy dispersive X‐ray spectroscopy (EDX), transmission electron microscopy (TEM), and atomic force microscopy (AFM). Electrochemical measurements via a cyclic voltammetry method revealed that the weak intramolecular electronic interactions presented between the attached imidazole derivatives groups and the nanotubes. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis of carbon nanotubes via Fe-catalyzed pyrolysis of phenolic resin

Carbon nanotubes (CNTs) with 40–100 nm in diameter and tens of micrometers in length were prepared via catalytic pyrolysis of phenol resin in Ar at 673–1273 K using ferric nitrate as a catalyst precursor. Structure and morphology of pyrolyzed resin were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Ferric nitrate was transformed to Fe₃O₄ at 673 K, and to metallic Fe and Fe_xC carbide at 873–1273 K. The optimal weight ratio of Fe catalyst to phenol resin for growing CNTs was 1.00 wt%, and the optimal temperature was 1073 K. In addition, use of a high pressure increased the yield of CNTs. Density functional theory (DFT) calculations suggest that Fe catalysts facilitate the CNTs growth by increasing the bond length and weakening the bond strength in C₂H₄ via donating electrons to the C atoms in it.     

Synthesis, characterization and cytotoxicity of surface amino-functionalized water-dispersible multi-walled carbon nanotubes

Surface functionalization of multi-walled carbon nanotubes (MWCNTs), with amino groups via chemical modification of carboxyl groups introduced on the nanotube surface, using O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate (N-HATU) and N,N-diisopropylethylamine (DIEA) is reported. The N-HATU coupling agent provides faster reaction rate and the reaction occurs at lower temperature compared to amidation and acylation-amidation chemistry. The amines, 1,6-hexanediamine (HDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and 1,4-phenylenediamine (PDA) were used. The resulting materials were characterized with different techniques such as FTIR, XRD, elemental analysis, TGA, TEM, UV-vis spectroscopy and cyclic voltammetry. MWCNTs functionalized with PDA posses the best dispersibility and electron transfer properties in comparison to the others amines. Functionalized MWCNTs, at the concentrations between 1 and 50 μg ml⁻¹, were not cytotoxic for the fibroblast L929 cell line. However, the concentrations of MWCNTs higher of 10 μg ml⁻¹ reduced cell growth and this effect correlated positively with the degree of their uptake by L929 cells.     

单壁碳纳米管的场发射特性研究

利用场发射显微镜(FEM)和四极质谱计分别研究了经过热处理的单壁碳纳米管的场发射图像和热处理过程中样品脱附的残气质谱.当热处理温度达到1000℃左右时得到了单壁碳纳米管的场发射像,此像可能是顶端开口的单根(16,0)锯齿形单壁碳纳米管的具有原子可分辨的场发射图像.四极质谱分析结果表明,在此温度范围W针尖晶粒间隙中有O原子和C原子释放出来.它们对单壁碳纳米管顶端的修饰是我们能观察到这些碳纳米管场发射像的可能原因. 关键词： 单壁碳纳米管(SWCNTs) 场发射显微镜(FEM) 四极质谱     

Synthesis, characterization and catalytic oxidation properties of multi-wall carbon nanotubes with a covalently attached copper(II) salen complex

Hydroxyl functionalized copper(II) Schiff-base, N,N′-bis(4-hydroxysalicylidene)-ethylene-1,2-diaminecopper(II), [Cu((OH)₂-salen)], has been covalently anchored on modified MWCNTs. The new modified MWCNTs ([Cu((OH)₂-salen)]-MWCNTs) have been characterized by TEM, thermal analysis, XRD, XPS, UV-vis, DRS, FT-IR spectroscopy and elemental analysis. The modified copper(II) MWCNTs solid was used to affect the catalytic oxidation of ethylbenzene with tert-butylhydroperoxide as the oxidant at 333 K. The system is truly heterogeneous (no leaching observed) and reusable (no decrease in activity) in three consecutive runs. Acetophenone was the major product though small amounts of o- and p-hydroxyacetophenones were also formed revealing that C-H bond activation takes place both at benzylic and aromatic ring carbon atoms. Ring hydroxylation was more over the “neat” complexes than over the encapsulated complexes.     

