We present a detailed experimental and theoretical study on how structural properties of carbon nanotubes can be derived from 13C NMR investigations. Magic angle spinning solid state NMR experiments have been performed on single-and multiwalled carbon nanotubes with diameters in the range from 0.7 to 100 nm and with number of walls from 1 to 90. We provide models on how diameter and the number of nanotube walls influence NMR linewidth and line position. Both models are supported by theoretical calculations. Increasing the diameter D, from the smallest investigated nanotube, which in our study corresponds to the inner nanotube of a double-walled tube to the largest studied diameter, corresponding to large multiwalled nanotubes, leads to a 23.5 ppm diamagnetic shift of the isotropic NMR line position d. We show that the isotropic line follows the relation d = 18.3/D + 102.5 ppm, where D is the diameter of the tube and NMR line position d is relative to tetramethylsilane. The relation asymptotically tends to approach the line position expected in graphene. A characteristic broadening of the line shape is observed with the increasing number of walls. This feature can be rationalized by an isotropic shift distribution originating from different diamagnetic shielding of the encapsulated nanotubes together with a heterogeneity of the samples. Based on our results, NMR is shown to be a nondestructive spectroscopic method that can be used as a complementary method to, for example, transmission electron microscopy to obtain structural information for carbon nanotubes, especially bulk samples.

The local magnetic properties of the one dimensional inner space of the nanotubes are investigated using C-13 nuclear magnetic resonance spectroscopy of encapsulated fullerene molecules inside single walled carbon nanotubes. Isotope engineering and magnetically purified nanotubes have been advantageously used on our study to discriminate between the different diamagnetic and paramagnetic shifts of the resonances. Ring currents originating from the pi electrons circulating on the nanotube, are found to actively screen the applied magnetic field by -36.9 ppm. Defects and holes in the nanotube walls cancel this screening locally. What is interesting, that at high magnetic fields, the modifications of the NMR resonances of the molecules from free to encapsulated can be exploited to determine some structural characteristics of the surrounding nanotubes, never observed experimentally. (C) 2011 Elsevier B.V. All rights reserved.

We report on the electronic properties of Cs-intercalated singlewalled carbon nanotubes (SWNTs). A detailed analysis of the ¹³C and¹³³Cs nuclear magnetic resonance (NMR) spectra reveals an increased metallization of the pristine SWNTs under Cs intercalation. The ‘metallization’ of Cs_xC materials where x =0–0.144 is evidenced from the increased local electronic density of states (DOS) n(EF)at the Fermi level of the SWNTs as determined from spin–lattice relaxation measurements. In particular, there are two distinct electronic phases called α and β and the transition between these occurs around x = 0.05. The electronic DOS at the Fermi level increases monotonically at low intercalation levels x <0.05 (α-phase), whereas it reaches a plateau in the range 0.05 < x < 0.143 at high intercalation levels (β-phase). The new β-phase is accompanied by a hybridization of Cs(6s) orbitals with C(sp2)orbitals of the SWNTs. In both phases, two types of metallic nanotubes are found with a low and a high local n(EF), corresponding to different local electronic band structures of the SWNTs.

Hydrogenation of C-60 molecules inside SWNT was achieved by direct reaction with hydrogen gas at elevated pressure and temperature. Evidence for the C-60 hydrogenation in peapods is provided by isotopic engineering with specific enrichment of encapsulated species and high resolution C-13 and H-1 NMR spectroscopy with the observation of characteristic diamagnetic and paramagnetic shifts of the NMR lines and the appearance of sp(3) carbon resonances. We estimate that approximately 78% of the C-60 molecules inside SWNTs are hydrogenated to an average degree of 14 hydrogen atoms per C-60 molecule. As a consequence, the rotational dynamics of the encapsulated C60Hx molecules is clearly hindered. Our successful hydrogenation experiments open completely new roads to understand and control confined chemical reactions at the nano scale

One-dimensional crystals of 25% ¹³C-enriched C₆₀ encapsulated inside highly magnetically purified SWNTs were investigated by following the temperature dependence of the ¹³C NMR line shapes and the relaxation rates from 300 K down to 5 K. High-resolution MAS techniques reveal that 32% of the encapsulated molecules, so-called the C₆₀^α, are blocked at room temperature and 68%, labeled C₆₀^β, are shown to reversly undergo molecular reorientational dynamics. Contrary to previous NMR studies, spin−lattice relaxation time reveals a phase transition at 100 K associated with the changes in the nature of the C₆₀^β dynamics. Above the transition, the C₆₀^β exhibits continuous rotational diffusion; below the transition, C₆₀^β executes uniaxial hindered rotations most likely along the nanotubes axis and freeze out below 25 K. The associated activation energies of these two dynamical regimes are measured to be 6 times lower than in fcc-C₆₀, suggesting a quiet smooth orientational dependence of the interaction between C₆₀^β molecules and the inner surface of the nanotubes.

