Free energetics of carbon nanotube association in aqueous inorganic NaI salt solutions: Temperature effects using all‐atom molecular dynamics simulations

In this study, we examine the temperature dependence of free energetics of nanotube association using graphical processing unit‐enabled all‐atom molecular dynamics simulations (FEN ZI) with two (10,10) single‐walled carbon nanotubes in 3 m NaI aqueous salt solution. Results suggest that the free energy, enthalpy and entropy changes for the association process are all reduced at the high temperature, in agreement with previous investigations using other hydrophobes. Via the decomposition of free energy into individual components, we found that solvent contribution (including water, anion, and cation contributions) is correlated with the spatial distribution of the corresponding species and is influenced distinctly by the temperature. We studied the spatial distribution and the structure of the solvent in different regions: intertube, intratube and the bulk solvent. By calculating the fluctuation of coarse‐grained tube‐solvent surfaces, we found that tube–water interfacial fluctuation exhibits the strongest temperature dependence. By taking ions to be a solvent‐like medium in the absence of water, tube–anion interfacial fluctuation shows similar but weaker dependence on temperature, while tube–cation interfacial fluctuation shows no dependence in general. These characteristics are discussed via the malleability of their corresponding solvation shells relative to the nanotube surface. Hydrogen bonding profiles and tetrahedrality of water arrangement are also computed to compare the structure of solvent in the solvent bulk and intertube region. The hydrophobic confinement induces a relatively lower concentration environment in the intertube region, therefore causing different intertube solvent structures which depend on the tube separation. This study is relevant in the continuing discourse on hydrophobic interactions (as they impact generally a broad class of phenomena in biology, biochemistry, and materials science and soft condensed matter research), and interpretations of hydrophobicity in terms of alternative but parallel signatures such as interfacial fluctuations, dewetting transitions, and enhanced fluctuation probabilities at interfaces. © 2015 Wiley Periodicals, Inc.     

Directly drawing self-assembled, porous, and monolithic graphene fiber from chemical vapor deposition grown graphene film and its electrochemical properties

Integration of graphene into macroscopic architectures represents the first step toward creating a new class of graphene-based nanodevices. We report a novel yet simple approach to fabricate graphene fibers, a porous and monolithic macrostructure, from chemical vapor deposition grown graphene films. Graphene is first self-assembled from a 2D film to a 1D fiberlike structure in an organic solvent (e.g., ethanol, acetone) and then dried to give the porous and crumpled structure. The method developed here is scalable and controllable, delivering tunable morphology and pore structure by controlling the evaporation of solvents with suitable surface tension. The fibers are 20-50 μm thick, with a typical electrical conductivity of ～1000 S/m. The cyclic voltammetric studies show typical capacitive behavior for the porous graphene fibers with good rate stability and capacitance values ranging from 0.6 to 1.4 mF/cm(2). Decorated with only 1-3 wt % MnO(2), the graphene/MnO(2) composites exhibit remarkable enhancement of combined performance both with respect to discharge capacitance (up to 12.4 mF/cm(2)) and cycling stability. This special structure could facilitate chemical doping and electrochemical energy storage and find applications in catalyst supports, sensors, supercapacitors, Li ion batteries, etc.     

Preparation and photocatalytic ability of highly defective carbon nanotubes

The highly defective carbon nanotubes (CNTs) were prepared using a heat-treatment technique and their photocatalytic ability was reported for the first time. The results showed that the highly defective CNTs had the photocatalytic ability in the range of visible light. The results also indicated that the electrical properties of CNTs were dependent not only on the diameter and helicity but also on the defect number of tubes. The defects of CNTs might be produced from vacancies, local lattice reordering and intertube reorientation during the course of the desorption of oxygen atoms, which could initiate defect states in the band gap. Absorption of visible light led to the formation of electron/hole pairs and hence caused photocatalytic oxidation. Consequently, the highly defective CNTs having the photocatalytic ability would be promising as a new photocatalytic material in the visible light.     

