Decoration of multi-walled carbon nanotubes with noble- and transition-metal clusters and formation of CNT–CNT networks

Carbon nanotubes are of great interest because of their outstanding mechanical, chemical and electric properties. The decoration of multi-walled carbon nanotubes with metal clusters of gold, palladium, iron, cobalt and nickel opens even more applications, especially the growth of complex conductor networks in microelectronic devices. PACS 81.07.De; 81.16.Be; 82.30.Nr; 82.33.Hk     

Size response of an SMPS–APS system to commercial multi-walled carbon nanotubes

Carbon nanotubes (CNTs) are representative-engineered nanomaterials with unique properties. The safe production of CNTs urgently requires reliable tools to assess inhalation exposure. In this study, on-line aerosol instruments were employed to detect the release of multi-walled CNTs (MWCNTs) in workplace environments. The size responses of aerosol instruments consisting of both a scanning mobility particle sizer (SMPS) and an aerodynamic particle sizer (APS) were examined using five types of commercial MWCNTs. A MWCNT solution and powder were aerosolized using atomizing and shaking methods, respectively. Regardless of the phase and purity, the aerosolized MWCNTs showed consistent size distributions with both SMPS and APS. The SMPS and APS measurements revealed a dominant broad peak at approximately 200–400 nm and a distinct narrow peak at approximately 2 μm, respectively. Comparing with field application of the two aerosol instruments, the APS response could be a fingerprint of the MWCNTs in a real workplace environment. A modification of the atomizing method is recommended for the long-term inhalation toxicity studies.     

Synthesis,characterization, and interactions of single-walled carbon nanotubes modified with doxorubicin with Langmuir–Blodgett biomimetic membranes

The synthesis, characterization, and the influence of single-walled carbon nanotubes (SWCNTs) modified with an anticancer drug doxorubicin (DOx) on the properties of model biological membrane as well as the comparison of the two modes of modification has been presented. The drug was covalently attached to the nanotubes either preferentially on the sides or at the ends of the nanotubes by the formation of hydrazone bond. The efficiency of the modification was proved by the results of FTIR, Raman, and thermogravimetric analysis. In order to characterize the influence of SWCNT-DOx conjugates on model biological membranes, Langmuir technique has been employed. The mixed monolayers composed of 1,2-dipalmitoyl-sn-glycero-3-phosphothioethanol (DPPTE) and SWCNT-DOx with different weight ratio have been prepared. It has been shown that changes in the isotherm characteristics depend on the SWCNTs content. While smaller amounts of SWCNTs do not exert significant differences, the introduction of the prevailing content of the nanotubes increases area per molecule and decreases the maximum value of compression modulus, leading to more fluid monolayer. However, upon increasing the surface pressure, the aggregation of carbon nanotubes within the thiolipid matrix has been observed. Mixed layers of DPPTE/SWCNT-DOx were also transferred onto gold electrodes by means of LB method. Cyclic voltammetry showed that SWCNT-DOx conjugates remain adsorbed at the electrode surface and are stable in time. Additionally, higher values of peak current and DOx surface concentration obtained for side modification prove that side modification allows for more efficient conjugation of the drug to carbon nanotubes.

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Synthesis and characterization of nickel–manganese oxide via the hydrothermal route for electrochemical capacitors

Nano-sized and well dispersed manganese oxide and nickel–manganese oxide (Ni–Mn–O) powders are synthesized via the hydrothermal route. The addition of nickel ions significantly affects the morphology, particle size and the electrochemical properties of the obtained powders. Adding nickel ions results in a significant change in the shape of the powders from rod-like to plate-like. The electrochemical analysis of the electrode reveals that the specific capacitance of the synthesized powders is greatly increased with the addition of nickel ions. When the hydrothermal temperature is increased to 125 °C, the specific capacitance also increases to 284 F/g and decreases by about 4% after 1500 cycles of charge and recharge. Ni–Mn–O is considered to be a promising material for the electrodes used in electrochemical capacitors.     