We examine a variant of so-called carbon nanotube peapods by packing C60 molecules inside the open edge ducts of collapsed carbon nanotubes. C60 insertion is accomplished through a facile single-step solution-based process. Theoretical modeling is used to evaluate favorable low-energy structural configurations. Overfilling of the collapsed tubes allows infiltration of C60 over the full cross-section of the tubes and consequent partial or complete reinflation, yielding few-wall, large diameter cylindrical nanotubes packed with crystalline C60 solid cores.

We report on a dip-coating method to prepare catalyst particles (mixture of iron and cobalt) with a controlled diameter distribution on silicon wafer substrates by changing the solution's concentration and withdrawal velocity. The size and distribution of the prepared catalyst particles were analyzed by atomic force microscopy. Carbon nanotubes were grown by chemical vapor deposition on the substrates with the prepared catalyst particles. By decreasing the catalyst particle size to below 10 nm, the growth of carbon nanotubes can be tuned from few-walled carbon nanotubes, with homogeneous diameter, to highly pure single-walled carbon nanotubes. Analysis of the Raman radial breathing modes, using three different Raman excitation wavelengths (488, 633, and 785 nm), showed a relatively broad diameter distribution (0.8-1.4 nm) of single-walled carbon nanotubes with different chiralities. However, by changing the composition of the catalyst particles while maintaining the growth parameters, the chiralities of single-walled carbon nanotubes were reduced to mainly four different types, (12, 1), (12, 0), (8, 5), and (7, 5), accounting for about 70% of all nanotubes.

Nitrogen doping in carbon nanostructures has attracted interest for more than a decade, and recent implementation of such structures in energy conversion systems has boosted the interest even more. Despite numerous studies, the structural conformation and stability of nitrogen functionalities in small diameter single-walled carbon nanotubes (SWNTs), and the impact of these functionalities on the electronic and mechanical properties of the SWNTs, are incomplete. Here we report a detailed study on nitrogen doping in SWNTs with diameters in the range of 0.8?1.0 nm, with well-defined chirality. We show that the introduction of nitrogen in the carbon framework significantly alters the stability of certain tubes, opening for the possibility to selectively grow nitrogen-doped SWNTs with certain chirality and diameter. At low nitrogen concentration, pyridinic functionalities are readily incorporated and the tubular structure is well pertained. At higher concentrations, pyrrolic functionalities are formed, which leads to significant structural deformation of the nanotubes and hence a stop in growth of crystalline SWNTs. Raman spectroscopy is an important tool to understand guest atom doping and electronic charge transfer in SWNTs. By correlating the influence of defined nitrogen functionalities on the electronic properties of SWNTs with different chirality, we make precise interpretation of experimental Raman data. We show that the previous interpretation of the double-resonance G?-peak in many aspects is wrong and instead can be well-correlated to the type of nitrogen doping of SWNTs originating from the p- or n-doping nature of the nitrogen incorporation. Our results are supported by experimental and theoretical data.

We report on the synthesis and decoration of high-aspect-ratio crystalline C-60 nanorods (NRs) by functionalized palladium nanoparticles with an average size of 4.78 +/- 0.66 nm. In their pristine form, C-60 NRs suffer from partial damage in the solution-based decoration process resulting in poor crystallinity. However, by modifying the NR surface via in situ photochemical transformation in the liquid state, we are able to prepare highly stable NRs that retain their crystalline structure during the decoration process. Our method thus opens up for the synthesis of highly crystalline nanocomposite hybrids comprising Pd nanoparticles and C-60 NRs. Bys measuring the electron mobility of different C-60 NRs, we relate both the effect of electron mobility and crystallinity to the final electrocatalytic performance of the synthesized hybrid structures. We show that the photo-transformed C-60 NRs exhibit highly advantageous properties for ethanol oxidation based on both a better crystallinity and a higher bulk conductivity. These findings give important information in the search for efficient catalyst support.

A modified liquid-liquid interface precipitation synthesis of C-60 nanorods, effects and opportunities following an in situ photochemical transformation in the liquid state, and an electronic characterization using a field-effect transistor (FET) geometry are reported. The nanorods feature a high aspect ratio of approximate to 10(3) and a notably small average diameter of 172 nm. Interestingly, it is found that a decreased nanorod diameter appears to correlate with distinctly improved electronic properties, and an average electron mobility of 0.30 cm(2) V-1 s(-1), as measured in a FET geometry, is reported for as-grown nanorods, with the peak value being an impressive 1.0 cm(2) V-1 s(-1). A photoexposure using green laser light ( = 532 nm) is demonstrated to result in the formation of a polymer-C-60 shell encapsulating a monomer-C-60 bulk; such photo-transformed nanorods exhibit an electron mobility of 4.7 x 10(-3) cm(2) V-1 s(-1). It is notable that the utilized FET geometry only probes the polymer-C-60 nanorod surface shell, and that the monomer-C-60 bulk is anticipated to exhibit a higher mobility. Importantly, photoexposed nanorods can be conveniently processed as a stabile dispersion in common hydrophobic solvents, and this finding is attributed to the insoluble character of the polymer-C-60 shell.