单壁碳纳米管中的金属-半导体转变与对称性

报道了最近作者对受压扶手椅形单壁碳纳米管中的金属-半导体转变机理的理论研究。这种转变在两种因素的共同作用下得以发生，即外加压力造成碳纳米管镜像对称破缺，以及被压碳纳米管两侧原子发生成键相互作用．作者还进一步揭示了发生这种转变的普遍机制：只要将单壁碳纳米管中两套原来等价的子晶格变得可以区分(对称性破缺)，在费米能附近就会产生能隙．     

锥顶碳纳米管的结构稳定性与场致发射性能

运用密度泛函理论研究了锥顶碳纳米管的结构稳定性与电子场致发射性能.结果表明:在外电场作用下,该体系的结构稳定性明显优于碳纳米锥体、C₃₀半球封口的碳纳米管,且电子发射性能与锥角大小、锥顶构型密切相关,特别是锥角38.9°及棱脊型顶部的cone₁@(6,6)综合性能最优,用其作为场致发射源的阴极时可显著提高发射电流密度并延长器件的使用寿命. 关键词： 锥顶碳纳米管 电子场致发射 结构稳定性 密度泛函理论     

Field—ion microscopy observation of single—walled carbon nanotubes

Field-ion microscopy(FIM),a tool for surface analysis with atomic resolution,has been employed to observe the end structure of single-walled carbon nanotubes(SWCNTs).FIM images revealed the existence of open SWCNT ends,Amorphous carbon atoms were also observed to occur around SWCNTs and traditional field evaporation failed to remove them.Heat treatment was found to be efficacious in altering the end structures of SWCNT bundles.Carbon and oxygen atoms released from heated tungsten filament are believed to be responsible for the decoration imposed on the SWCNT ends.     

Characteristics of Co-filled carbon nanotubes

The Co-filled carbon nanotubes (CNTs) film was produced on silicon substrate by electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-CVD). The effects of different plasma powers of 200, 300, 400 and 500 W, on the morphology, structure and electrical properties of the CNTs film, were studied. The results showed that the surface density of the vertical nanotubes decreased when the plasma power was higher than 200 W. When plasma power of 300 W was used, the ends of the metal-filled carbon nanotubes (MF-CNTs) became straighter and more uniform. The Co-filled CNTs grown at 300 and 400 W had a current discharge at the applied voltages of 30 and 40 V, respectively. In addition, the surface morphology and the structure of the CNTs film were examined using scanning electron microscopy (SEM) and high-resolution field emission gun transmission electron microscopy (TEM). Energy dispersive X-ray spectroscopy (EDXS) analyses were performed to identify the composition of the material inside the CNTs.     

Diameter-dependent thermal-oxidative stability of single-walled carbon nanotubes synthesized by a floating catalytic chemical vapor deposition method

In this paper, purified single-walled carbon naotubes (SWCNTs) with three different diameters were synthesized using a floating catalytic chemical vapor deposition method with ethanol as carbon feedstock, ferrocene as catalyst, and thiophene as growth promoter. The thermal-oxidative stability of different-diameter SWCNTs was studied by using thermal analysis (TG, DTA), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analysis. The results indicate that small diameter SWCNTs (∼1 nm) are less stable and burn at lower temperature (610 °C), however, the larger diameter SWCNTs (∼5 nm) survive after burning at higher temperature (685 °C), the oxidation rate varies inversely with the tube diameter of SWCNTs, which may be concluded that the higher oxidation-resistant temperature of larger diameter SWCNTs can be attributed to the lower curvature-induced strain by rolling the planar graphene sheet for the larger diameter, so small tubes will become thermodynamically unstable.     

Filling of single-walled carbon nanotubes by CuI nanocrystals via capillary technique

The present study is focused on the synthesis and investigation of the nanocomposite CuI@SWNT obtained by the filling of metallic single-walled carbon nanotubes (SWNTs) (inner diameter 1–1.4 nm) by wide-gap semiconducting CuI nanocrystals using so-called capillary technique. The method is based on the impregnation of pre-opened SWNTs by molten CuI in vacuum with subsequent slow cooling to room temperature. SWNTs and CuI@SWNT nanocomposites were studied by nitrogen capillary adsorption method, EDX microanalysis, HRTEM microscopy and Raman spectroscopy. The changing of electronic properties of CuI@SWNT as compare to row nanotubes was observed.