催化化学气相沉积法制备螺旋形多壁碳纳米管(英文)

以乙炔为碳源、FeMo/MgO催化剂为模板,采用催化化学沉积法制备了螺旋状多壁碳纳米管(hs-MWC-NTs)。其中FeMo/MgO模板,由作为发泡和助燃剂的柠檬酸燃烧而制成。FeMo/MgO催化剂的XRD谱图揭示其具有微晶的通性。应用SEM、TEM和Raman光谱剖析了合成的炭材料。SEM和TEM观察表明获得了hs-MWC-NTs;Raman光谱的D峰和G峰确认了所获碳纳米管(CNTs)的结晶状态。结果表明:此法乃是合成直径10nm～20nm螺旋形多壁碳纳米管的最容易和简便方法。     

Undoped, nitrogen-doped and boron-doped multiwalled carbon nanotube/poly(vinyl alcohol) composite as active layer in simple hydrostatic pressure sensors

We report on hydrostatic pressure sensors prepared using 10 % w/w multiwalled carbon nanotube (MWCNT)/poly(vinyl alcohol) composites. Three types of carbon nanotubes were used in the composites: undoped MWCNTs, nitrogen-doped MWCNTs and boron-doped MWCNTs (B-MWCNTs). The sensor response was tested using an alternating current input, measuring the capacitance and conductance outputs. The sensors based on the three composites show a linear capacitance and conductance sensitivity pressure dependence in the range 50–120 kPa, but a higher sensitivity to pressure dependence above this interval. The highest angular coefficient of the sensitivity, which reached 0.092 kPa^?1, was observed for the capacitance sensitivity of the B-MWCNT based composite.     

Preparation of poly (vinyl alcohol) fibers strengthened using multiwalled carbon nanotubes functionalized with tea polyphenols

Poly (vinyl alcohol) (PVA) fibers were strengthened using multiwalled carbon nanotubes (MWCNTs) functionalized using a green modifier tea polyphenols (TP). MWCNTs were first modified using TP to increase their dispersity in dimethyl sulfoxide (DMSO)/water solution, and then PVA was added to the dispersion to form new dispersion of PVA/MWCNTs/TP/DMSO/water. The homogeneous dispersion was extruded through a spinning hole into cold methanol to form continuous fibers using gel-spinning process followed by a hot-drawing. The tensile strength of the well-oriented PVA/MWCNTs composite fibers containing merely 0.6 wt% of MWCNTs was surprisingly more than 2.6 times that of pure PVA fiber. Structure characterization showed that well-dispersed MWCNTs were caused by the interfacial interactions between PVA matrix and MWCNTs through the bridge effect of TP.     

Biocompatibility and toxicological studies of carbon nanotubes doped with nitrogen

In this report, we compare the toxicological effects between pure carbon multiwalled nanotubes (MWNTs) and N-doped multiwalled carbon (CNx) nanotubes. Different doses of tubes were administered in various ways to mice: nasal, oral, intratracheal, and intraperitoneal. We have found that when MWNTs were injected into the mice's trachea, the mice could die by dyspnea depending on the MWNTs doses. However, CNx nanotubes never caused the death of any mouse. We always found that CNx nanotubes were far more tolerated by the mice when compared to MWNTs. Extremely high concentrations of CNx nanotubes administrated directly into the mice's trachea only induced granulomatous inflammatory responses. Importantly, all other routes of administration did not induce signs of distress or tissue changes on any treated mouse. We therefore believe that CNx nanotubes are less harmful than MWNTs or SWNTs and might be more advantageous for bioapplications.     

多壁碳纳米管/聚亚苯基苯并二噁唑复合材料的微结构与性能

以甲基磺酸(MSA)为溶剂通过溶液共混法制备了不同多壁碳纳米管(MWNTs)含量的多壁碳纳米管/聚亚苯基苯并二噁唑(MWNTs/PBO)复合材料, 用扫描电镜(SEM)对热处理前后复合材料的微结构进行了分析, 并对其导电、力学和耐热性能进行了研究。结果表明: MWNTs能均匀地分散在聚合物基体中, 并能形成一定的网络结构, 热处理后的复合材料较热处理前的结构更致密, 导电性能和力学性能都有所改善, 其中MWNTs质量分数为10％的热处理后复合材料与纯PBO聚合物相比, 体积电阻率降低约9个数量级, 而拉伸强度和拉伸模量分别提高了95％和53％, 耐热性能也有一定的提高。      

Electrospinning of porphyrin/polyvinyl alcohol (PVA) nanofibers and their acid vapor sensing capability

