Influence of graphite oxide drying temperature on ultra-fast microwave synthesis of graphene

Ultra-fast synthesis of graphene has been reported by microwave assisted graphene oxide reduction. In this article, the graphene oxide was initially dried above room temperature. The initial heat treatment of graphene oxide demonstrates a distinct improvement of exfoliation rate of graphene sheets. This method provides an efficient way for mass production of high quality graphene sheets. Raman spectroscopy, scanning electron microscopy, and X-ray diffraction techniques has been used to characterize reduced graphene sheets. The quality of reduced graphene was found to be affected by the initial drying temperature of graphite oxide.     

Facile preparation of nitrogen-doped few-layer graphene via supercritical reaction

To achieve the applications of graphene, the modulation of its electrical properties is of great significance. The element doping might give a promising approach to produce fascinating properties of graphene. Herein we report a facile chemical doping method to obtain nitrogen-doped (N-doped) few-layer graphene sheets through supercritical (SC) reaction in acetonitrile at temperature as low as 310 °C, using expanded graphite as starting material. X-ray photoelectron spectroscopy analysis revealed that the level of nitrogen-doping (N-doping) increased from 1.57 to 4.56 at % when the reaction time was tuned from 2 to 24 h. Raman spectrum confirmed that the resulting N-doped few-layer graphene by SC reaction maintain high quality without any significant structural defects. Electrical measurements indicated that N-doped few-layer graphene sheets exhibit a typical n-type field-dependent behavior, suggesting the N-doping into the lattice of graphene. This work provides a convenient chemical route to the scalable production of N-doped graphene for potential applications in nanoelectronic devices.     

The production of nitrogen-doped graphene from mixed amine plus ethanol flames

A simple process is described for directly synthesizing pure graphene and N-doped graphene sheets from ethanol flame and amine plus ethanol flames respectively. The microstructures and nitrogen contents of the graphenes were characterized using scanning and transmission electron spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. The results reveal that: (1) The graphene sheets from flame exhibit good transparency and a large size up to 400 μm² with few layers and folded edges; (2) The nitrogen-doped graphene sheets have a dominant ‘pyridine-type’ structure with CN bonds (one N atom bonded to two C atoms); (3) Compared with other methods, the graphene sheets from flame have more surface defects due to the environmental conditions and introduction of nitrogen atoms, which makes it a promising material for supercapacitors and catalyst supports.     

Solvothermal-assisted exfoliation process to produce graphene with high yield and high quality

Monolayer and bilayer graphene sheets have been produced by a solvothermal-assisted exfoliation process in a highly polar organic solvent, acetonitrile, using expanded graphite (EG) as the starting material. It is proposed that the dipole-induced dipole interactions between graphene and acetonitrile facilitate the exfoliation and dispersion of graphene. The facile and effective solvothermal-assisted exfoliation process raises the low yield of graphene reported in previous syntheses to 10 wt%–12 wt%. By means of centrifugation at 2000 rpm for 90 min, monolayer and bilayer graphene were separated effectively without the need to add a stabilizer or modifier. Electron diffraction and Raman spectroscopy indicate that the resulting graphene sheets are high quality products without any significant structural defects.      

Highly conducting graphene sheets and Langmuir-Blodgett films

Graphene is an intriguing material with properties that are distinct from those of other graphitic systems. The first samples of pristine graphene were obtained by 'peeling off' and epitaxial growth. Recently, the chemical reduction of graphite oxide was used to produce covalently functionalized single-layer graphene oxide. However, chemical approaches for the large-scale production of highly conducting graphene sheets remain elusive. Here, we report that the exfoliation-reintercalation-expansion of graphite can produce high-quality single-layer graphene sheets stably suspended in organic solvents. The graphene sheets exhibit high electrical conductance at room and cryogenic temperatures. Large amounts of graphene sheets in organic solvents are made into large transparent conducting films by Langmuir-Blodgett assembly in a layer-by-layer manner. The chemically derived, high-quality graphene sheets could lead to future scalable graphene devices.     