Thermoelectric properties of nanocomposite thin films prepared with poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) and graphene

Carbon nanotubes (CNTs), either single wall carbon nanotubes (SWNTs) or multiwall carbon nanotubes (MWNTs), can improve the thermoelectric properties of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT?:?PSS), but it requires addition of 30-40 wt% CNTs. We report that the figure of merit (ZT) value of PEDOT?:?PSS thin film for thermoelectric property is increased about 10 times by incorporating 2 wt% of graphene. PEDOT?:?PSS thin films containing 1, 2, 3 wt% graphene are prepared by solution spin coating method. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy analyses identified the strong π-π interactions which facilitated the dispersion between graphene and PEDOT?:?PSS. The uniformly distributed graphene increased the interfacial area by 2-10 times as compared with CNT based on the same weight. The power factor and ZT value of PEDOT?:?PSS thin film containing 2 wt% graphene was 11.09 μW mK(-2) and 2.1 × 10(-2), respectively. This enhancement arises from the facilitated carrier transfer between PEDOT?:?PSS and graphene as well as the high electron mobility of graphene (200,000 cm(2) V(-1) s(-1)). Furthermore the porous structure of the thin film decreases the thermal conductivity resulting in a high ZT value, which is higher by 20% than that for a PEDOT?:?PSS thin film containing 35 wt% SWNTs.     

Ultralight,Ultraflexible, Anisotropic,Highly Thermally Conductive Graphene Aerogel Films

Graphene aerogels have attracted much attention as a promising material for various applications. The unusually high intrinsic thermal conductivity of individual graphene sheets makes an obvious contrast with the thermal insulating performance of assembled 3D graphene materials. We report the preparation of anisotropy 3D graphene aerogel films (GAFs) made from tightly packed graphene films using a thermal expansion method. GAFs with different thicknesses and an ultimate low density of 4.19 mg cm⁻³ were obtained. GAFs show high anisotropy on average cross-plane thermal conductivity (K_⊥) and average in-plane thermal conductivity (K_||). Additionally, uniaxially compressed GAFs performed a large elongation of 11.76% due to the Z-shape folding of graphene layers. Our results reveal the ultralight, ultraflexible, highly thermally conductive, anisotropy GAFs, as well as the fundamental evolution of macroscopic assembled graphene materials at elevated temperature.     

Oxidation, deformation, and destruction of carbon nanotubes in aqueous ceric sulfate

A simple wet chemical method involving only ultrasonic processing in dilute ceric sulfate (CS) was used to functionalize carbon nanotubes (CNTs). Unexpectedly, single-walled and multiwalled carbon nanotubes (SWCNTs and MWCNTs) were cut, oxidized, and disintegrated by sonication in 0.1 N CS for 2-5 h. Transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction spectroscopy (XRD), Raman scattering, and photoacoustic Fourier transform infrared spectroscopy (FTIR) were used to probe wall damage during the chemical processing. Cyclic voltammetry and impedance spectroscopy were used to evaluate the conductivity of the CS-treated CNTs. This one-step process resulted in the destruction of SWCNTs to produce nonconducting amorphous carbon. MWCNTs were oxidized and converted to graphitic materials and amorphous carbon with retained conductivity.     

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.     

Sidewall alkylcarboxylation of carbon nanotubes through reactions of fluoronanotubes with functional free radicals

Addition of carboxyalkyl radicals to carbon nanotube (CNT) graphene surface is a non-destructive to nanotube framework method of sidewall functionalization of CNTs with the carboxylic group terminated moieties. Fluorination activates the CNT surface towards addition reactions due to transformation of the graphene aromatic structure to a more chemically reactive polyene ??-system structure of fluoronanotubes. As a result, the sidewall addition reactions to fluoronanotubes are completed in a much shorter time spans than in the case of pristine CNTs. Carboxyalkyl CNT derivatives prepared by this method form stable suspensions in water and polar organic solvents. This enables their applications in biomedical research; for the preparation of water-based paints, inks, and coatings; and for processing and fabrication of nanocomposites.     