Fluorescing 5,10,15,20-terakis(1-methyl-4-pyridinio)porphyrin tetra(p-toluenesulfonate) (TMPyP)-embedded and -coated polyvinyl alcohol (PVA) nanofibers were fabricated by using the electrospinning technique. To improve nonpolar solvent solubility of TMPyP/PVA nanofibers, tetraethyl orthosilicate (TEOS) was used as a cross-linking agent. UV-vis spectroscopy showed a strong Q band and two relatively weak Soret bands from the TMPyP/PVA nanofibers, and revealed that the TMPyP molecules were homogeneously loaded to the fibers. Scanning electron microscopy revealed that the electrospun nanofibers had ultrafine structures with an average diameter of ca. 250 nm. X-ray photoelectron spectroscopy confirmed the compositional structure of TMPyP/PVA/TEOS nanofibers and revealed the relative coverage of TMPyP molecules on the surface of TMPyP-embedded and TMPyP-coated PVA/TEOS fibers. For the comparison of the acid vapor sensitivity, TMPyP-embedded PVA/TEOS films, and TMPyP-embedded PVA/TEOS fibers, TMPyP-coated PVA/TEOS fibers were exposed to 1N nitric-acid vapor for 20-60 seconds. Fluorescence microscopy revealed that TMPyP-coated PVA/TEOS nanofibers exhibited better acid-sensing capability than TMPyP-embedded PVA/TEOS nanofibers and films.     

Adsorption of diuron and dichlobenil on multiwalled carbon nanotubes as affected by lead

The effect of lead on the adsorption of diuron and dichlobenil on multiwalled carbon nanotubes (MWCNTs) was investigated to explore the possible application of MWCNTs for removal of both herbicides from contaminated water. The adsorption of diuron and dichlobenil on MWCNTs at pH 6 was nonlinear and fit the Polanyi-Manes model well. The adsorption of diuron and dichlobenil was closely correlated with specific surface areas and micropore volumes of MWCNTs. An increase in oxygen content of MWCNTs with same diameters and similar surface areas decreased the adsorption of diuron and dichlobenil, while increased the adsorption of lead. Micro-Fourier transform infrared spectroscopic study indicated that hydrogen bonding is a main mechanism responsible for the adsorption of diuron or dichlobenil onto MWCNTs-O. Oxygen containing groups, mainly carboxylic groups, significantly increased the adsorption of lead through the formations of outer-sphere and inner-sphere complexes, which are verified by X-ray absorption spectroscopic measurements. Oxygen containing groups and the presence of lead diminished the adsorption of diuron and dichlobenil. The suppression mechanisms of lead were ascribed to hydration and complexation of lead with carboxylic groups, which may occupy part of surface of MWCNTs-O. The large hydration shell of lead cations may intrude or shield hydrophobic and hydrophilic sites, resulting in a decreased adsorption of diuron and dichlobenil at the lead-complexed moieties.     

Removal of Pb(II) from aqueous solution by oxidized multiwalled carbon nanotubes

Oxidized multiwalled carbon nanotubes (MWCNTs) were employed as sorbent to study the sorption characteristic of Pb(II) from aqueous solution as a function of contact time, pH, ionic strength, foreign ions, and oxidized MWCNTs' contents under ambient conditions using batch technique. The results indicate that sorption of Pb(II) on oxidized MWCNTs is strongly dependent on pH values, and independent of ionic strength and the type of foreign ions. The removal of Pb(II) to oxidized MWCNTs is rather quickly and the kinetic sorption can be described by a pseudo-second-order model very well. Sorption of Pb(II) is mainly dominated by surface complexation rather than ion exchange. The efficient removal of Pb(II) from aqueous solution is limited at pH 7-10. X-ray photoelectron spectroscopy (XPS) is performed to study the sorption mechanism at a molecular level and thereby to identify the species of the sorption processes. The 3-D relationship of pH, Ceq and q indicates that all the data of Ceq-q lie in a straight line with slope -V/m and intercept C0V/m for the same initial concentration of Pb(II) and same content of oxidized MWCNTs of each experimental data.     

