Concise Synthesis of 3D π‐Extended Polyphenylene Cylinders

The synthesis of structurally well‐defined, monodisperse carbon nanotube (CNT) sidewall segments poses a challenge in materials science. The synthesis of polyphenylene cylinders that comprise typical benzene connectivity to resemble precursors of [9,9] and [15,15] CNTs is now reported, and the products were characterized by X‐ray crystallography. To investigate the oxidative cyclodehydrogenation of ring‐strained molecules as a final step towards a bottom‐up synthesis of CNT sidewall segments, phenylene‐extended cyclic p‐hexaphenylbenzene trimers ([3]CHPB) were prepared, and NMR studies revealed a strain‐induced 1,2‐phenyl shift. It was further shown that an increase in ring size leads to selectively dehydrogenated macrocycles. Larger homologues are envisioned to give smooth condensation reactions toward graphenic sidewalls and should be used in the future as seeds for CNT formation.     

Curvature effect in the longitudinal unzipping carbon nanotubes

Density functional theory (DFT) calculations are performed to analyze curvature effects in the oxidative longitudinal unzipping of carbon nanotubes (CNTs) of different diameters. The reactions considered involve the adsorption of permanganate, followed by the oxidation of the nanotube, which results in dione and hole formation. The study was performed with armchair CNTs of different diameters and with corrugated graphene layers, which emulate the curvature of CNT of larger radii, with the finding that the curvature and the pyramidalization angle of the these structures strongly affects the stability of the intermediate dione structure formed during the unzipping process. Permanganate adsorption energies increase for more curved surfaces promoting the oxidation reaction in surfaces of small radius, making this reaction spontaneous for small radius. The second permanganate adsorbs on the parallel carbon–carbon bond to first diona formation resulting the longitudinal unzipping of the CNT.     

Probing the Electronic Effect of Carbon Nanotubes in Catalysis: NH3 Synthesis with Ru Nanoparticles

Carbon nanotubes (CNTs) have been shown to modify some properties of nanomaterials and to modify chemical reactions confined inside their channels, which are formed by curved graphene layers. Here we studied ammonia synthesis over Ru as a probe reaction to understand the effect of the electron structure of CNTs on the confined metal particles and their catalytic activity. The catalyst with Ru nanoparticles dispersed almost exclusively on the exterior nanotube surface exhibits a higher activity than the CNT‐confined Ru, although both have a similar metal particle size. Characterization with TEM, N₂ physisorption, H₂ chemisorption, temperature‐programmed reduction, CO adsorption microcalorimetry, and first‐principles calculations suggests that the outside Ru exhibits a higher electron density than the inside Ru. As a result, the dissociative adsorption of N₂, which is an electrophilic process and the rate‐determining step of ammonia synthesis, is more facile over the outside Ru than that over the inside one.     

Facile One‐Pot,One‐Step Synthesis of a Carbon Nanoarchitecture for an Advanced Multifunctonal Electrocatalyst

A one‐pot/one‐step synthesis strategy was developed for the preparation of a nitrogen‐doped carbon nanoarchitecture with graphene‐nanosheet growth on the inner surface of carbon nanotubes (CNTs). The N‐graphene/CNT hybrids exhibit outstanding electrocatalytic activity for several important electrochemical reactions as a result of their unique morphology and defect structures, such as high but uniform nitrogen doping, graphene insertion into CNTs, considerable surface area, and the presence of iron nanoparticles. The high‐yield synthetic process features high efficiency, low‐cost, straightforward operation, and simple equipment.     