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.     

Carbon nanostructure-derived polyaniline metacomposites: electrical, dielectric, and giant magnetoresistive properties

Polyaniline (PANI) nanocomposites incorporating different loadings of graphene and various other carbon nanostructures including carbon nanotubes (CNTs) and carbon nanofibers (CNFs) have been synthesized using a surface-initiated polymerization (SIP) method. Transmission electron microscopy (TEM) results indicate that the graphene has been exfoliated into a few layers (typically one, two, and three layers) during polymerization and has been uniformly dispersed in the PANI matrix. The graphene layer dispersion degree is quantified by a free-path spacing measurement (FPSM) method based on the TEM microstructures. The SIP method also demonstrates its feasibility for coating PANI on one-dimensional (1D) CNFs and CNTs without introducing additional surface functional groups. The effects of graphene size, loading level, and surface functionality on the electrical conductivity and dielectric permittivity of their corresponding nanocomposites have been systematically studied. The temperature-dependent conductivity behavior revealed a quasi-3D variable range hopping (VRH) electron transport mechanism for all the nanocomposites. Giant magnetoresistance (GMR) at room temperature is observed in pure PANI, which can be enhanced by the incorporation of a high loading of graphene (5%) due to the π-π stacking-induced efficient electron transport at the PANI/graphene interface. More interestingly, negative permittivity is found in each composite which can be easily tuned by adjusting the filler loading, morphology, and surface functionality.     

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.     

Homogeneous Electrochemical Assay for Real‐time Monitoring of Exonuclease III Activity Based on a Graphene Monolayer

A homogeneous electrochemical assay based on a graphene monolayer electrode was developed for simple, sensitive, rapid and quantitative analysis of the exonuclease III (Exo III) activity. The method utilized a methylene blue (MB) tagged DNA substrate with hairpin structure, and a graphene monolayer attached on the working electrode. Before digestion, the hairpin structure prevents the adsorption of the DNA substrate to the graphene surface. Degradation of the substrate by the 3′–5′ Exo III, however, yields single‐stranded DNA (ssDNA), resulting in its subsequent binding to the graphene surface through π‐π stacking, which produces the voltammetric current from electrochemical reduction of the MB tag anchoring at the end of ssDNA. A direct quantification of the Exo III activity can be achieved by measuring the reductive peak current of the MB tag under easily attainable potential (∼ −0.1 V vs Ag/AgCl) range comparably sensitive to the conventional methods such as a gel‐based or fluorescence‐based assays. Our approach can be applied to measure various exonucleases activity by adjusting the structure of DNA substrate suggesting a new assay method in drug screening and basic research related to the enzymes.     

PtRu catalysts supported on heteropolyacid and chitosan functionalized carbon nanotubes for methanol oxidation reaction of fuel cells

A simple self-assembly approach has been developed to functionalize carbon nanotubes (CNTs) with chitosan (CS) and heteropolyacids (HPAs) of phosphomolybdic acid (H(3)PMo(12)O(40), HPMo) and phosphotungstic acid (H(3)PW(12)O(40), HPW). The non-covalent functionalization method, which introduces homogenous surface functional groups with no detrimental effect on graphene structures of CNTs, can be carried out at room temperature without the use of corrosive acids. The PtRu nanoparticles supported on HPAs-CS-CNTs have a uniform distribution and much smaller size as compared to those of the PtRu nanoparticles supported on conventional acid treated CNTs (PtRu/AO-CNTs). The onset and peak potentials for CO(ad) oxidation on PtRu/HPAs-CS-CNTs catalysts are more negative than those on PtRu/AO-CNTs, indicating that HPAs facilitate the electro-oxidation of CO. The PtRu/HPMo-CS-CNTs catalyst has a higher electrocatalytic activity for methanol oxidation and higher tolerance toward CO poisoning than PtRu/HPW-CS-CNTs. The better electrocatalytic enhancement of HPMo on the PtRu/HPAs-CS-CNTs catalyst is most likely related to the fact that molybdenum-containing HPAs such as HPMo have more labile terminal oxygen to provide additional active oxygen sites while accelerating the CO and methanol oxidation in a similar way to that of Ru in the PtRu binary alloy system.     