Synthesis and characterization of cobalt–manganese oxides

Cobalt doped/un-doped manganese oxides materials were synthesized at various doping rates by soft chemical reactions, oxidation-reduction method, which allows generating a metal-mixed oxide. The synthesized materials were characterized using several techniques including chemical analysis, X-rays diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The chemical analysis confirmed the presence of cobalt in the samples. XRD patterns reveal mainly a spinel-like structure and SEM micrographs exhibited morphology with fine aggregate of particles. TGA profiles showed weight loss due to loss of water in a first step, followed by a loss of oxygen from the lattice associated with partial reduction of Mn⁴⁺ to Mn³⁺. VSM was used to measure the magnetization as a function of the applied magnetic field at temperatures T=50 and 300 K. Different magnetic behaviors were observed when cobalt percentage changed in the samples. These behaviors are considered to be related to the size of the particles and composition of the materials. Higher coercive field and lesser magnetization were observed for the sample with higher cobalt content.     

Synthesis and characterization of multi–wall carbon nanotubes supported-hydrated iron phosphate cathode material for lithium–ion cells by a novel homogeneous precipitation method

Iron phosphate (FePO₄) is a promising candidate for the cathode material in lithium-ion cells due to its easy synthesis and low cost. However, the intrinsic drawbacks of FePO₄ material (i.e., the low electronic conductivity and the low lithium-ion diffusion coefficient) result in poor capacity. To overcome the shortcomings, multi-wall carbon nanotubes (MWNTs) supported hydrated iron phosphate nanocomposites (FePO₄·2H₂O/MWNTs) are prepared using a novel homogeneous precipitation method. Meanwhile, the formation mechanism of highly dispersed and ultrafine FePO₄·2H₂O nanoparticles is discussed in detail. Electrochemical measurements show that FePO₄·2H₂O/MWNTs nanocomposites have a superior discharge capacity and stability. For example, FePO₄·2H₂O/MWNTs nanocomposites exhibit a high initial discharge capacity (129.9?mAhg^?1) and a stable capacity retention (114.3?mAhg^?1 after 20 cycles). The excellent electrochemical performance is attributed to the small particle size of FePO₄·2H₂O nanoparticles, the good electronic conductivity of MWNTs, and the three-dimensional conductive network structure of FePO₄·2H₂O/MWNTs nanocomposites.     

Synthesis and characterization of CdS nanoparticle based multiwall carbon nanotube–maleic anhydride–1-octene nanocomposites

CdS nanoparticles were synthesized by sonication from cadmium chloride and thiourea using a multiwall carbon nanotube (MWCNT)–maleic anhydride (MA)–1-octene system as the matrix. The matrix was obtained by the “grafting from” approach from oxidized carbon nanotubes and maleic anhydride–1-octene. Multiwall carbon nanotubes used for reinforcing the matrix were synthesized by Catalytic Chemical Vapor Deposition using Fe–Co/Al₂O₃ as the catalyst. The obtained nanostructures were characterized by FTIR, XRD, Raman spectroscopy, TEM, SEM and UV–vis spectroscopy. The average CdS particle diameter was 7.9 nm as confirmed independently by TEM and XRD. UV–vis spectroscopy revealed that the obtained nanostructure is an appropriate base material for making optical devices. The novelty of this work is the use of the MWCNT–MA–1-octene matrix obtained via the “grafting from” approach for the synthesis of uniformly dispersed CdS nanocrystals by ultrasonic cavitation to obtain a polymer nanocomposite.     

Ultrasound-promoted direct functionalization of multi-walled carbon nanotubes in water via Diels-Alder “click chemistry”

A facile and environmentally friendly strategy for grafting polymers onto the surface of multi-walled carbon nanotubes (CNTs) was demonstrated by Diels-Alder “click chemistry”. Firstly, the copolymers of poly(styrene-alt-maleic anhydride) (PSM) were prepared by the reversible addition-fragmentation chain transfer (RAFT) polymerization and subsequently functionalized with furfuryl amine to introduce anchoring groups. The copolymers were then grafted on CNTs via the Diels-Alder reaction in water through a conventional heating-stirring route and ultrasound-assisted method. The obtained nanocomposite materials were characterized by thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and transmission electron microscopy. The results indicated that the reaction rate under ultrasound irradiation was accelerated about 12 times than the one under the conventional heating-stirring condition without losing the grafting efficiency. The direct functionalization of CNTs formed a stably dispersed solution in water, promising a green and effective method for industrial process.     