C-60 nanorods with hexagonal cross sections are grown using a static liquid-liquid interfacial precipitation method in a system of C-60/m-dichlorobenzene solution and ethanol. Adding water to the ethanol phase leads instead to C-60 tubes where both length and diameter of the C-60 tubes can be controlled by the water content in the ethanol. Based on our observations we find that the diameter of the rods/tubes strongly depends on the nucleation step. We propose a liquid-liquid interface growth model of C-60 rods and tubes based on the diffusion rate of the good C-60 containing solvent into the poor solvent as well as on the size of the crystal seeds formed at the interface between the two solvents. The grown rods and tubes exhibit a hexagonal solvate crystal structure with m-dichlorobenzene solvent molecules incorporated into the crystal structure, independent of the water content. An annealing step at 200 degrees C at a pressure <1 kPa transforms the grown structures into a solvent-free face centered cubic structure. Both the hexagonal and the face centered cubic structures are very stable and neither morphology nor structure shows any signs of degradation after three months of storage.

The nuclear magnetic resonance (NMR) analytical technique was used to investigate the double walled carbon nanotubes (DWNTs) electromagnetic properties of inner walls. The local magnetic and electronic properties of inner nanotubes in DWNTs were analyzed using 25% (13) C enriched C-60 by which the effect of dipolar coupling could be minimized. The diamagnetic shielding was determined due to the ring currents on outer nanotubes in DWNTs. The NMR chemical shift anisotropy (CSA) spectra and spin-lattice relaxation studies reveal the metallic properties of the inner nanotubes with a signature of the spin-gap opening below 70 K.

We present 13 C high-resolution magic-angle-turning (MAT) and magic angle spinning nuclear magnetic resonance data of Cs and Rb intercalated single walled carbon nanotubes. We find two distinct phases at different intercalation levels. A simple charge transfer is applicable at low intercalation level. The new phase at high intercalation level is accompanied by a hybridization of alkali (s) orbitals with the carbon (sp2) orbitals of the single walled nanotubes, which indicate bundle surface sites is the most probable alkali site.

Rhombohedral C₆₀ polymer was subjected to high-pressure-high-temperature treatment at P =13 GPa, T =620-1620 K. After quenching, crystalline and disordered structures with densities in the range of 2.1-2.9 g cm^-1 were obtained. The structures of the samples have been investigated by powder X-ray diffraction and Raman scattering. DSC analysis showed a transformation of the polymeric structure into monomeric on annealing in the range 400-640 K. The temperature dependence of the electrical resistance of samples with disordered structure was measured in the range 2.5-300K. For different samples, the conductivity was proportional to T^1/2, T^3/2, T⁴ and exp(-1/T^1/4).

We have investigated thin-film field-effect transistors (TFTs) with C60 as the active material, and we report the effects of photo-induced polymerization of the C60 film. We find that the effects of a complete polymerization for a typical top-contact C60 TFT is as follows: the electron mobility (μn) at room temperature drops slightly from 0.074 to 0.068 cm2/Vs, the activation energy of μn decreases from 0.10 meV to 0.09 meV, and the threshold voltage for TFT operation decreases markedly by ~15 %. The latter observation suggests that the effective number of electron traps in the C60 film decreases following polymerization. Considering that the polymerization was achieved with a low-energy HeNe laser, it is conceivable that the polymerization approach could be of interest for applications, e.g., organic bulk-heterojunction solar cells, where a stabilized C60 morphology attained with benign means is desired

We report a novel and potentially generic method for the efficient patterning of films of organic semiconductors and demonstrate the merit of the method on the high-solubility fullerene [6,6]-phenyl C61- butyric acid methyl ester (PCBM). The patterning technique is notably straightforward as it requires no photoresist material and encompasses only two steps: (i) exposure of select film areas to visible laser light during which the PCBM mononer is photochemically converted into a dimeric state, and (ii) development via solvent washing after which the nonexposed portions of the PCBM film are selectively removed. Importantly, the method is highly benign in that it leaves the electronic properties of the remaining patterned material intact, which is directly evidenced by the fact that we fabricate fully functional arrays of micrometersized field-effect transistors with patterned PCBM as the active material.