Surface chemistry in the process of coating mesoporous SiO2 onto carbon nanotubes driven by the formation of Si-O-C bonds

The deposition of mesoporous silica (SiO(2)) on carbon nanotubes (CNTs) has opened up a wide range of assembling possibilities by exploiting the sidewall of CNTs and organosilane chemistry. The resulting systems may be suitable for applications in catalysis, energy conversion, environmental chemistry, and nanomedicine. However, to promote the condensation of silicon monomers on the nanotube without producing segregated particles, (OR)(4-x)SiO(x)(x-) units must undergo nucleophilic substitution by groups localized on the CNT sidewall during the transesterification reaction. In order to achieve this preferential attachment, we have deposited silica on oxidized carbon nanotubes (single-walled and multiwalled) in a sol-gel process that also involved the use of a soft template (cetyltrimethylammonium bromide, CTAB). In contrast to the simple approach normally used to describe the attachment of inorganic compounds on CNTs, SiO(2) nucleation on the tube is a result of nucleophilic attack mainly by hydroxyl radicals, localized in a very complex surface chemical environment, where various oxygenated groups are covalently bonded to the sidewall and carboxylated carbonaceous fragments (CCFs) are adsorbed on the tubes. Si-O-C covalent bond formation in the SiO(2)-CNT hybrids was observed even after removal of the CCFs with sodium hydroxide. By adding CTAB, and increasing the temperature, time, and initial amount of the catalyst (NH(4)OH) in the synthesis, the SiO(2) coating morphology could be changed from one of nanoparticles to mesoporous shells. Concomitantly, pore ordering was achieved by increasing the amount of CTAB. Furthermore, preferential attachment on the sidewall results mostly in CNTs with uncapped ends, having sites (carboxylic acids) that can be used for further localized reactions.     

Facile One‐Pot,One‐Step Synthesis of a Carbon Nanoarchitecture for an Advanced Multifunctonal Electrocatalyst

A one‐pot/one‐step synthesis strategy was developed for the preparation of a nitrogen‐doped carbon nanoarchitecture with graphene‐nanosheet growth on the inner surface of carbon nanotubes (CNTs). The N‐graphene/CNT hybrids exhibit outstanding electrocatalytic activity for several important electrochemical reactions as a result of their unique morphology and defect structures, such as high but uniform nitrogen doping, graphene insertion into CNTs, considerable surface area, and the presence of iron nanoparticles. The high‐yield synthetic process features high efficiency, low‐cost, straightforward operation, and simple equipment.     

Curvature‐dependent adsorption of water inside and outside armchair carbon nanotubes

The curvature dependence of the physisorption properties of a water molecule inside and outside an armchair carbon nanotube (CNT) is investigated by an incremental density‐fitting local coupled cluster treatment with single and double excitations and perturbative triples (DF‐LCCSD(T)) study. Our results show that a water molecule outside and inside (n, n) CNTs (n = 4, 5, 6, 7, 8, 10) is stabilized by electron correlation. The adsorption energy of water inside CNTs decreases quickly with the decrease of curvature (increase of radius) and the configuration with the oxygen pointing toward the CNT wall is the most stable one. However, when the water molecule is adsorbed outside the CNT, the adsorption energy varies only slightly with the curvature and the configuration with hydrogens pointing toward the CNT wall is the most stable one. We also use the DF‐LCCSD(T) results to parameterize Lennard‐Jones (LJ) force fields for the interaction of water both with the inner and outer sides of CNTs and with graphene representing the zero curvature limit. It is not possible to reproduce all DF‐LCCSD(T) results for water inside and outside CNTs of different curvature by a single set of LJ parameters, but two sets have to be used instead. Each of the two resulting sets can reproduce three out of four minima of the effective potential curves reasonably well. These LJ models are then used to calculate the water adsorption energies of larger CNTs, approaching the graphene limit, thus bridging the gap between CNTs of increasing radius and flat graphene sheets. © 2016 Wiley Periodicals, Inc.     

A Review Featuring Fabrication,Properties and Applications of Carbon Nanotubes (CNTs) Reinforced Polymer and Epoxy Nanocomposites