定向碳纳米管的化学气相沉积制备法

报道了一种简便有效的合成定向碳纳米管 (CNTs)的化学气相沉积 (CVD)制备方法。以铁为催化剂 ,乙炔为碳源 ,采用单一反应炉 ,直接在石英基底上沉积催化剂颗粒薄膜 ,成功合成了定向性好、管径均匀的高质量大密度的碳纳米管     

Syntheses and catalytic applications of the high-N-content,the cup-stacking and the macroscopic nitrogen doped carbon nanotubes

The high-N-content, the cup-stacking and the macroscopic nitrogen doped carbon nanotubes(NCNT)were synthesized via an easily manufactured catalytic chemical vapor deposition(CCVD) method. Nitrogen physisorption, transmission electron microscopy(TEM), thermogravimetric analysis(TGA), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS) were used to characterize the as-obtained NCNTs. High reaction temperatures were found to be the key point to the formation of inner-cup-stacking NCNTs. However, the synthesis of the outer-cup-stacking NCNT needs special demands not only to the reaction temperature but also to the catalyst and the carrier gas. The possibility of CO oxidation by NCNT was proved to be very small, and the outer-cup-stacking NCNT showed obvious advantage in the oxidative dehydrogenation(ODH) of butene to butadiene compared to a bamboo-like NCNT with an even higher N content.     

The effects of contacts and ambipolar electrical transport in nitrogen doped multiwall carbon nanotubes

The electrical transport properties of pristine single wall carbon nanotubes (SWCNTs) and lower nitrogen content doped multiwall carbon nanotubes (MWCNTs) (lower than in the experiments of Xiao et al (2005?J. Am. Chem. Soc.?127?8614)) in contact with Au and Pt were studied. Compared with pristine SWCNTs, the Fermi level of the lower nitrogen content doped MWCNTs also moved to the valence band edge with the contact metal's work function increasing. In contrast to Derycke et al' s results (2002?Appl.?Phys.?Lett.?80?2773), the lower nitrogen content doped MWCNTs exhibited ambipolar behavior, and increasing the doping level led to a reduction of the Schottky barrier height of electrons. Consistent with theoretical calculations, the results support the opinion that the degree of Fermi level pinning is minor for doped carbon nanotubes.     

Poly(ethylene-co-vinyl alcohol) functionalized single-walled carbon nanotubes and related nanocomposites

Single-walled carbon nanotubes (SWNTs) were functionalized by poly(ethylene-co-vinyl alcohol) (EVOH) copolymer under carbodiimide-activated esterification reaction conditions. Similar to the parent EVOH copolymer, the EVOH-functionalized carbon nanotubes are soluble in highly polar solvent systems such as DMSO and hot ethanol-water mixtures. The soluble EVOH-SWNT sample was characterized by various techniques, including optical absorption, Raman, NMR, electron microscopy, and thermogravimetric analysis. The common solubility of EVOH and EVOH-SWNT allowed their intimate mixing in solution, and thus the fabrication of nanocomposites in which the SWNTs are homogeneously dispersed in the polymer matrix.     

多壁碳纳米管/杂萘联苯聚醚砜酮复合材料的制备及性能

采用溶液共混及原位复合法制备多壁碳纳米管/杂萘联苯聚醚砜酮复合材料.通过扫描电镜观察材料的形貌,并对材料性能进行研究.对比两种方法,结果表明通过原位复合法制备,碳管在基体中有较好的分散和界面结合,其力学性能和导电性优于溶液共混法制备的复合材料.当碳管含量为3%(质量分数)时,原位复合材料的拉伸模量和强度分别为2.4GPa和107.6MPa,其体积电阻率达到1.0×106 Ω·cm,5%热失重温度提高了20℃.     

Synthesis and electrochemical probing of water-soluble poly(sodium 4-styrenesulfonate-co-acrylic acid)-grafted multiwalled carbon nanotubes

Water-soluble poly(sodium 4-styrenesulfonate-co-acrylic acid)-grafted multiwalled carbon nanotubes (MWNT-g-P(SSS-co-AA)) with core-shell nanostructure were successfully synthesized by in situ free radical copolymerization of sodium 4-strenesulfonate (SSS) and acrylic acid (AA) in the presence of MWNTs terminated with vinyl groups; their structure was characterized by FTIR, (1)H NMR, Raman, TGA and TEM. The results showed that the thickness and content of the copolymer layer grafted onto the MWNT surface are about 7-12?nm and 82.3%, respectively. The P(SSS-co-AA) covalently grafted on MWNTs provides MWNT-g-P(SSS-co-AA) with good hydrophilicity and solubility in water. Then a novel MWNT-g-P(SSS-co-AA)-modified glassy carbon electrode was fabricated by coating; its electrochemical properties were evaluated by electrochemical probe of K(3)[Fe(CN)(6)], and its catalytic behaviors to the electrochemical oxidation processes of dopamine (DA) and serotonin (5-HT) were investigated. Since the MWNT-g-P(SSS-co-AA)-modified electrode possesses strong electron transfer capability, high electrochemical activity and catalytic ability, it can be used in sensitive, selective, rapid and simultaneous monitoring of biomolecules.     