Studies on noble-metal-decorated carbon nanostructures are reported almost on a daily basis, but detailed studies on the nanoscale interactions for well-defined systems are very rare. Here we report a study of reduced graphene oxide (rGOx) homogeneously decorated with palladium (Pd) nanoclusters with well-defined shape and size (2.3 +/- 0.3 nm). The rGOx was modified with benzyl mercaptan (BnSH) to improve the interaction with Pd clusters, and N,N-dimethylformamide was used as solvent and capping agent during the decoration process. The resulting Pd nanoparticles anchored to the rGOx-surface exhibit high crystallinity and are fully consistent with six-shell cuboctahedral and icosahedral clusters containing similar to 600 Pd atoms, where 45% of these are located at the surface. According to X-ray photoelectron spectroscopy analysis, the Pd clusters exhibit an oxidized surface forming a PdOx shell. Given the well-defined experimental system, as verified by electron microscopy data and theoretical simulations, we performed ab initio simulations using 10 functionalized graphenes (with vacancies or pyridine, amine, hydroxyl, carboxyl, or epoxy groups) to understand the adsorption process of BnSH, their further role in the Pd cluster formation, and the electronic properties of the graphene-nanoparticle hybrid system. Both the experimental and theoretical results suggest that Pd clusters interact with fiinctionalized graphene by a sulfur bridge while the remaining Pd surface is oxidized. Our study is of significant importance for all work related to anchoring of nanoparticles on nanocarbon-based supports, which are used in a variety of applications.

Graphene and its derivatives hold great potential as support for nanocatalyst in various energy applications, such as fuel cells, batteries, and capacitors. In this work, we used density functional theory to analyze substrate effect on the electrocatalytic activity of Pt–Ni bimetallic nanoparticles for oxygen reduction reaction (ORR). The dissociative mechanism is used to evaluate the ORR performance (energy barrier for O2 dissociation, free energy of intermediates, d-band center, overpotential, and electrochemical activity) for a Pt–Ni core–shell-like nanoparticle (PtNiCS) deposited on nondefective graphene (GS) or nitrogen-doped graphene (N-GS). The electronic and catalytic properties of PtNiCS on N-GS designate N-doped graphene as the best substrate to use for ORR, showing better interaction with the bimetallic cluster, improved charge transfer between constitutes, and a superior ORR performance when compared to PtNiCS on GS. The N-GS has a significant effect in reducing the energy barrier for O2 dissociation and decrease the energetic stability of HO* intermediates, resulting in enhanced ORR activity compared with the PtNiCS on GS. In addition, the strong interaction between PtNiCS cluster and N-GS substrate may lead to an improved long-term stability of the catalytic particle during ORR cycles.

NMR spectroscopy is so far the only analytical technique that has been used to get a detailed structural characterization of hydrogenated fullerenes. A substantial amount of information derived from different NMR experiments can thus be found in the literature for a number of fullerenes hydrogenated to various degrees. These studies have benefitted from the fact that chemical shifts of H-1 and C-13 and in some cases also He-3 can be used to obtain structural information of these compounds. Such results, together with discussions about different NMR experiments and general considerations regarding sample preparations, are summarized in this chapter. The unique information, both structural and physicochemical, that can be derived from different NMR experiments ensures that this technique will continue to be of central importance in characterization of hydrogenated fullerenes.

We present the synthesis of palladium nanocrystals self-assembled on helical carbon nanofibers functionalized with benzyl mercaptan (Pd-S-HCNFs) and their electrocatalytic activity toward the oxidation of formic acid, methanol and ethanol. Helical carbon nanofibers (HCNFs) were first functionalized with benzyl mercaptan based on the pi-pi interactions between phenyl rings and the graphitic surface of HCNFs. Palladium nano crystals (PdNC) were fixed on the surface of functionalized HCNF by Pd-S bonds in a simple self-assembly method. The as-prepared materials were characterized by high resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), cyclic voltammetry (CV), and fuel cell tests. CV characterization of the as-prepared materials shows a very high electrocatalytic activity for oxidation of formic acid, ethanol and methanol in strong alkaline electrolyte. In comparison to commercial catalyst Vulcan XC-72 decorated with Pd nanoparticles, the proposed Pd-S-HCNFs nano composite material shows oxidation currents for formic acid, ethanol and methanol at the Pd-S-HCNF-modified electrode that are higher than that at the Pd/XC-72 modified electrode with a factor of 2.0, 1.5, and 2.3, respectively. In a formic acid fuel cell the Pd-S-HCNF modified electrode yields equal power density as commercial Pd/XC-72 catalyst. Our results show that Pd-decorated helical carbon nanofibers with diameters around 40-60 nm have very high potential as active material in fuel cells, electrocatalysts and sensors. (C) 2012 Elsevier B.V All rights reserved.