First-principles study of electronic and elastic properties of Stone–Wales defective zigzag carbon nanotubes

The interaction and coupling between the electrical, mechanical properties and formation energy for SW defective (10,0) carbon nanotube is studied in density functional theory. The investigated configurations include the axial and circumferential orientations for single defect as well as four distribution types for double ones. The more stable defective configurations, namely, SW-I configurations for single SW defective carbon nanotube and II–II-(2) and I–I ones for double SW defective tubes are related to high symmetry distribution of the defects. Moreover, we found that the σ^?–π^* hybridization induced by curvature effect causes the semiconductor to metal transition for double axial SW defects case. Young's modulus reduction of SW defective carbon nanotube with respect to defect-free one is less than 8%. The energy bands and Young's moduli of double SW defective tubes are mostly affected by the defect distribution and concentration but insensitive to the circumferential distance between the double defects.     

Surface plasmon–polariton modes of metallic single-walled carbon nanotubes

Propagation of surface plasmon–polariton modes in metallic single-walled carbon nanotubes is investigated within the framework of the classical electrodynamics. Electronic excitations on the nanotube's surface are modeled by an infinitesimally thin layer of free-electron gas which is described by means of the linearized hydrodynamic theory. General expression of surface modes dispersion is obtained by solving Maxwell and hydrodynamic equations with appropriate boundary conditions. It is shown that the system generally disallows the separation of the transverse electric (TE) modes and transverse magnetic (TM) modes, except for the case of modes with no angular dependence.     

Structure of Lennard–Jones nanowires encapsulated by carbon nanotubes

Molecular dynamics simulations have been performed to investigate the structures of Lennard–Jones(LJ) nanowires(NWs) encapsulated in carbon nanotubes(CNTs). We find that the structures of NWs in a small CNT only adopt multi-shell motifs, while the structures of NWs in a larger CNT tend to adopt various motifs. Among these structures, three of them have not been reported previously. The phase boundaries among these structures are obtained regarding filling fractions, as well as the interaction between NWs and CNTs.     

Synthesis and characterization of highly textured Pt–Bi thin films

Pt–Bi films were synthesized on glass and thermally oxidized silicon substrates by e-beam evaporation and annealing. The structures were characterized using X-ray diffraction (XRD) and transmission electron microscopy/selected area electron diffraction (TEM/SAED) techniques. Single-phase PtBi was obtained at an annealing temperature of 300°C, whereas a higher annealing temperature of 400°C was required to obtain the highly textured γ-PtBi₂ phase. TEM/SAED analysis showed that the films annealed at 400°C contain a dominant γ-PtBi₂ phase with a small amount of β-PtBi₂ and α-PtBi₂ phases. Both the PtBi and γ-PtBi₂ phases are highly textured in these two kinds of film: the c-axis of the hexagonal PtBi phase is mostly in the film plane, whereas the c-axis of the trigonal γ-PtBi₂ phase is perpendicular to the film plane. The electrical resistivity of the film with the γ-PtBi₂ phase was smaller by one order of magnitude than that of the film with the PtBi phase.     

Synthesis,characterization, and electrochemical performance of nitrogen-modified Pt–Fe alloy nanoparticles supported on ordered mesoporous carbons

A method has been demonstrated to synthesize nitrogen-modified Pt–Fe alloyed nanoparticles (9.2–11.3 nm) supported on ordered mesoporous carbon (Pt _x Fe_100?x N/OMC), which is fabricated by a conventional wet chemical synthesis of Pt–Fe alloyed nanoparticles and followed by carbonization of the nanoparticles with tetraethylenepentamine as nitrogen chelating agent. Among these electrocatalysts, the Pt₃₀Fe₇₀N/OMC has highly catalytic activity for the oxygen reduction reaction (ORR) with significantly enhanced methanol tolerance as well. Combining the results from X-ray diffraction and X-ray absorption spectroscopy, it can be observed that Pt metal in the Pt₃₀Fe₇₀N/OMC is present in the outer shell of Pt–Fe alloys with face-centered cubic crystalline structure. By X-ray photoelectron spectroscopy, the nitrogen-modified Pt surface of Pt₃₀Fe₇₀N/OMC exhibits significant selectivity toward the ORR in the presence of methanol. This enhancement of methanol tolerance could be attributed to the inhibition of methanol adsorption resulting from the modification of the Pt surface with nitrogen.     