Carbon nanotubes (CNTs) have long been recognized as the stiffest and strongest man-made material known to date.In addition,their high electrical conductivity has roused interest in the areas of electrical appliances and communication related applications.However,due to their miniature size,the excellent properties of these nanostructures can only be exploited if they are homogeneously embedded into light-weight matrices as those offered by a whole series of engineering polymers.In order to enhance their chemical affinity to engineering polymer matrices,chemical modification of the graphitic sidewalls and tips is necessary.The mechanical and electrical properties to date of a whole range of nanocomposites of various carbon nanotube contents are also reviewed in this attempt to facilitate progress in this emerging area.Recently,carbonaceous nano-fillers such as graphene and carbon nanotubes (CNTs) play a promising role due to their better structural and functional properties and broad range of applications in every field.Since CNTs usually form stabilized bundles due to van der Waals interactions,they are extremely difficult to disperse and align in a polymer matrix.The biggest issues in the preparation of CNTs reinforced composites reside in efficient dispersion of CNTs into a polymer matrix,the assessment of the dispersion,and the alignment and control of the CNTs in the matrix.An overview of various CNT functionalization methods is given.In particular,CNT functionalization using click chemistry and the preparation of CNT composites employing hyperbranched polymers are stressed as potential techniques to achieve good CNT dispersion.In addition,discussions on mechanical,thermal,electrical,electrochemical and applications ofpolymer/CNT composites are also included.     

基于弱相互作用的石墨化CNT/PMMA复合材料的热电传输性能

从理论上计算了碳纳米管(CNT)与聚甲基丙烯酸甲酯(PMMA)的相互作用及浸润性, 并测试了CNT/PMMA复合材料的电学、热学和光学性能. 发现石墨化CNT/PMMA复合材料具有较好的导热和导电性能, 其渗流阈值在0.8%左右, 当CNT质量分数为3%时, 复合材料的导热系数提高193%. 这种电学及热学性能的提高一方面与石墨化CNTs的规整结构有关, 另一方面与石墨化CNT-PMMA体系的弱相互作用、CNT间的有效接触以及高效的CNT网络输运性能有密切关系. 研究结果表明, 通过调控CNT与聚合物基体的表面性质、相互作用及浸润性, 可以有效地构建优化的CNT输运网络, 获得性能优异的功能复合材料.     

FIB-SEM imaging of carbon nanotubes in mouse lung tissue

Ultrastructural characterisation is important for understanding carbon nanotube (CNT) toxicity and how the CNTs interact with cells and tissues. The standard method for this involves using transmission electron microscopy (TEM). However, in particular, the sample preparation, using a microtome to cut thin sample sections for TEM, can be challenging for investigation of regions with agglomerations of large and stiff CNTs because the CNTs cut with difficulty. As a consequence, the sectioning diamond knife may be damaged and the uncut CNTs are left protruding from the embedded block surface excluding them from TEM analysis. To provide an alternative to ultramicrotomy and subsequent TEM imaging, we studied focused ion beam scanning electron microscopy (FIB-SEM) of CNTs in the lungs of mice, and we evaluated the applicability of the method compared to TEM. FIB-SEM can provide serial section volume imaging not easily obtained with TEM, but it is time-consuming to locate CNTs in the tissue. We demonstrate that protruding CNTs after ultramicrotomy can be used to locate the region of interest, and we present FIB-SEM images of CNTs in lung tissue. FIB-SEM imaging was applied to lung tissue from mice which had been intratracheally instilled with two different multiwalled CNTs; one being short and thin, and the other longer and thicker. FIB-SEM was found to be most suitable for detection of the large CNTs (Ø ca. 70 nm), and to be well suited for studying CNT agglomerates in biological samples which is challenging using standard TEM techniques.

Printing graphene-carbon nanotube-ionic liquid gel on graphene paper: Towards flexible electrodes with efficient loading of PtAu alloy nanoparticles for electrochemical sensing of blood glucose

The increasing demands for portable, wearable, and implantable sensing devices have stimulated growing interest in innovative electrode materials. In this work, we have demonstrated that printing a conductive ink formulated by blending three-dimensional (3D) porous graphene–carbon nanotube (CNT) assembly with ionic liquid (IL) on two-dimensional (2D) graphene paper (GP), leads to a freestanding GP supported graphene–CNT–IL nanocomposite (graphene–CNT–IL/GP). The incorporation of highly conductive CNTs into graphene assembly effectively increases its surface area and improves its electrical and mechanical properties. The graphene–CNT–IL/GP, as freestanding and flexible substrates, allows for efficient loading of PtAu alloy nanoparticles by means of ultrasonic-electrochemical deposition. Owing to the synergistic effect of PtAu alloy nanoparticles, 3D porous graphene–CNT scaffold, IL binder and 2D flexible GP substrate, the resultant lightweight nanohybrid paper electrode exhibits excellent sensing performances in nonenzymatic electrochemical detection of glucose in terms of sensitivity, selectivity, reproducibility and mechanical properties.     