The sluggish kinetics of the oxygen reduction reaction at the cathode side of proton exchange membrane fuel cells is one major technical challenge for realizing sustainable solutions for the transportation sector. Finding efficient yet cheap electrocatalysts to speed up this reaction therefore motivates researchers all over the world. Here we demonstrate an efficient synthesis of palladium-tungsten bimetallic nanoparticles supported on ordered mesoporous carbon. Despite a very low percentage of noble metal (palladium: tungsten = 1:8), the hybrid catalyst material exhibits a performance equal to commercial 60% platinum/Vulcan for the oxygen reduction process. The high catalytic efficiency is explained by the formation of small palladium islands embedded at the surface of the palladium-tungsten bimetallic nanoparticles, generating catalytic hotspots. The palladium islands are similar to 1 nm in diameter, and contain 10-20 palladium atoms that are segregated at the surface. Our results may provide insight into the formation, stabilization and performance of bimetallic nanoparticles for catalytic reactions.

The development of easy and environmentally benign synthesis methods of efficient electrocatalysts for use in energy conversion applications motivates researchers all over the world. Here we report a novel and versatile method to synthesize well-dispersed palladium-functionalized ordered mesoporous carbons (Pd/OMCs) at room temperature without any reducing agent by one-pot mixing of tri(dibenzylideneacetone)palladium(0) (Pd2DBA3) and OMCs together in a common N,N-dimethylformamide (DMF) solution. The formation of Pd nanoparticles and their crystallization on the OMC is catalyzed by protons in the solution and can thus be controlled by the solution pH. The complete process and the as-prepared nanocomposite was characterized by UV-spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (HTEM), X-ray photoelectron spectrum (XPS), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The electrocatalytic property of the as-decorated material was examined with cyclic voltammetry (CV). The Pd/OMC composite shows up to two times higher electrocatalytic ability with a significantly better durability towards ethanol and methanol oxidation in alkaline media compared to commercial high surface area conductive carbon black Vulcan XC-72 decorated with equivalent Pd nanoparticles. Our described method provides new insight for the development of highly efficient carbon based nanocatalysts by simple and environmentally sound methods.

We present a novel approach to prepare helical carbon nanofibers homogeneously functionalized with single crystal palladium nanoparticles via a phase-transfer method. The materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA) and electrochemical measurements. We find that homogeneous and small single-crystal Pd nanoparticles can be easily functionalized with phenyl mercaptan, transferred into the toluene phase from the dimethyl sulfoxide (DMSO) phase and then non-covalently self-assembled onto the surface of helical carbon nanofibers with a very good dispersion and homogeneous diameters of 4.5 +/- 0.6 nm. The palladium-helical carbon nanofiber composite exhibits significantly higher electrochemical active area and electrocatalytic activity towards the electrooxidation of formic acid, ethanol and methanol than the commercial electrocatalyst Pd/Vulcan XC-72. Our results show that the prepared material can be potentially used as an advanced nano-electrocatalyst in a direct alkaline fuel cell system.

Amorphous palladium nanoparticles functionalized helical carbon nanofibers (ApPd-HCNFs) were synthesized using a phase-transfer method. Palladium nanoparticles (Pd-NP) were first prepared using n-dodecyl sulfide as reducing agent and stabilizing ligands in ethanol. The Pd-NPs were then modified with benzyl mercaptan and transferred into a toluene solution with HCNFs which were decorated with amorphous palladium. The materials were characterized with high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy and cyclic voltammetry showing that amorphous palladium nanoparticles were uniformly anchored at the HCNFs surface and that the ApPd-HCNFs exhibit high electrocatalytic activity towards hydrazine oxidation. (C) 2012 Elsevier B.V. All rights reserved.

We present the results of direct resistance measurements on Rb4C60 under pressures up to 2 GPa. At all pressures covered by this study and over the temperature range of 90–450 K Rb4C60 is a semiconductor with a weakly pressure dependent band gap near 0.7 eV. We do not observe the insulator-to-metal transition previously reported to occur below 1.2 GPa, although we cannot rule out the possibility that such a transition might occur at some significantly higher pressure. The measured resistivity is surprisingly low and is dominated by carriers excited over a 0.1 eV gap. Because the corresponding conductivity increases with deformation of the sample, we assign these states to structural or orientational defects. The known structural transformation below 0.5 GPa leads to a decrease in resistivity under high pressure, but the material remains semiconducting. A Rb6C60 control sample showed a similar behavior, also being a semiconductor under all conditions studied. At temperatures above 460 K, Rb was partially lost from our samples, resulting in metallization by a transformation into Rb3C60.

We report the results of direct in situ resistance measurements of Rb4C60 under high pressure up to 2 GPa, in the temperature range 90–400 K. The resistance changes smoothly with pressure and temperature without sharp anomalies, and all data sets can be fitted to the same theoretical semiconductor model. We find no signs of the insulator-to-metal transition previously reported in this range, but the fitted band gap decreases with pressure and such a transition may possibly take place above 5 GPa.

