Enhanced weak localization effect in few-layer graphene

We have investigated the weak localization correction to magnetoresistance in one to six layer graphene structures. The magnetoresistance measurements have revealed that, in addition to the known transition from weak anti-localization in monolayer graphene to weak localization in bilayer graphene, the weak localization effect becomes more pronounced as the number of graphene layers increases. The obtained results substantiate that because few-layer graphene suppresses mesoscopic corrugations and increases intervalley scattering it leads to the observed enhancement of negative resistance, resulting in the restoration of the weak localization in graphene materials. High field magnetoresistance measurements show non-linear behavior, which indicates the breaking of sub-lattice symmetry and the formation of excitonic gap in the Landau level.     

Multilayer graphene nanoribbons exhibit larger capacitance than their few-layer and single-layer graphene counterparts

This article demonstrates that it is not always beneficial to exfoliate graphitic structures to single-layer graphene to achieve maximum electrochemical performance. Using electrochemical impedance spectroscopy, we show that multilayer graphene nanoribbons with cross sections of 100 × 100 nm provide larger capacitance (15.6 F/g) than do few-layer graphene nanoribbons (14.9 F/g) and far larger capacitance than single-layer graphene nanoribbons (10.9 F/g) with the same cross section.     

Supercapacitive performances of few-layer MoS2 on reduced graphene oxides

Journal of Solid State Electrochemistry - Reduced graphene oxide/molybdenum disulfide composites (RGO/MoS2s) with steric structures were directly synthesized via a hydrothermal approach using a...     

Three-dimensional nano-foam of few-layer graphene grown by CVD for DSSC

We report a robust and direct route to fabricate a three-dimensional nano-foam of few-layer graphene (3D-NFG) with large area coverage via a chemical vapor deposition (CVD) technique. Pyrolysis of polymer/nickel precursor film under a hydrogen environment, simply prepared by spin-coating, leads to the creation of nano-foam in the film and the reduction process of nickel ions. Carbonized-C and the nickel nano-frame formed from the pyrolysis are used as a solid carbon source and as a catalyst for the growth of graphene under CVD conditions, respectively. We investigate the use of 3D-NFG, with the advantage of large surface area and high conductivity, as an alternative to the Pt counter electrode material in dye sensitized solar cells. The excellent properties of 3D-NFG, fabricated in this simple and direct manner, suggest a great potential for interconnected graphene networks in electronic devices and photocatalytic sensors as well as in energy-related materials.     

Millimeter-sized few-layer graphene sheets with aligned channels for fast lithium-ion charging kinetics

Assembly of the top-down graphene units mostly results in 3D porous structure with randomly organized pores.The direct bottom-up synthesis of macroscopic 2D graphene sheets with organized pores are long sought in materials chemistry field,but rarely achieved.Herein,we present a self-catalysisassisted bottom-up route usingL-glutamic acid and iron chloride as starting materials for the fabrication of the millimeter-sized few-layer graphene sheets with aligned porous channels parallel to the 2D direction.The amino-and carboxyl-functional groups inL-glutamic acid can coordinate with iron cations,thus allowing an atomic dispersion of iron cations.The pyrolysis thus initiated the growth of graphene catalyzed by in-situ generated iron nanoparticles,and a dynamic flow of iron nanoparticles eventually led to the formation of millimeter-sized few-layer graphene sheets with aligned channels(60-85 nm in diameter).Used as anodes in lithium-ion batteries,these graphene sheets showed a good rate capability(142 m A h g^-1 at 2 A g^-1)and high capacity retention of 93%at 2 A g^-1 after 1200 cycles.Kinetic analysis revealed that lithium ions storage was dominated by diffusion behavior and capacitive behavior together,in that graphene sheets with aligned channels could accelerate electron transfer and shorten lithium ions transport pathway.This work provides a novel approach to prepare unique porous graphene materials with specific structure for energy storage.     