锂离子电池负极材料中间相炭微球的表面镀镍修饰研究

采用化学镀的方法在石墨化中间相炭微球的表面镀覆金属镍,采用扫描电镜对镀覆后的炭微球进行了表面分析,采用X-射线衍射的方法对镀镍炭微球进行了物相分析,将镀覆后的中间相炭微球用于锂离子电池负极材料,并进行了不同倍率的充放电分析及交流阻抗研究。结果表明,在不使用活化剂和敏化剂的情况下,金属镍仍然能够沉积在炭微球的表面;炭微球的大电流放电性能大大提高,在2C放电电流下的放电容量提高了23%,镀镍后交换电流密度增大并且SEI膜电阻减小,炭微球的反应活性大大提高。     

Growth of graphene sheets under an oxyacetylene flame without a catalyst北大核心CSCD

High quality graphene sheets that had a low I-D/I-G and a high 2D intensity in Raman spectra were prepared by a catalyst-free acetylene flame method. The sheets were grown vertically on the surface of carbon particles to form a petal-like morphology. A high temperature, high pressure and short residence time of the flame intensified the decomposition and cyclization reaction's of acetylene, leading to the formation of graphene sheets in the gas phase. The turbulent flame and the gases released during the formation of the graphene sheets from carbon nuclei could be responsible for their petal-like morphology instead of an onion-like structure.     

Synthesis and characterization of electrochemically-reduced graphene

Graphene has superior electrical conductivity than graphite and other allotropes of carbon because of its high surface area and chemical tolerance. Electrochemically processed graphene sheets were obtained through the reduction of graphene oxide from hydrazine hydrate. The prepared samples were heated to different temperatures such as 673 and 873 K. X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), transmission electron microscopy (TEM), Raman spectra and conductivity measurements were made for as-prepared and heat-treated graphene samples. XRD pattern of graphene shows a sharp and intensive peak centred at a diffraction angle (2θ) of 26·350. FTIR spectra of as-prepared and heated graphene were used to confirm the oxidation of graphite. TEM results indicated that the defect density and number of layers of graphene sheets were varied with heating temperature. The hexagonal sheet morphology and purity of as-prepared and heat treated samples were confirmed by SEM–EDX and Raman spectroscopy. The conductivity measurements revealed that the conductivity of graphene was decreased with an increase in heating temperature. The present study explains that graphene with enhanced functional properties can be achieved from the as-prepared sample.     

Substrate Doping Effect and Unusually Large Angle van Hove Singularity Evolution in Twisted Bi‐ and Multilayer Graphene

Graphene has demonstrated great potential in new‐generation electronic applications due to its unique electronic properties such as large carrier Fermi velocity, ultrahigh carrier mobility, and high material stability. Interestingly, the electronic structures can be further engineered in multilayer graphene by the introduction of a twist angle between different layers to create van Hove singularities (vHSs) at adjustable binding energy. In this work, using angle‐resolved photoemission spectroscopy with sub‐micrometer spatial resolution, the band structures and their evolution are systematically studied with twist angle in bilayer and trilayer graphene sheets. A doping effect is directly observed in graphene multilayer system as well as vHSs in bilayer graphene over a wide range of twist angles (from 5° to 31°) with wide tunable energy range over 2 eV. In addition, the formation of multiple vHSs (at different binding energies) is also observed in trilayer graphene. The large tuning range of vHS binding energy in twisted multilayer graphene provides a promising material base for optoelectrical applications with broadband wavelength selectivity from the infrared to the ultraviolet regime, as demonstrated by an example application of wavelength selective photodetector.     

Large and flat graphene flakes produced by epoxy bonding and reverse exfoliation of highly oriented pyrolytic graphite

We present a fabrication method producing large and flat graphene flakes that have a few layers down to a single layer based on substrate bonding of a thick sample of highly oriented pyrolytic graphite (HOPG), followed by its controlled exfoliation down to the few to single graphene atomic layers. As the graphite underlayer is intimately bonded to the substrate during the exfoliation process, the obtained graphene flakes are remarkably large and flat and present very few folds and pleats. The high occurrence of single-layered graphene sheets being tens of microns wide in lateral dimensions is assessed by complementary probes including spatially resolved micro-Raman spectroscopy, atomic force microscopy and electrostatic force microscopy. This versatile method opens the way for deposition of graphene on any substrates, including flexible ones.     