We report on a novel sensing platform for H2O2 and glucose based on immobilization of palladium-helical carbon nanofiber (Pd-HCNF) hybrid nanostnictures and glucose oxidase (GOx) with Nafion on a glassy carbon electrode (GCE). HCNFs were synthesized by a chemical vapor deposition process on a C-60-supported Pd catalyst. Pd-HCNF nanocomposites were prepared by a one-step reduction free method in dimethylformamide (DMF). The prepared materials were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy. The Nafion/Pd-HCNF/GCE sensor exhibits excellent electrocatalytic sensitivity toward H2O2 (315 mA M-1 cm(-2)) as probed by cyclic voltammetry (CV) and chronoamperometry. We show that Pd-HCNF-modified electrodes significantly reduce the overpotential and enhance the electron transfer rate. A linear range from 5.0 mu M to 2.1 mM with a detection limit of 3.0 mu M (based on the S/N = 3) and good reproducibility were obtained. Furthermore, a sensing platform for glucose was prepared by immobilizing the Pd-HCNFs and glucose oxidase (GOx) with Nafion on a glassy carbon electrode. The resulting biosensor exhibits a good response to glucose with a wide linear range (0.06-6.0 mM) with a detection limit of 0.03 mM and a sensitivity of 13 mA M-1 cm(-2). We show that small size and homogeneous distribution of the Pd nanoparticles in combination with good conductivity and large surface area of the HCNFs lead to a H2O2 and glucose sensing platform that performs in the top range of the herein reported sensor platforms.

In this paper, CeO2 nanocubes with the (200)-terminated surface/graphene sheet composites have been prepared successfully by a simple hydrothermal method. It is found that the CeO2 nanocubes with high crystallinity and specific exposed surface are well dispersed on well-exfoliated graphene surface. The (200)-terminated surface/graphene sheet composites modified electrode showed much higher sensitivity and excellent selectivity in its catalytic performance compared to a CeO2 nanoparticle-modified electrode. The photoluminescence intensity of the CeO2 anchored on graphene is about 30 times higher than that of pristine CeO2 crystals in air. The higher oxygen vacancy concentration in CeO2 is supposed to be an important cause for the higher photoluminescence and better electrochemical catalytic performance observed in the (200)-terminated surface/graphene sheet composites. Such ingenious design of supported well-dispersed catalysts in nanostructured ceria catalysts, synthesized in one step with an exposed high-activity surface, is important for technical applications and theoretical investigations.

The understanding and control of the magnetic properties of carbon-based materials is of fundamental relevance in applications in nano- and biosciences. Ring currents do play a basic role in those systems. In particular the inner cavities of nanotubes offer an ideal environment to investigate the magnetism of synthetic materials at the nanoscale. Here, by means of 13 C high resolution NMR of encapsulated molecules in peapod hybrid materials, we report the  largest diamagnetic shifts (down to -68.3 ppm) ever observed in carbon allotropes, which is connected to the enhancement of the aromaticity of the nanotube envelope upon doping. This diamagnetic shift can be externally controlled by in situ modifications such as doping or electrostatic charging. Moreover, defects such as C-vacancies, pentagons, and chemical functionalization of the outer nanotube quench this diamagnetic effect and restore NMR signatures to slightly paramagnetic shifts compared to nonencapsulated molecules. The magnetic interactions reported here are robust phenomena independent of temperature and proportional to the applied magnetic field. The magnitude, tunability, and stability of the magnetic effects make the peapod nanomaterials potentially valuable for nanomagnetic shielding in nanoelectronics and nanobiomedical engineering.

Theunderstanding and control of the magnetic properties of carbon-based materialsis of fundamental relevance in applications in nano- and biosciences.Ring currents do play a basic role in those systems.In particular the inner cavities of nanotubes offer an idealenvironment to investigate the magnetism of synthetic materials at thenanoscale. Here, by means of ¹³C high resolution NMR ofencapsulated molecules in peapod hybrid materials, we report the largestdiamagnetic shifts (down to −68.3 ppm) ever observed in carbonallotropes, which is connected to the enhancement of the aromaticityof the nanotube envelope upon doping. This diamagnetic shift canbe externally controlled by in situ modifications such as dopingor electrostatic charging. Moreover, defects such as C-vacancies, pentagons, andchemical functionalization of the outer nanotube quench this diamagnetic effectand restore NMR signatures to slightly paramagnetic shifts compared tononencapsulated molecules. The magnetic interactions reported here are robust phenomenaindependent of temperature and proportional to the applied magnetic field.The magnitude, tunability, and stability of the magnetic effects makethe peapod nanomaterials potentially valuable for nanomagnetic shielding in nanoelectronicsand nanobiomedical engineering

Single-walled carbon nanotubes substitutionally doped with the light-element phosphorus are synthesized and are investigated by electrical and nuclear magnetic resonance measurements. Decreased spin lattice relaxation times compared to undoped tubes point toward enhanced spin-sensitive scattering. Temperature dependence of the zero-bias conductance shows step-like features, a signature of scattering from a very low density (few sites per nanotube) of localized spin moments at oxidized phosphorus sites, consistent with density functional calculations. This supports recent predictions that localized magnetic moments must be indirectly magnetically coupled through the nanotube conduction electrons.

