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.     

Electrical Conductivity of Films Formed by Few-Layer Graphene Structures

Current–voltage characteristics of few-layer graphene structures produced by electrochemical exfoliation of graphite in an electrolyte solution were measured. It was shown that few-layer graphene structures possess an electronic conductivity, which is indicative of the small degree of surface functionalization of the structures. The resistance of films formed by these structures grows with increasing relative humidity of the medium because of the shielding of fl akes of the few-layer graphene structures by a film of water.     

Linking photo- and redoxactive phthalocyanines covalently to graphene

"Green" graphene: For the first time, the covalent attachment of a light-harvesting and electron-donating phthalocyanine to the basal plane of few-layer graphene is reported. Physicochemical characterizations reveal an ultrafast charge separation from the photoexcited phthalocyanine to few-layer graphene followed by a slower charge recombination.     

Magnetic property and structural study of nickel supported on reduced graphene oxide prepared by chemical vapor deposition

Nickel supported on reduced graphene oxide was synthesized by chemical vapor deposition technique. The crystal structure and magnetic properties of the prepared sample were studied by means of Raman spectrometry, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectrometry (ICP-OES), and vibrating sample magnetometry (VSM). The result of Raman spectroscopy revealed the structure of few-layer graphene as the support for Ni nanoparticles. XP spectrum confirmed the presence of metallic Ni on the a few-layer graphene surface. TE micrograph showed that the nickel nanoparticles were sphere shaped and the mean particle size is about 20 nm deposited on the reduced graphene oxide. The magnetic study showed the ferromagnetic behavior of 3.2 wt% nickel over reduced graphene oxide at room temperature.     

石墨烯的纳米摩擦与磨损性质

采用乙醇溶剂剥离的方法制备石墨烯. 通过对溶剂温度、超声时间、超声功率和溶剂离心速度及时间的控制, 从高定向热解石墨(HOPG)制备得到少层石墨烯. 用原子力显微镜(AFM)研究了云母基底上不同层数石墨烯在真空中的纳米摩擦过程, 发现从约4 个原子单层(4 ML)起, 摩擦系数基本不再变化, 但摩擦力仍随着厚度的增加而显著减小, 7 ML之后, 其摩擦系数基本接近于零. 在磨损实验中, 少层石墨烯表面存在刮坏的现象,且不同厚度的石墨烯的磨损现象明显不同, 其中2 ML石墨烯相比4 ML石墨烯表现出较好的耐磨损性能, 且不具有摩擦方向依赖性. 测试了真空下少层石墨烯和云母表面的粘附力, 发现不同层厚的石墨烯相差不大, 因此认为基底效应并不是磨损性质差异的主要原因. 相对于单层石墨烯, 少层石墨烯在抗磨损涂层等领域有着很大的潜在应用价值.     

Selective etching of graphene edges by hydrogen plasma

We devised a controlled hydrogen plasma reaction at 300 °C to etch graphene and graphene nanoribbons (GNRs) selectively at the edges over the basal plane. Atomic force microscope imaging showed that the etching rates for single-layer and few-layer (≥2 layers) graphene are 0.27 ± 0.05 nm/min and 0.10 ± 0.03 nm/min, respectively. Meanwhile, Raman spectroscopic mapping revealed no D band in the planes of single-layer or few-layer graphene after the plasma reaction, suggesting selective etching at the graphene edges without introducing defects in the basal plane. We found that hydrogen plasma at lower temperature (room temperature) or a higher temperature (500 °C) could hydrogenate the basal plane or introduce defects in the basal plane. Using the hydrogen plasma reaction at the intermediate temperature (300 °C), we obtained narrow, presumably hydrogen terminated GNRs (sub-5 nm) by etching of wide GNRs derived from unzipping of multiwalled carbon nanotubes. Such GNRs exhibited semiconducting characteristics with high on/off ratios (～1000) in GNR field effect transistor devices at room temperature.     

A Study of the Key Factors on Production of Graphene Materials from Fe-Lignin Nanocomposites through a Molecular Cracking and Welding (MCW) Method

In this work, few-layer graphene materials were produced from Fe-lignin nanocomposites through a molecular cracking and welding (MCW) method. MCW process is a low-cost, scalable technique to fabricate few-layer graphene materials. It involves preparing metal (M)-lignin nanocomposites from kraft lignin and a transition metal catalyst, pretreating the M-lignin composites, and forming of the graphene-encapsulated metal structures by catalytic graphitization the M-lignin composites. Then, these graphene-encapsulated metal structures are opened by the molecule cracking reagents. The graphene shells are peeled off the metal core and simultaneously welded and reconstructed to graphene materials under a selected welding reagent. The critical parameters, including heating temperature, heating time, and particle sizes of the Fe-lignin composites, have been explored to understand the graphene formation mechanism and to obtain the optimized process parameters to improve the yield and selectivity of graphene materials.     

Solution-gated epitaxial graphene as pH sensor

A solution-gate field effect transistor (SGFET) has been fabricated on few-layer graphene (FLG). The ideally polarizable graphene/aqueous electrolyte interface allows the capacitive charging of the surface by hydroxyl (OH-) and hydroxonium ions (H3O+). The conductivity versus gate potential curve exhibits "V" shaped ambipolar transfer characteristics of graphene, with hole and electron mobilities of 3600 cm2/Vs and 2100 cm2/Vs, respectively. The shift of the negative gate potential with pH shows a supra-Nernstian response of 99 meV/pH. Our work points to the potential application of graphene in ultrafast and ultralow noise chemical or biological 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).     