Synthesis of few-layer N-doped graphene from expandable graphite with melamine and its application in supercapacitors

In this paper,we introduced a novel method to prepare the few-layer nitrogen-doped graphene(FNG)from expandable graphite with melamine.The super-capacitive properties of FNG were thoroughly characterized by a three-electrode system,and the results showed the FNG electrode achieved a specific capacitance as high as 83.8 mF/cm2 together with excellent cycling stability.This method could be a novel approach to combine the pseudo-capacitors and electric double layer capacitors.     

High-yield synthesis of few-layer graphene flakes through electrochemical expansion of graphite in propylene carbonate electrolyte

High-yield production of few-layer graphene flakes from graphite is important for the scalable synthesis and industrial application of graphene. However, high-yield exfoliation of graphite to form graphene sheets without using any oxidation process or super-strong acid is challenging. Here we demonstrate a solution route inspired by the lithium rechargeable battery for the high-yield (>70%) exfoliation of graphite into highly conductive few-layer graphene flakes (average thickness <5 layers). A negative graphite electrode can be electrochemically charged and expanded in an electrolyte of Li salts and organic solvents under high current density and exfoliated efficiently into few-layer graphene sheets with the aid of sonication. The dispersible graphene can be ink-brushed to form highly conformal coatings of conductive films (15 ohm/square at a graphene loading of <1 mg/cm(2)) on commercial paper.     

Surface-enhanced Raman scattering of single- and few-layer graphene by the deposition of gold nanoparticles

Surface-enhanced Raman scattering (SERS) of graphene on a SiO(2)(300 nm)/Si substrate was investigated by depositing Au nanoparticles using thermal evaporation. This provided a maximum enhancement of 120 times for single-layer graphene at 633 nm excitation. SERS spectra and scan images of single-layer and few-layer graphene were acquired. Single-layer graphene provides much larger SERS enhancement compared to few-layer graphene, while in single-layer graphene the enhancement of the G band was larger than that of the 2D band. Furthermore, the D bands were identified in the SERS spectra; these bands were not observed in a normal Raman spectrum without Au deposition. Appearance of the D band is ascribed to the considerable SERS enhancement and not to an Au deposition-induced defect. Lastly, SERS enhancement of graphene on a transparent glass substrate was compared with that on the SiO(2)(300 nm)/Si substrate to exclude enhancement by multiple reflections between the Si substrate and deposited Au nanoparticles. The contribution of multiple reflections to total enhancement on the SiO(2)(300 nm)/Si substrate was 1.6 times out of average SERS enhancement factor, 71 times.     

Phase separation in potassium-doped ZnPc thin films

In this study synchrotron radiation was used to investigate the electronic properties of a thin film of zinc-phthalocyanine (ZnPc) deposited on Si(001)-2x1 and progressively doped with K atoms. The molecular orientation was probed by angular-dependent x-ray absorption spectroscopy and the molecules were found to lie with the macrocycle plane roughly perpendicular to the surface. The evolution of the electronic properties of the film was then followed by measuring the photoemission spectra upon in situ evaporation of K atoms on the pristine ZnPc film. The results show that doping proceeds through charge donation from the K atoms to the molecular units whose lowest unoccupied molecular orbital (LUMO) becomes progressively filled. Despite the fact that the LUMO spectral weight increases as the stoichiometry x in the K(x)ZnPc compound varies from about 1 to 4 (as determined by core level photoemission), no detectable density of states was observed at the Fermi level, showing that the film remains insulating for all the investigated stoichiometries. On the other hand the C 1s spectra, which appear merely broadened at the earliest stages of doping (x approximately 1), clearly develop two distinct components when x exceeds 2, suggesting that the charge state is not the same for all the molecules. At the same time, the modification of the valence band points towards the coexistence of two distinct phases with x=2 and x=4.     

Synthesis of transparent vertically aligned TiO2 nanotubes on a few-layer graphene (FLG) film

Novel transparent 1D-TiO(2)/few-layer graphene electrodes are realised by the anodic growth of vertically aligned TiO(2) nano-tubes on a few-layer graphene film coated on a glass substrate.     

