Search

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.

Hierarchical structures based on carbon paper and multi-walled nitrogen-doped carbon nanotubes were fabricated and subsequently decorated with hematite nanorods to obtain advanced 3D architectures for Li-ion battery negative electrodes. The carbon paper provides a versatile metal-free 3D current collector ensuring a good electrical contact of the active materials to its carbon fiber network. Firstly, the nitrogen-doped carbon nanotubes onto the carbon paper were studied and a high footprint area capacity of 2.1 mAh cm(-2) at 0.1 mA cm(-2) was obtained. The Li can be stored in the inter-wall regions of the nanotubes, mediated by the defects formed on their walls by the nitrogen atoms. Secondly, the incorporation of hematite nanorods raised the footprint area capacity to 2.25 mAh cm(-2) at 0.1 mA cm(-2). However, the repeated conversion/de-conversion of Fe2O3 limited both coulombic and energy efficiencies for these electrodes, which did not perform as well as those including only the N-doped carbon nanotubes at higher current densities. Thirdly, long-cycling tests showed the robust Li insertion mechanism in these N-doped carbonaceous structures, which yielded an unmatched footprint area capacity enhancement up to 1.95 mAh cm(-2) after 60 cycles at 0.3 mA cm(-2) and an overall capacity of 204 mAh g(-1) referred to the mass of the entire electrode. De 2 första författarna delar förstaförfattarskapet.

We present a detailed experimental study on how magnetic and electronic properties of Rb, K-intercalated C-60 encapsulated inside carbon nanotubes called peapods can be derived from C-13 nuclear magnetic resonance investigations. 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 at the nanoscale. 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 intercalation. The metallization of intercalated peapods is evidenced from the chemical shift anisotropy and spin-lattice relaxation (T-1) measurements. The observed relaxation curves signal a three-component model with two slow and one fast relaxing components. We assigned the fast component to the unpaired electrons charged C-60 that show a phase transition near 100 K. The two slow components can be rationalized by the two types of charged C-60 at two different positions with a linear regime following Korringa behavior, which is typical for metallic system and allow us to estimate the density of sate at Fermi level n(E-F).

Raman results for different single-walled carbon nanotube bundles doped with Br2 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 nanotube bundles as a form of polymer.

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.

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 ~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 PdO(x) 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 functionalized 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.

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 irr ...

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.

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-cry ...

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), ...

We present high resolution ${}^{133}\mathrm{Cs}{\ensuremath{-}}^{13}\mathrm{C}$ double resonance NMR data and ${}^{13}\mathrm{C}{\ensuremath{-}}^{13}\mathrm{C}$ NMR correlation spectra of ${}^{13}\mathrm{C}$ enriched samples of the polymeric phase of ${\mathrm{CsC}}_{60}$. These data lead to a partial assignment of the lines in the ${}^{13}\mathrm{C}$ NMR spectrum of ${\mathrm{CsC}}_{60}$ to the carbon positions on the ${\mathrm{C}}_{60}$ molecule. A plausible completion of the assignment can be made on the basis of an ab initio calculation. The data support the view that the conduction electron density is concentrated at the ${\mathrm{C}}_{60}$ ``equator,'' away from the interfullerene bonds.

We show in this paper that characteristic features in the Raman spectra, especially the frequency of the pentagonal pinch mode, can give information about the polymeric structure of pressure polymerised C60. High-pressure treatment at 1 GPa below 510 K for 3 h results in the formation of a low fraction of dimers only, while treatment at the same pressure and time above 540 K affords a fully polymerised material. In the latter case, different relative fractions of dimers and polymer chains are obtained depending on whether the final reaction conditions were reached by isobaric or isothermal path. We suggest that this difference results from different reaction dynamics in the two cases. The polymerisation rate depends on T and p and on the rotational and orientational states of the molecules. At 1 GPa no polymerisation is observed in sc C60, while in “hexagon” oriented sc C60 at 1.7 GPa dimers are already formed 175 K below the fcc–sc transition and a fully polymerised material is obtained just below the transition to the fcc phase.

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 discuss the structural and dynamic properties of C60 polymerized under low-P, low-T conditions, and suggest that the disordered mixed orthorhombic-tetragonal-rhombohedral phases produced under t ...

We have studied the structural, thermophysical, and spectroscopic properties of polymeric C60 obtained by high pressure treatment at pressures and temperatures near 1 GPa and 600 K. We present here ...

are reported. Although prepared according to different routes the Raman spectra of the two polymeric phases of C60 show a quantitative agreement with respect to mode positions and intensity. We conclude from this that both materials have the same structure at least in the short range order, i.e. the same type of bonding and co-ordination between neighbouring C60 molecules. An investigation of the time dependence of the thermal decomposition of high pressure polymerised C60 is also presented. The rate of decomposition of the polymeric phase is found to be multi-exponential at all temperatures investigated. From an Arrhenius-type analysis of the short time data and the long time data, respectively, the activation energy for thermal dissociation of polymeric bonds was found to increase with time.