A review on the mechanical,electrical and EMI shielding properties of carbon nanotubes and graphene reinforced polycarbonate nanocomposites

Recently, it has been found that carbon nanotubes (CNTs) and graphene could prove to be the most promising carbonaceous fillers in polymers nanocomposites field because of their better structural and functional properties. Their uniform dispersion in polymer matrix leads to significant improvements in their several properties. This paper reviews the effect of nanofillers, ie, CNTs, derivatized CNTs, and graphene on the polycarbonate nanocomposite and its application in aerospace, automobile, sports, electronic sectors, and various industries. The comparative analysis of carbon‐based fillers on the different properties of polycarbonate nanocomposites is also included.     

拉曼光谱表征石墨烯材料的研究进展

石墨烯独特的二元化电子价键结构使其在纳米电子器件中具有良好的应用发展前景。拉曼光谱作为一种灵敏、便捷的技术,已被成功地用作表征石墨烯的结构和特性。本综述着重对沉积在不同基底以及掺杂的石墨烯拉曼光谱研究做了一个简单的总结。通过对铟锡氧化物、蓝宝石和玻璃基底上的石墨烯拉曼光谱进行观察,发现在不同基底上的石墨烯拉曼G峰与2D峰峰值会有不同程度的偏移,但2D峰峰值可判断石墨烯层数这一结论仍适用。掺杂可改变石墨烯的荷电状态,使石墨烯表现出空穴（p）型或电子（n）型掺杂特性,通过石墨烯拉曼光谱的变化可以定性石墨烯的掺杂类别并定量表征石墨烯的载流子浓度。     

Graphene oxides/multi-walled carbon nanotubes hybrid-modified carbon electrodes for fast and sensitive voltammetric determination of the anticancer drug 5-fluorouracil in spiked human plasma samples

The electrochemical oxidation of anticancer drug 5-fluorouracil (5-FU) at graphene oxides (GOs)/carbon nanotubes (CNTs) nanohybrid-modified screen-printed carbon and glassy carbon electrodes was studied by voltammetric techniques. The modified electrodes showed better performance toward the electro-oxidation and determination of 5-FU compared to CNTs-modified or GOs-modified electrodes. The oxidation peak current obtained at about + 1.156 V (vs. Ag/AgCl) from square wave voltammetry was linearly dependent on the 5-FU concentration in the ranges of 0.05–5 and 5–1200 µM in phosphate buffer solution of pH 7.0. The developed method was applied successfully to the electrochemical sensing of 5-FU in human plasma samples at micro-molar concentration levels with satisfactory results. It is hopeful that the developed method in the future can be used for the simple and fast determination of 5-FU in clinical test and pharmacokinetics.     

Hydrogen bond dynamics and microscopic structure of confined water inside carbon nanotubes