Electrochemical Introduction of Active Sites into Super-long Carbon Nanotubes for Enhanced Capacitance

Electrochemical cyclic voltammetric(CV)scan was applied to inducing the partial oxidation and defects of carbon nanotubes(CNTs).The electrochemically induced functional groups and physical defects were...     

An X-ray spectroscopy study of CdS nanoparticles formed by the Langmuir–Blodgett technique on the surface of carbon nanotube arrays

The composition and electronic structure of cadmium sulfide (CdS) nanoparticles formed by the Langmuir–Blodgett (LB) technique on clean silicon wafers and the surface of vertically aligned carbon nanotube (CNT) arrays are studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The samples were annealed in a vacuum at 175 °C and 225 °C to remove the organic matrix of the LB film. From the analysis of the XPS data the increased concentration of sulfate groups on the surface of CdS nanoparticles formed on CNTs and the electron density transfer from CdS to CNTs are determined. An increase in the LB film annealing temperature causes an increase in the degree of crystallinity and the CdS crystallite size and a decrease in the photoluminescence intensity of a CdS–CNT hybrid.     

多壁碳纳米管的纯化及其表面含氧基团的表征

用兼具酸性和氧化性的HNO3水溶液可方便地除去残留在原生态多壁碳纳米管(CNT)上的Ni-MgO催化剂组分,同时在其表面产生某些含氧官能团,使原生态多壁碳纳米管的疏水性表面变为亲水性表面.采用Boehm中和滴定法以及X射线衍射(XRD)、热脱附谱(TPD)、傅里叶变换红外(FTIR)光谱和X射线光电子能谱(XPS)等技术对HNO3处理过的多壁碳纳米管的相组成和表面含氧官能团进行测量和表征.结果表明:所生成表面含氧官能团的总量以经7.0mol·L-1硝酸378K处理24h的CNT为最高;3种主要表面含氧官能团的含量高低顺序为,羧基内酯型羧基酚型羟基.     

Predicting whether aromatic molecules would prefer to enter a carbon nanotube: A density functional theory study

The interaction of a carbon nanotube (CNT) with various aromatic molecules, such as aniline, benzophenone, and diphenylamine, was studied using density functional theory able to compute intermolecular weak interactions (B3LYP-D3). CNTs of varying lengths were used, such as 4-CNT, 6-CNT, and 8-CNT (the numbers denoting relative lengths), with the lengths being chosen appropriately to save computation times. All aromatic molecules were found to exhibit strong intermolecular binding energies with the inner surface of the CNT, rather than the outer surface. Hydrogen bonding between two aromatic molecules that include N and O atoms is shown to further stabilize the intermolecular adsorption process. Therefore, when benzophenone and diphenylamine were simultaneously allowed to interact with a CNT, the aromatic molecules were expected to preferably enter the CNT. Furthermore, additional calculations of the intermolecular adsorption energy for aniline adsorbed on a graphene surface showed that the concavity of graphene-like carbon sheet is in proportion to the intermolecular binding energy between the graphene-like carbon sheet and the aromatic molecule.     

Using ONIOM calculations to investigate the abilities of simple and nitrogen,boron, sulfur-doped carbon nanotubes in sensing of carbon monoxide

In this work, geometries, stabilities, and electronic properties of the carbon monoxide (CO) molecule as an adsorbent in a simple carbon nanotube (CNT) and nitrogen (N), boron (B), sulfur (S)-doped CNTs (NCNT, BCNT, and SCNT) with parallel and perpendicular configurations are fully considered using ONIOM, natural bond orbital, and quantum theory of atom in molecule (QTAIM) calculations. The adsorption energies (E_ad) demonstrate that a CO molecule could be adsorbed on the surface of the simple CNT with parallel configuration and N-doped CNT with perpendicular configuration in an exothermic process. QTAIM calculations showed the close-shell (noncovalent) interactions between the CO molecule and CNT or N, B, S-doped CNTs. In addition, the energy gap (E_g) values between the highest occupied molecular orbital and the lowest unoccupied molecular orbital are calculated. In accordance with the results of energy gap, simple and N-doped CNTs could be used as CO sensors.     