We have examined intercalated compounds of C60 containing four light alkali metal atoms per molecule. The single-metal compounds Na4C60 and Li4C60 form two-dimensional polymers with intermolecular ...

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%13C enriched C60by 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.

Molecular hydrogen can be generated renewably by water splitting with an artificial-leaf device, which essentially comprises two electrocatalyst electrodes immersed in water and powered by photovoltaics. Ideally, this device should operate efficiently and be fabricated with cost-efficient means using earth-abundant materials. Here, a lightweight electrocatalyst electrode, comprising large surface-area NiCo2O4 nanorods that are firmly anchored onto a carbon-paper current collector via a dense network of nitrogen-doped carbon nanotubes is presented. This electrocatalyst electrode is bifunctional in that it can efficiently operate as both anode and cathode in the same alkaline solution, as quantified by a delivered current density of 10 mA cm(-2) at an overpotential of 400 mV for each of the oxygen and hydrogen evolution reactions. By driving two such identical electrodes with a solution-processed thin-film perovskite photovoltaic assembly, a wired artificial-leaf device is obtained that features a Faradaic H-2 evolution efficiency of 100%, and a solar-to-hydrogen conversion efficiency of 6.2%. A detailed cost analysis is presented, which implies that the material-payback time of this device is of the order of 100 days.

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 °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 of10(4) for a single-crystal nanorod transistor, fabricated with a solution-based and low-temperature process that is compatible with flexible substrates.

The local magnetic properties of the one dimensional inner space of the nanotubes are investigated using 13C 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 π 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.

In this article the alkali metal-intercalated two-dimensional (2D) polymer Na4C60 is studied under pressure up to 41 GPa at room temperature by Raman spectroscopy and x-ray diffraction (XRD) measur ...

We report on the electronic properties of Cs-intercalated single-walled carbon nanotubes (SWNTs). A detailed analysis of the C-13 and Cs-133 nuclear magnetic resonance (NMR) spectra reveals an increased metallization of the pristine SWNTs under Cs intercalation. The 'metallization' of CsxC materials where x = 0-0.144 is evidenced from the increased local electronic density of states (DOS) n(E-F) at the Fermi level of the SWNTs as determined from spin-lattice relaxation measurements. In particular, there are two distinct electronic phases called alpha and beta 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 (alpha-phase), whereas it reaches a plateau in the range 0.05

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 C70.

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.

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.

We have encapsulated adamantane (C10H16) in single- and multi-walled carbon nanotubes. Adamantane is a high symmetry cage like molecule with point group symmetry T-d and can be considered as a hydrogen-terminated diamond fragment. We confirmed and identified the successful filling by high resolution transmission electron microscopy, C-13 nuclear magnetic resonance, infrared and Raman spectroscopy. C-13 nuclear magnetic resonance of the adamantane filled nanotubes reveals that the adamantane molecules stop rotating after encapsulation. A blue-shift of the Raman active radial breathing modes of the carbon nanotubes supports this and suggests a significant interaction between encapsulated adamantane molecules and the single wall nanotubes. The encapsulated adamantane molecules exhibit red shifted infrared C-H vibration modes which we assign to a slight elongation of the C-H bonds. We observe both a nanotube diameter dependence of the adamantane filling ratio and a release rate of adamantane from the CNTs that depends on the CNT diameters. (C) 2010 Elsevier Ltd. All rights reserved.

In situ resistance measurements have been carried out on Li4C60 under pressures up to 2 GPa at temperatures from below 100 to 400 K. In agreement with recent reports we find an Arrhenius law behavi ...

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 1H and 13C and in some cases also 3He 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 direct resistance measurements on Na2C60 under high pressure up to 2 GPa in the temperature range ~90–500 K. We show that fresh, nominally pure Na2C60 exhibits a semiconductor-type condu ...

Wepresent Raman spectra for Rb4C60 at pressures up to 13GPa. Above 1 GPa we observe a phase separation ofRb4C60 into Rb6C60 and Rb3C60, identified by a splitting ofthe Ag(2) mode and the appearance ...

Hydrogenation of C60 molecules inside SWNT was achieved by direct reaction with hydrogen gas at elevated pressure and temperature. Evidence for the C60 hydrogenation in peapods is provided by isotopic engineering with specific enrichment of encapsulated species and high resolution 13C and 1H NMR spectroscopy with the observation of characteristic diamagnetic and paramagnetic shifts of the NMR lines and the appearance of sp3 carbon resonances. We estimate that approximately 78% of the C60 molecules inside SWNTs are hydrogenated to an average degree of 14 hydrogen atoms per C60 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. © 2009 American Chemical Society., This work was supported by the Wenner-Gren Foundations and Vetenskapsrädet, by the Spanish MEC (FIS2007-65702-C02-01), Grupos Consolidados UPV/EHU of the Basque Country Government (IT-319-07) European Community e-I3 ETSF project, by the Centre National de la Recherche Scientifique and the region Languedoc-Roussillon.