A comparative study on hydrostatic pressure response of sensors based on N-doped, B-doped and undoped carbon-sphere poly (vinyl alcohol) composites

We determine the conductance and capacitance sensitivity of simple hydrostatic pressure sensors based on carbon sphere (undoped, N-doped and B-doped)—poly(vinyl alcohol) composite films deposited onto interdigitated electrodes. We observe that the use of doped carbon spheres results in increased sensitivity variation with respect to pressure when compared to undoped ones, in a range near to atmospheric pressure. For higher pressures of ca. 200?kPa, however, the conductance and capacitance sensitivity of sensors based on undoped carbon spheres is significantly higher, due to a superlinear dependence of both sensitivities on pressure.     

Barrier properties of poly(vinyl alcohol) membranes containing carbon nanotubes or activated carbon

Carbon nanotube addition has been shown to improve the mechanical properties of some polymers. Because of their unique adsorptive properties, carbon nanotubes may also improve the barrier performance of polymers used in contaminant containment. This study compares the barrier performance of poly(vinyl alcohol) (PVA) membranes containing single-walled carbon nanotubes (SWCNTs) to that for PVA containing powdered activated carbon (PAC). Raw and surface-functionalized versions of each sorbent were tested for their abilities to adsorb 1,2,4-trichlorobenzene and Cu(2+), representing the important hydrophobic organic and heavy metal contaminant classes, as they diffused across the PVA. In both cases, PAC (for 1,2,4-trichlorobenzene) and functionalized PAC (for Cu(2+)) outperformed SWCNTs on a per mass basis by trapping more of the contaminants within the barrier membrane. Kinetics of sorption are important in evaluating barrier properties, and poor performance of SWCNT-containing membranes as 1,2,4-TCB barriers is attributed to kinetic limitations.     

Synthesis and characterization of undoped and TM (Co,Mn) doped ZnO nanoparticles

Antibacterial activity of Transition metals (Mn, Co) doped ZnO nanopowders prepared by a DC thermal plasma method against Escherichia coli and Staphylococcus aureus are investigated. The phase and morphology studies have been carried out by X-ray diffraction, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) respectively. All the samples of the present investigation are found to have hexagonal wurtzite structure and crystallite sizes are found to vary from 25 nm to 30 nm. Our bacteriological study showed the enhanced antibacterial activity of transition metals doped ZnO nanoparticles than undoped ZnO indicating the great potential of ZnO nanoparticles in relevant clinical and biomedical applications.     

Preparation of porous chromium oxide nanotubes using carbon nanotubes as templates and their application as an ethanol sensor

Chromium oxide nanotubes were successfully prepared using multi-walled carbon nanotubes (MWCNTs) as a template via a supercritical fluid-mediated route. In this method, with chromium (III) nitrate nonahydrate as precursor, chromium oxide was first deposited on MWCNTs in supercritical ethanol in the presence of NH(4)HCO(3). The as-prepared chromium oxide/MWCNT nanocomposites were characterized by transmission electron microscopy, x-ray diffraction, infrared spectroscopy and thermogravimetric analysis. It was demonstrated that the MWCNTs were coated with a layer of amorphous Cr(2)O(3)·xH(2)O. The thickness of the Cr(2)O(3)·xH(2)O sheath on MWCNTs could be tuned by manipulating the ratio of precursor to MWCNTs. Calcining the composites at 550?°C, the MWCNTs were removed, producing polycrystalline α-Cr(2)O(3) nanotubes. The as-prepared α-Cr(2)O(3) sample was used as a sensor material to detect ethanol vapor, and it was demonstrated that the α-Cr(2)O(3) nanotubes exhibited good performance even at 400?°C.     

Effect of heat treatment on the structure and stability of multiwalled carbon nanotubes produced by catalytic chemical vapor deposition technique

The multiwalled carbon nanotubes (MWCNTs) produced by catalytic chemical vapor deposition (CCVD) route were heat treated to 2500 °C to improve the structure, morphology and purity level. The process has lead to substantial reduction in the catalytic impurity along with an improved thermal stability and degree of graphitization of these tubes that can possibly lead to its better utilization in various applications. The structural changes following heat treatment have been correlated using various characterization techniques such as Raman spectroscopy, X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, thermo gravimetric analysis and electron paramagnetic resonance spectroscopy. The electrical and mechanical properties of the polymer composites prepared with heat treated MWCNT show improved properties over the one prepared by as produced MWCNT.