Superconductivity in potassium-doped few-layer graphene

Here we report the successful synthesis of superconducting potassium-doped few-layer graphene (K-doped FLG) with a transition temperature of 4.5 K, which is 1 order of magnitude higher than that observed in the bulk potassium graphite intercalation compound (GIC) KC(8) (T(c) = 0.39 K). The realization of superconductivity in K-doped FLG shows the potential for the development of new superconducting electronic devices using two-dimensional (2D) graphene as a basis material.     

Bipolar Electrochemical Exfoliation of Graphite for Synthesizing Electrocatalysts of Oxygen Reduction

Russian Journal of Electrochemistry - A nanocomposite of few-layer graphene structures with cobalt oxides is synthesized for the first time in an aqueous electrolyte containing Co2+ ions by the...     

Number of graphene layers exhibiting an influence on oxidation of DNA bases: Analytical parameters

This article investigates the analytical performance of double-, few- and multi-layer graphene upon oxidation of adenine and guanine. We observed that the sensitivity of differential pulse voltammetric response of guanine and adenine is significantly higher at few-layer graphene surface than single-layer graphene. We use glassy carbon electrode as substrate coated with graphenes. Our findings shall have profound influence on construction of graphene based genosensors.     

Photocatalytic patterning and modification of graphene

TiO(2)-based photocatalysis has been widely used to decompose various organic pollutants for the purpose of environmental protection. Such a "green" photochemical process can ultimately degrade organic compounds into CO(2) and H(2)O under ambient conditions. We demonstrate here its extended application on the engineering of single- or few-layer graphene. Using a patterned TiO(2) photomask, we have achieved various photochemical tailorings of graphene, including ribbon cutting, arbitrary patterning on any substrate, layer-by-layer thinning, and localized graphene to graphene oxide conversion. UV-visible spectroscopic studies indicate that the photogenerated, highly reactive ·OH radicals work as sharp chemical scissors. Being a solution-free, cost-effective, scalable, and easy handling technique, the presented photocatalytic patterning and modification approach allows for the versatile design and fabrication of graphene-based devices and circuits, compatible with current microelectronic technology, as demonstrated by this fabricated all-carbon field effect transistor (FET) array.     

Local current mapping and patterning of reduced graphene oxide

Conductive atomic force microscopy (C-AFM) has been used to correlate the detailed structural and electrical characteristics of graphene derived from graphene oxide. Uniform large currents were measured over areas exceeding tens of micrometers in few-layer films, supporting the use of graphene as a transparent electrode material. Moreover, defects such as electrical discontinuities were easily detected. Multilayer films were found to have a higher conductivity per layer than single layers. It is also shown that a local AFM-tip-induced electrochemical reduction process can be used to pattern conductive pathways on otherwise-insulating graphene oxide. Transistors with micrometer-scale tip-reduced graphene channels that featured ambipolar transport and an 8 order of magnitude increase in current density upon reduction were successfully fabricated.     

Solvent-exfoliated graphene at extremely high concentration

We describe three related methods to disperse graphene in solvents with concentrations from 2 to 63 mg/mL. Simply sonicating graphite in N-methyl-2-pyrrolidinone, followed by centrifugation, gives dispersed graphene at concentrations of up to 2 mg/mL. Filtration of a sonicated but uncentrifuged dispersion gives a partially exfoliated powder that can be redispersed at concentrations of up to 20 mg/mL. However, this process can be significantly improved by removing any unexfolaited graphite from the starting dispersion by centrifugation. The centrifuged dispersion can be filtered to give a powder of exfoliated few-layer graphene. This powder can be redispersed at concentrations of at least 63 mg/mL. The dispersed flakes are ~1 μm long and ~3 to 4 layers thick on average. Although some sedimentation occurs, ~26-28 mg/mL of the dispersed graphene appears to be indefinitely stable.     

One-Stage Plasma-Assisted Electrochemical Synthesis of Cobalt-Containing Catalysts for Oxygen Reduction

Russian Journal of Electrochemistry - t—The potentialities of single-stage plasma-assisted electrochemical synthesis of few-layer graphene structures with high electrocatalytic...     

Mono- and Few-Layer Nitrogen-Containing Graphenes as Sensitive Layers of Electrochemical Sensors for Selective Determination of Dopamine and Uric Acid in the Presence of Ascorbic Acid

Theoretical and Experimental Chemistry - A comparative study of electrochemical properties of mono- and few-layer samples of nitrogen-doped graphene as nanosized sensor materials for the...     

Few-layer graphenes from ball-milling of graphite with melamine

We report a simple, practical scalable procedure to produce few-layer graphene sheets using ball-milling. Commercially available melamine can be efficiently used to exfoliate graphite and generate concentrated water or DMF dispersions.     

Control of electronic structure of graphene by various dopants and their effects on a nanogenerator

It is essential to control the electronic structure of graphene in order to apply graphene films for use in electrodes. We have introduced chemical dopants that modulate the electronic properties of few-layer graphene films synthesized by chemical vapor deposition. The work function, sheet carrier density, mobility, and sheet resistance of these films were systematically modulated by the reduction potential values of dopants. We further demonstrated that the power generation of a nanogenerator was strongly influenced by the choice of a graphene electrode with a modified work function. The off-current was well quenched in graphene films with high work functions (Au-doped) due to the formation of high Schottky barrier heights, whereas leakage current was observed in graphene films with low work functions (viologen-doped), due to nearly ohmic contact.