Synthesis,characterization and thermodynamic study of carbon dioxide adsorption on akaganéite

A mixture of akaganéite nanoparticles and sodium salts was synthesized and modified, first by washing, and then by Li exchange. The structural characterization of the produced materials was performed with: powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, thermo-gravimetric analysis, diffuse reflectance infrared Fourier transform spectrometry, Mössbauer spectroscopy and magnetization measurements. Additionally low pressure nitrogen and high pressure carbon dioxide adsorption experiments were performed. The sum of the characterization information made possible to conclude that the produced akaganéite phases crystallized in a structure exhibiting the symmetry of the I2/m space group, where the measured equivalent spherical diameter of the akaganéite crystallites yielded 9 nm, as well, the tested phases exhibited a standard behaviour under heating and displayed a superparamagnetic behaviour. Finally the high pressure carbon dioxide adsorption experiments demonstrated a pressure-responsive framework opening event due to a structural transformation of the adsorbent framework induced by the guest molecules. This fact opens new applications for akaganéite as a high pressure adsorbent.     

A numerical-analytical model for the characterization of composites reinforced by carbon nanotubes

A mixed model, numerical-analytical, is presented that allows one to predict the elastic properties of carbon nanotube (CNT)/polymer composites containing a random distribution of CNTs, while taking account of the curvature that they show when immersed in the polymer. This hybrid approach is a significant advance over micromechanical modeling and can be applied to all nanostructured composites.     

Darcy–Forchheimer 3D flow of carbon nanotubes with homogeneous and heterogeneous reactions

This article deals with Darcy–Forchheimer three dimensional (3D) flow of water-based carbon nanotubes (CNTs) with heterogeneous–homogeneous reactions. A bidirectional nonlinear extendable surface has been employed to create the flow. Flow in porous space is represented by Darcy–Forchheimer expression. Heat transfer mechanism is explored through convective heating. Equal diffusion coefficients are considered for both auto catalyst and reactants. Results for single-wall (SWCNT) and multi-wall (MWCNT) carbon nanotubes have been presented and compared. The diminishment of partial differential framework into nonlinear ordinary differential framework is made through suitable transformations. Optimal homotopy scheme is used for arrangements development of governing flow problem. Optimal homotopic solution expressions for velocities and temperature are studied through plots by considering various estimations of physical variables. Moreover the surface drag coefficients and heat transfer rate are analyzed through plots.     

Covalent marriage of multi-walled carbon nanotubes (MWNTs) and β-cyclodextrin (β-CD) by silicon coupling reagents

In this study, β-cyclodextrin (β-CD) polymer was covalently bonded to multi-walled carbon nanotubes (MWNTs) with the aid of γ-glycidoxypropyltrimethoxysilane (GPTMS) for the fabrication of novel porous materials with special surface properties. The success of synthesis and physicochemical properties of β-CD polymer grafted MWNTs (MWNTs-g-CDP) were characterized by FT-IR, XPS, TGA, TEM and BET. The novel materials were further utilized to remove the typical contaminant of resorcinol in industrial wastewater. The results illustrated that MWNTs-g-CDP possessed much higher adsorption capability and demonstrated the shorter saturation adsorption time than that of pristine MWNTs. Therefore, MWNTs-g-CDP with the unique pore and surface characteristics may have great potentials in environmental applications.     

Intrinsic spin–orbit interaction in carbon nanotubes and curved nanoribbons

We present a theoretical study of spin–orbit interaction effects on single wall carbon nanotubes and curved graphene nanoribbons by means of a realistic multiorbital tight-binding model, which takes into account the full symmetry of the honeycomb lattice. Several effects relevant to spin–orbit interaction, namely, the importance of chirality, curvature, and a family-dependent anisotropic conduction and valence band splitting are identified. We show that chiral nanotubes and nanoribbons exhibit spin-split states. Curvature-induced orbital hybridization is crucial to understand the experimentally observed anisotropic spin–orbit splittings in carbon nanotubes. In fact, spin–orbit interaction is important in curved graphene nanoribbons, since the induced spin-splitting on the edge states gives rise to spin-filtered states.