Flexible and high-aspect-ratio C-60 nanorods are synthesized using a liquid-liquid interfacial precipitation process. As-grown nanorods are shown to exhibit a hexagonal close-packed single-crystal structure, with m-dichlorobenzene solvent molecules incorporated into the crystalline structure in a C-60:m-dichlorobenzene ratio of 3.2. An annealing step at 200 degrees C transforms the nanorods into a solvent-free face-centred-cubic polycrystalline structure. The nanorods are deposited onto field-effect transistor structures using two solvent-based techniques: drop-casting and dip-coating. We find that dip-coating deposition results in a preferred alignment of non-bundled nanorods and a satisfying transistor performance. The latter is quantified by the attainment of an electron mobility of 0.08 cm(2) V-1 s(-1) and an on/off ratio of >10(4) for a single-crystal nanorod transistor, fabricated with a solution-based and low-temperature process that is compatible with flexible substrates.

Raman results for different single-walled carbon nanotube bundles doped withBr2 were studied both at ambient pressure and under high pressure up to 6 GPa.Our study indicates that bromine resides in the interstitial channel of nanotubebundles as a form of polymer.

The electric resistance of single-walled nanotube mats has been studied systematically under both ambient and high hydrostatic pressures up to 1.5 GPa. Both the temperature dependence of the resistance and the magnetoresistance indicate that electrical transport occurs by variable range hopping, apparently in 2D. We suggest that this unexpected dimensionality arises from a fractal network of tubes and bundles. Under hydrostatic pressure (HP) the resistance still shows 2D variable range hopping and decreases with increasing HP. An irreversible increase in localization length and DOS is induced below 0.5 GPa. The behavior is reversible and due to strong interaction of tubes from 0.5 GPa up to 1.05 GPa. These results indicate that 2D variable range hopping occurs within bundles.

The study of electrical transport properties of bulk single-walled carbon nanotube (SWNT) materials attracts a lot of attention. However, the transport results differ from sample to sample[l]. Some results show semiconducting behavior with different laws and whether the behavior is dominated by on-tube or on-bundle effects or by interbundle contacts is still unknown. Therefore, further investigation is still meaningful. The effect of hydrostatic pressure(HP), which is expected to significantly change the interaction between tubes or bundles, gives us a further possibility to understand the characteristic properties. Under HP, Raman spectra and electric resistance show pronounced changes at 1.5GPa[2]. In this study, we systematically studied the electric resistance up to 1.5 GPa, giving a different image of the transport behavior.

We have studied the effect of using rare-earth elements C (typically +4 oxide state) and Eu (typically +2 oxide state) together with nanometer Ni as catalysts to synthesize SWNT in high yield by arc evaporation. A black collar deposit containing mainly SWNT was formed in the presence of Ce/Ni while only nanometer carbon particles were formed using Eu/Ni, as identified by SEM, TEM and Raman spectra. The Raman spectra of our SWNT mats show difference from spectra shown in the literature in a low frequency range, indicating that our mats contain chiral tubes. The temperature dependent resistance of SWNT mats was also measured. A semiconducting behaviour was observed with a negative dR/dT and no resistance minimum from 2 to 350 K. The resistance follows a 2D variable range hopping behaviour.

SWNTs were synthesized in high yield in the presence of Ce/Ni as catalyst. Raman and SEM results show that a fraction of the tubes are chiral and have small diameters (the smallest one is 0.79 nm), indicating that Ce plays an important role in the formation. Acid treatment is effective in eliminating impurities but changes the morphology and the electric resistance of mats with increasing treatment time. The resistance of as-grown and short time acid-treated mats follow a 2D VRH behaviour while mats treated for a long time follow a 3D model. The results indicate that hopping conduction occurs on bundles or on tubes and that there are intrinsic links between tubes in as-grown mats.

C₆₀ nanotubes with outer diameters ranging from 400–800 nm were polymerized at 1.5 GPa, 573 K and 2.0 GPa, 700 K, respectively. Raman and photoluminescence spectroscopy were employed to characterize the polymeric phases of the treated samples. Both Raman and photoluminescence spectra showed that the C₆₀ nanotubes transformed into the dimer and orthorhombic phases under the two different conditions, respectively. The photoluminescence peaks were tuned from visible to near infrared range. Comparative studies indicated that C₆₀ nanotubes were more difficult to polymerize than bulk C₆₀ material under the same conditions due to the nanoscale size effect in the C₆₀ nanotubes.