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 C60α, are blocked at room temperature and 68%, labeled C60β, 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 C60β dynamics. Above the transition, the C60β exhibits continuous rotational diffusion; below the transition, C60β 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 C60β molecules and the inner surface of the nanotubes., This work was supported by Wenner-Gren Foundations and Vetenskapsrådet, by Spanish MEC (FIS2007-65702-C02-01), Grupos Consolidados UPV/EHU of the Basque Country Government (IT-319-07) European Community e-I3 ETSF project, by the Office of Energy Research, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, via the sp2-bonded nanostructures program, the Molecular Foundry, the Centre National de la Recherche Scientifique and the Region Languedoc-Roussillon.

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 semicon ...

A resonant Raman spectroscopy study has been carried out under high pressure, using a diamond anvil cell,on carbon nanotube peapods (C60@SWNT) synthesized in high yield in our laboratory. The Raman ...

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 o ...

We show specific heat data for Na4C60 and Li4C60 in the range 0.4-350 K for samples characterized by Raman spectroscopy and X-ray diffraction. At high temperatures, the two different polymer structures have very similar specific heats both in absolute values and in general trend. The specific heat data are compared with data for undoped polymeric and pristine C60. At high temperatures, a difference in specific heat between the intercalated and undoped C60 polymers of 100 J K(-1) mol(-1) is observed, in agreement with the Dulong-Petit law. At low temperatures, the specific heat data for Li4C60 and Na4C60 are modified by the stiffening of vibrational and librational molecular motion induced by the polymer bonds. The covalent twin bonds in Li4C60 affect these motions to a somewhat higher degree than the single intermolecular bonds in Na4C60. Below 1 K, the specific heats of both materials become linear in temperature, as expected from the effective dimensionality of the structure. The contribution to the total specific heat from the inserted metal ions can be well described by Einstein functions with TE = 386 K for Li4C60 and TE = 120 K for Na4C60, but for both materials we also observe a Schottky-type contribution corresponding to a first approximation to a two-level system with ΔE = 9.3 meV for Li4C60 and 3.1 meV for Na4C60, probably associated with jumps between closely spaced energy levels inside "octahedral-type" ionic sites. Static magnetic fields up to 9 T had very small effects on the specific heat below 10 K.

We present 13C NMR results on the intercalated 2D C60-polymers Li4-xNaxC60 (x=0-4 with half integer steps) showing that while Li4C60 forms a tetragonal polymer with double polymer bonds between the ...

We present a Raman investigation of the monoclinic two-dimensionally polymerized phase Na4C60 and a comparison with the pure tetragonal C60 polymer and the doped K3C60 structure. The Raman spectrum ...

Swedish and Chinese researchers have shown how a unique nano-alloy composed of palladium nano-islands embedded in tungsten nanoparticles creates a new type of catalyst for highly efficient oxygen reduction, an important reaction in hydrogen fuel cells.

We present electrical transport studies of single-walled carbon nanotube mats, synthesized by the arc discharge method with Ce/Ni as catalysts, under hydrostatic pressure up to 1.5 GPa with a liquid pressure medium. These data were compared with the results at ambient pressure. The transport phenomena were described in terms of Mott’s 2D variable range hopping (VRH) conduction up to 1.05 GPa. An irreversible change is induced below 0.5 GPa, and the resistance behavoiur is reversible due to the strong interaction between tubes above 0.5 GPa. These results indicate that 2D VRH occurs within bundles.

High-pressure polymerization of C60 leads to a variety of new crystalline or amorphous phases which display interesting physical properties. We have prepared one-dimensional (1D, C60 chains) and two-dimensional (2D, C60 layers) polymers from C60 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” 1D orthorhombic polymer had been characterized previously [1]. We have now determined the specific stacking of the C60 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.

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.

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. (C) 2011 American Institute of Physics. [doi:10.1063/1.3631052]

The alkali fulleride Rb4C60 has been investigated by studies of the resistance and by Raman spectroscopy under pressures up to 2 GPa and 13 GPa, respectively. Our data show a reversible phase separation into metallic Rb3C60 and Rb6C60 at pressures above 1 GPa. The reversibility indicates that the phase separation primarily occurs on the nanometer length scale. The data explain several puzzling results reported in the recent literature. OPEN ACCESS. Editor in Chief: Kenichi Takemura. Editorial Board: Tadashi Kondo, Hitoshi Matsuki, Nobuyuki Matubayasi, Yoshihisa Mori, Osamu Ohtaka, Chihiro Sekine

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 C13 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., This work was supported by the Centre National de la Recherche Scientifique and the Region Languedoc Roussillon, the Office of Basic Energy Sciences, Materials Sciences and Engineering Division, the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, via the sp2-bonded nanostructures program and the Molecular Foundry, the Wenner-Gren Foundations, and Vetenskapsrådet, the Spanish MEC Grant No. FIS2007-65702-C02-01, Grupos Consolidados UPV/EHU of the Basque Country Government Grant No. IT-319-07, and European Community e-I3 ETSF project.

Two-dimensional polymerisation of a C60 single crystal has been obtained under high-pressure high temperature conditions (700 K - 2 GPa). Crystalline order is preserved but the crystal splits into ...