An infrared study of the few-layer graphene | ionic liquid interface: Reintroduction of in situ electroreflectance spectroscopy

A simple method of producing high quality few-layer graphene (FLG) electrodes (< 5 nm thick) has been described and the in situ infrared measurements of the FLG/1-ethyl-3-methylimidazolium tetrafluoroborate system have been reported. Ideal polarizability of the system has been established and three different spectral modes have been discussed in order to provide a varied understanding of both the electronic and structural effects at the interface. The method of in situ electroreflectance spectroscopy has been extended to the study of FLG | ionic liquid interface, providing new information about the method and possibilities for future studies of specific adsorption and electronic structure of the interface. Plasmonic enhancement of the spectra has been demonstrated, providing excellent opportunities for the study of the electric double layer and infrared sensors.     

Self-assembly of C60, SWNTs and few-layer graphene and their binary composites at the organic-aqueous interface

Self-assembly of C(60), single-walled carbon nanotubes (SWNTs) and few-layer graphene at the toluene-water interface has been investigated, starting with different concentrations of the nanocarbons in the organic phase and carrying out the assembly to different extents. Morphologies and structures of the films formed at the interface have been investigated by electron microscopy and other techniques. In the case of C(60), the films exhibit hcp and fcc structures depending on the starting concentration in the organic phase, the films being single crystalline under certain conditions. Self-assembly of the composites formed by pairs of nanocarbons (C(60)-SWNT, C(60)-few-layer graphene and SWNT-few-layer graphene) at the interface has been studied by electron microscopy. Raman spectroscopy and electronic absorption spectroscopy of the films formed at the interface have revealed the occurrence of charge-transfer interaction between SWNTs and C(60) as well as between few-layer graphene and C(60).     

Nernstian Li+ intercalation into few-layer graphene and its use for the determination of K+ co-intercalation processes

Alkali ion intercalation is fundamental to battery technologies for a wide spectrum of potential applications that permeate our modern lifestyle, including portable electronics, electric vehicles, and the electric grid. In spite of its importance, the Nernstian nature of the charge transfer process describing lithiation of carbon has not been described previously. Here we use the ultrathin few-layer graphene (FLG) with micron-sized grains as a powerful platform for exploring intercalation and co-intercalation mechanisms of alkali ions with high versatility. Using voltammetric and chronoamperometric methods and bolstered by density functional theory (DFT) calculations, we show the kinetically facile co-intercalation of Li⁺ and K⁺ within an ultrathin FLG electrode. While changes in the solution concentration of Li⁺ lead to a displacement of the staging voltammetric signature with characteristic slopes ca. 54–58 mV per decade, modification of the K⁺/Li⁺ ratio in the electrolyte leads to distinct shifts in the voltammetric peaks for (de)intercalation, with a changing slope as low as ca. 30 mV per decade. Bulk ion diffusion coefficients in the carbon host, as measured using the potentiometric intermittent titration technique (PITT) were similarly sensitive to solution composition. DFT results showed that co-intercalation of Li⁺ and K⁺ within the same layer in FLG can form thermodynamically favorable systems. Calculated binding energies for co-intercalation systems increased with respect to the area of Li⁺-only domains and decreased with respect to the concentration of –K–Li– phases. While previous studies of co-intercalation on a graphitic anode typically focus on co-intercalation of solvents and one particular alkali ion, this is to the best of our knowledge the first study elucidating the intercalation behavior of two monovalent alkali ions. This study establishes ultrathin graphitic electrodes as an enabling electroanalytical platform to uncover thermodynamic and kinetic processes of ion intercalation with high versatility.

Nernstian signatures and swift voltammetry at graphene electrodes help elucidate alkali ion (co-)intercalation.     

In-situ infrared spectroscopy of a photoirradiated potassium-doped C60 film

Photodimerization between C₆₀ molecules in a potassium-doped C₆₀ film (a mixture of α-C₆₀ and K₃C₆₀ phases) has been investigated using in-situ Fourier-transform (FT) infrared spectroscopy in combination with tight-binding molecular dynamics calculations. A comparison of the experimental spectrum of C₆₀ dimers, which was found to be a main product in the photoirradiated K-doped film using an FT mass spectrometer, with the theoretical spectra for several isomers of C₁₂₀ suggests that C₁₂₀ species with structures similar to a bucky peanut were formed in the photoirradiated film.     