Single crystalline C₇₀ nanotubes having a face-centered-cubic (fcc) structure with diameters on a nanometer scale were synthesized by a facile solution method. In situ high pressure Raman spectroscopy and X-ray diffraction have been employed to study the structural stability and phase transitions of the pristine sample. We show that the molecular orientation-related phase transition from the fcc structure to a rhombohedral structure occurs at about 1.5 GPa, which is 1 GPa higher than in bulk C₇₀. Also, the C₇₀ molecules themselves are more stable in the nanotubes than in bulk crystals, manifested by a partial amorphization at 20 GPa. The crystal structure of C₇₀ nanotubes could partially return to the initial structure after a pressure cycle above 30.8 GPa, and the C₇₀ molecules were intact up to 43 GPa. The bulk modulus of C₇₀ nanotubes is measured to be 50 GPa, which is twice larger than that of bulk C_70.

In situ high-pressure angle-dispersive synchrotron X-ray diffraction and high-pressure mid-infrared (IR) spectrum measurements of C60H18 were carried out up to 32 and 10.2 GPa, respectively. Our diffraction data indicated that the fcc structure of C60H18 was stable up to 32 GPa. The bulk modulus B0 was determined to be 21 ± 1.16 GPa, about 40% higher than that of C60. The C−H vibrations still existed up to 10.2 GPa, and the vibrational frequencies decreased with increasing pressure. IR-active vibrational frequencies and their corresponding eigenvectors of C60H18 were simulated by DMOL3. The effects of the hydrogen atoms attached to the fullerene molecular cage on the stability of the structure under high pressure are discussed.

Electrical properties of polymerized fullerenes C60 are governed by the type of polymerization which is in turn determined by the initial (P or H) orientation of molecules, the pressure and the temperature of polymerization. The mixed tetragonal - rhombohedral polymerized structure shows a semiconductor-like behavior. An increase in the polymerization temperature results in a decrease in the activation energy and an increase in conductivity. The conductivity prefactor and the activation energy are interconnected by the Meyer-Neldel rule. The pure rhombohedral phase shows highly anisotropic electrical properties. The conductivity in the polymerized (111) planes exhibits a metal-insulator transition and shows the features of 2D weak localization.

The general trend in the shift of electronic properties as the result of polymerization has been studied with the aid of temperature dependences of conductivity. Samples representing the pure rhombohedral phase exhibit great anisotropy in their electrical properties. The main features of the behaviour of these samples are: (i) in the z-direction the resistivity is of the order of several kOhm cm and decreases with temperature; (ii) in the x-y direction resistivity is less than 1 Ohm cm and shows a minimum at a certain temperature.

We have examined several samples of first- to third-stage PdAl2Cl8-intercalated graphite under hydrostatic pressures up to 1 GPa. In stage-1 highly oriented pyrolytic graphite–(HOPG) and single-crystal-graphite-based materials, the c-axis resistivity decreases sharply above a few kilobars; pressure release induces a reversible return to the initial value only in the case of the latter sample. Raman spectra taken in situ under pressure on a HOPG-based material show similarly irreversible effects. Analysis of the spectra taken on higher-stage samples leads to the conclusion that hydrostatic pressure beyond a few kilobars increases the density of the intercalate within the graphitic galleries, transforming the initial sample to a higher-stage material. Since there is no loss of intercalate, the overall intercalate-to-host charge transfer remains constant so that the Raman frequency is approximately the same for both first- and second-stage products. This is an unusual situation in which there is thus an apparent lack of Raman signature in spite of the stage change.

The structural stability of the tetragonal two-dimensional (2D) polymeric phase of C60 has been studied under pressure up to 24 GPa and room temperature by means of in situ Raman scattering. An irreversible transformation of the material to a new phase was observed at pressure 20 GPa. The phonon spectrum of the high-pressure phase provides a strong indication that the fullerene molecular cage is retained and therefore this phase may be related to a three-dimensional (3D) network of C60 cages. The new phase remains stable upon slow release of pressure to ambient conditions. The recovered material is metastable and transforms in air by detonation under laser irradiation to partially dimerized C60.,

High-pressure polymerisation of C^o leads to a variety of new crystalline or amorphous phases which display interesting physical properties. We have prepared onedimensional (ID, C6o chains) and two-dimensional (2D, C60 layers) polymers from C6o single crystals. The resulting multi-domain crystals have been studied using x-ray diffraction and Raman spectroscopy. The relative orientations of the chains in the "low-pressure" ID orthorhombic polymer had been characterized previously [1]. We have now determined the specific stacking of the Ceo layers in the 2D tetragonal and rhombohedral polymers. Using these results we analyze the relations between the different polymers and the intermolecular environments which may play a role in stabilizing the observed polymer structures.