We have investigated the density and temperature dependences of microscopic structure and hydrogen bond dynamics of water inside carbon nanotubes (CNTs) using molecular dynamics simulation. The CNTs are treated as rigid, and smoothly truncated extended simple point charge water model is adopted. The results show that as the overall density increases, the atomic density profiles of water inside CNTs become sharper, the peaks shift closer to the wall, and a new peak of hydrogen atomic density appears between the first (outermost) and second layer. The intermittent hydrogen bond correlation function C(HB)(t) of water inside CNTs decays slower than that of bulk water, and the rate of decay decreases as the tube diameter decreases. C(HB)(t) clearly decays more slowly for the first layer of water than for other regions inside CNTs. The C(HB)(t) of the interlayer hydrogen bonds decays faster than those of the other regions and even faster than that of the bulk water. On the other hand, the hydrogen bond lifetimes of the first layer are shorter than those of the inner layer(s). Interlayer hydrogen bond lifetimes are clearly shorter than those of the constituent layers. As a whole, the hydrogen bond lifetimes of water inside CNTs are shorter than those of bulk water, while the relaxation of C(HB)(t) is slower for the confined water than for bulk water. In other words, hydrogen bonds of water inside CNTs break more easily than those of bulk water, but the water molecules remain in each other's vicinity and can easily reform the bonds.     

Photochemical Evidence of Electronic Interwall Communication in Double‐Wall Carbon Nanotubes

Single‐ and double‐wall carbon nanotubes (CNTs) having dimethylanilino (DMA) units covalently attached to the external graphene wall have been prepared by the reaction of the dimethylaminophenylnitronium ion with the corresponding CNT. The samples have been characterized by Raman and XPS spectroscopies, thermogravimetry, and high‐resolution transmission electron microscopy in which the integrity of the single or double wall of the CNT and the percentage of substitution (one dimethylanilino group every 45 carbons of the wall for the single‐ and double‐wall samples) has been determined. Nanosecond laser flash photolysis has shown the generation of transients that has been derived from the charge transfer between the dimethylanilino (as the electron donor) to the CNT graphene wall (as the electron acceptor). Importantly, the lifetime of the double‐wall CNT is much shorter than that monitored for the single‐wall CNT. Shorter‐lived transients were also observed for the pentyl‐esterified functionalized double‐wall CNT with respect to the single‐wall analogue in the presence of hole (CH₃OH) and electron quenchers (O₂, N₂O), which has led to the conclusion that the inner, intact graphene wall that is present in double‐wall CNT increases the charge mobility significantly, favoring charge recombination processes. Considering the importance that charge mobility has in microelectronics, our finding suggests that double‐wall CNT or two‐layer graphene may be more appropriate to develop devices needing fast charge mobility.     

EMI shielding and dynamic mechanical analysis of graphene oxide-carbon nanotube-acrylonitrile butadiene styrene hybrid composites

Carbon nanomaterials such as carbon nanotubes (CNTs), graphene and their hybrid have been studied extensively. Despite having excellent properties of CNTs and graphene have not yet been fully realized in the polymer composites. During fabrication agglomeration of CNTs and restacking of graphene is a serious concern that results in the degradation of properties of nanomaterials into the final composites. To improve the dispersion of CNTs and restacking graphene, in the present research work, we focused on the hybridization of graphene oxide and CNTs. Multiwalled carbon nanotubes (MWCNTs), functionalized carbon nanotubes (FCNTs), and graphene oxide-carbon nanotubes (GCNTs) reinforced acrylonitrile butadiene styrene (ABS) composites were prepared separately by vacuum filtration followed by hot compression molding. Further, dynamic mechanical analysis (DMA), and electromagnetic interference (EMI) shielding properties of ABS composites reinforced carbon nanofillers were investigated. The dynamic mechanical properties of polymers strongly depend on the adhesion of fillers and polymer, entanglement density of polymer chains in the presence of carbon fillers. The dynamic mechanical characteristics such as storage, loss modulus, and damping factor of prepared composites were significantly affected by the incorporation of MWCNTs, FCNTs, and GCNTs. Maximum EMI shielding effectiveness of −49.6 dB was achieved for GCNT-ABS composites which were highest compared to MWCNTs-ABS composites (−38.6 dB) and FCNTs-ABS composites (−36.7 dB) in the Ku band (12.4–18 GHz). These results depict the great potential of GCNTs-ABS composites to be used in various applications of efficient heat dissipative EMI shielding materials for electronic devices.