Kinetics of nitric oxide reduction with pure and potassium-doped carbon

Summary The kinetics of the reduction of nitric oxide with pure and potassium-doped carbon, NO+C=1/2 N₂+CO, were investigated. For the reaction of NO with pure carbon, measurements were made in the temperature range from 1750 K to 2130 K and at initial NO pressures between 5×10^–3 Pa and 7×10^–2 Pa. The reaction was first order with respect to nitric oxide at NO pressures below 3×10^–2 Pa. The activation energy was 54 kJ/mol for temperatures below 2000 K, while at higher temperatures a second (parallel) reaction became noticeable with a definitely higher activation energy. Potassium-doped carbon was prepared by a molecular beam technique. AES studies verified that potassium was intercalated into the graphite surface and that the potassium-to-carbon ratio changed continuously with sample temperature. The reduction of NO with K-doped carbon was investigated in the temperature range from 710 K to 1080 K and at initial NO pressures between 7×10^–5 Pa and 6×10^–4 Pa while monitoring, in-situ using AES the K/C-ratio of the surface. The NO reduction rate rose linearly with K/C. Compared to pure carbon, the reaction rate for the NO reduction with K-doped carbon increased by a factor in the range of 10⁴. The activation energy for the NO reduction with K-doped carbon was found to be 82 kJ/mol.     

Room temperature LPG resistive sensor based on the use of a few-layer graphene/SnO<Subscript>2</Subscript> nanocomposite

A nanocomposite consisting of a few layers of graphene (FLG) and tin dioxide (SnO₂) was prepared by ultrasound-assisted synthesis. The uniform SnO₂ nanoparticles (NPs) on the FLG were characterized by X-ray diffraction in terms of lattice and phase structure. The functional groups present in the composite were analyzed by FTIR. Electron microscopy (HR-TEM and FE-SEM) was used to study the morphology. The effect of the fraction of FLG present in the nanocomposite was investigated. Sensitivity, selectivity and reproducibility towards resistive sensing of liquid propane gas (LPG) was characterized by the I-V method. The sensor with 1% of FLG on SnO₂ operated at a typical voltage of 1 V performs best in giving a rapid and sensitive response even at 27 °C. This proves that the operating temperature of such sensors can be drastically decreased which is in contrast to conventional metal oxide LPG sensors.

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Graphical abstract Schematic of a room temperature gas sensor for liquefied petroleum gas (LPG). It is based on the use of a few-layered graphene (1 wt%)/SnO₂ nanocomposite that was deposited on an interdigitated electrode (IDEs). A sensing mechanism for LPG detection has been established.

     

Recent Advances in Fullerene Superconductivity

Superconducting transition temperatures in bulk chemically intercalated fulleride salts reach 33 K at ambient pressure and in hole-doped C₆₀ derivatives in field-effect-transistor (FET) configurations, they reach 117 K. These advances pose important challenges for our understanding of high-temperature superconductivity in these highly correlated organic metals. Here we review the structures and properties of intercalated fullerides, paying particular attention to the correlation between superconductivity and interfullerene separation, orientational order/disorder, valence state, orbital degeneracy, low-symmetry distortions, and metal- C₆₀ interactions. The metal-insulator transition at large interfullerene separations is discussed in detail. An overview is also given of the exploding field of gate-induced superconductivity of fullerenes in FET electronic devices.     

One-step synthesis of nitrogen-doped few-layer graphene structures decorated with Mn1.5Co1.5O4 nanoparticles for highly efficient electrocatalysis of oxygen reduction reaction

A nanocomposite consisting of nitrogen-doped few-layer graphene structures, the surface of which is decorated with nanocrystallites of Mn_1.5Co_1.5O₄ spinel oxide, was prepared by a single-stage method of plasma-assisted electrochemical exfoliation of graphite in a solution of 1 M NaNO₃ + 0.005 M MnSO₄ + 0.005 M CoSO₄ + 0.01 M melamine. The high catalytic activity of the synthesized catalyst in the oxygen reduction reaction is due to pyridine nitrogen atoms and Mn_1.5Co_1.5O₄ spinel nanoparticles.