Synthesis and characterization of unbranched and branched multi-walled carbon nanotubes using Cu as catalyst

Unbranched and branched carbon nanotubes (CNTs) were synthesized by catalytic chemical vapor deposition from methane at 900 °C over a Cu/MgO catalyst. Morphology and structure of the CNTs were characterized by scanning and transmission electron microscopy, and Raman spectroscopy. The effect of methane flow rate on the CNT growth was investigated. The results suggest that the products were transformed from unbranched to branched CNTs with an increase in methane flow rate. The simplicity and controllability of such a preparation technique make it a promising method to synthesize different carbon nanotube structures.     

Tailoring wettability change on aligned and patterned carbon nanotube films for selective assembly

The effects of oxygen reactive ion etching (RIE) on the surface wettability of aligned carbon nanotube (CNT) films have been systematically investigated. It was found that 3 s of RIE treatment could change the surface of CNT films from hydrophobic to more hydrophilic. The degree of modification in the surface wettability of the film could be controlled by the flow rate of O2 gas during the RIE process. It is proposed that such a surface hydrophobicity change is related to the opened structure and functionalized tip of as-treated CNTs by oxygen reactive ions. More importantly, after the RIE treatment, focused laser pruning was utilized to trim the surface layer of treated CNTs and revert them back to a hydrophobic surface. Combined with the laser pruning technique and O2 RIE treatment, CNT templates with interlaced wettability surfaces in a stripe pattern have been fabricated. It has been demonstrated that this interlaced and structured wettability pattern can be used to selectively assemble microspheres or quantum dots on the aligned CNT films with desired patterns.     

Facile preparation of carbon nanotube/poly(ethyl 2-cyanoacrylate) composite electrode by water-vapor-initiated polymerization for enhanced amperometric detection

A carbon nanotube/poly(ethyl 2-cyanoacrylate) (CNT/PECA) composite electrode was developed for enhanced amperometric detection. The composite electrode was fabricated on the basis of water-vapor-initiated polymerization of a mixture of CNTs and ethyl 2-cyanoacrylate in the bore of a piece of fused silica capillary. The morphology and structure of the composite were investigated by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis. The results indicate that the CNTs were well dispersed and embedded throughout the PECA matrix to form an interconnected CNT network. The analytical performance of this unique CNT-based detector has been demonstrated by separating and detecting six flavones in combination with capillary electrophoresis. The advantages of the CNT/PECA composite detector include lower operating potential, higher sensitivity, low expense of fabrication, satisfactory resistance to surface fouling, and enhanced stability; these properties indicate great promise for a wide range of applications.     

Carbon Nanotube‐phenolic Resin Composite Electrode Fabricated by Far Infrared‐assisted Crosslinking for Enhanced Amperometric Detection

The composite of carbon nanotube (CNT) and phenolic resin was prepared in a piece of fused silica capillary based on the far infrared‐assisted crosslinking of phenolic novolac resin in the presence of CNTs and hexamethylenetetramine for electrochemical sensing. The surface morphology and structure of the prepared materials were investigated by scanning electron microscopy, energy dispersive X‐ray spectroscopy and Fourier transform infrared spectroscopy. The results indicated that CNTs in the composite was adhered by the crosslinked phenolic resin to form an electrically conductive network. Many broken ends of CNTs appeared on the surface of the composite electrode in the form of a nanoelectrode array. The novel electrode was employed in the amperometric detection of synephrine and hesperidin in Citri Reticulatae Pericarpium in combination with capillary zone electrophoresis. The novel CNT‐based electrode owned the advantages of high sensitivity, low fabrication expense and excellent electrocatalytic performances, indicating great promise for the electrochemical detection in other analysis systems.