功能化石墨烯片的表面性能调控

以氧化石墨为前驱体,采用真空辅助热膨胀法在低温下即获得功能化石墨烯片。将所得石墨烯在不同温度下热处理,制备了表面化学结构不同的石墨烯片,并用透射电子显微镜、X射线衍射、X射线光电子能谱、傅里叶变换红外光谱等方法对样品进行分析表征。结果表明,还原氧化石墨烯片中含氧官能团的种类和数量均随热还原温度的升高而减小。     

Effects of functional groups on the graphene sheet for improving the thermomechanical properties of polyurethane nanocomposites

Dispersibility of graphene sheets in polymer matrices and interfacial interaction are challenging for producing graphene-based high performance polymer nanocomposites. In this study, three kinds nanofillers; pristine graphene nanoplatelets (GNPs), graphene oxide (GO), and functionalized graphene sheet (FGS) were used to prepare polyurethane (PU) composite by in-situ polymerization. To evaluate the efficacy of functional groups on the graphene sheets, PU reinforced with GNPs, GO, and FGS were compared through tensile testing and dynamic mechanical thermal analysis. The Young's moduli of 2 wt% GO and FGS based PU nanocomposites were found significantly higher than that of same amount of GNPs loading as an evidence of the effect of functional groups on graphene sheets for the mechanical reinforcement. The strong interaction of FGS with PU was responsible to exhibit notably high modulus (25.8 MPa) of 2 wt% FGS/PU composite than the same amount of GNPs and GO loading even at elevated temperature (100 °C).     

Substrate-free gas-phase synthesis of graphene sheets

We present a novel method for synthesizing graphene sheets in the gas phase using a substrate-free, atmospheric-pressure microwave plasma reactor. Graphene sheets were synthesized by passing liquid ethanol droplets into an argon plasma. The graphene sheets were characterized by transmission electron microscopy, electron energy loss spectroscopy, Raman spectroscopy, and electron diffraction. We prove that graphene can be created without three-dimensional materials or substrates and demonstrate a possible avenue to the large-scale synthesis of graphene.     

Managing the degree of exfoliation and number of graphene layers using probe sonication approach

We have demonstrated a fast, versatile, and scalable approach to synthesize high-quality few layer graphene sheets with low defect ratio and high crystallinity produced from exfoliation of graphite flakes in DMF by using probe sonication. The effect of sonication time on degree of exfoliation and number of graphene layers has been fully investigated. The degree of exfoliation of graphene sheets as a function of sonication time has been successfully analyzed by XRD, UV-Vis spectroscopy, TEM, and BET studies. The morphological changes at different sonication times have also been observed by SEM. A structural and defect characterization of graphene sheets has been discussed in detail by Raman spectroscopic technique. The shift in position of 2D Raman band and its de-convolution provided information about formation of multi to few layer graphene sheets with sonication. Moreover, Raman results are highly consistent with TEM studies as per number of graphene layers is concerned.     

Noncovalent functionalization of graphene with pyrene-terminated liquid crystalline polymer

Pyrene-terminated liquid crystalline polymers (poly [8-(4-cyano-4′-biphenyl)-1-octanoylacrylate] and poly [6-(4-cyano-4′-biphenyl)-1-hexanoylacrylate]) were synthesized and used to functionalize graphene sheets via π–π interactions. The resulting liquid crystalline polymers functionalized graphene sheets were characterized by UV–vis spectroscopy, fluorescence spectroscopy, thermal gravimetric analysis, Fourier transform infrared spectroscopy, X-ray diffraction, atomic force microscopy and Raman spectroscopy. It was found that an intercalated layer structure was formed when polymer was grafted onto graphene sheets. The liquid crystalline polymers were able to effectively disperse graphene in N,N-dimethylformamide that were stable for months. Additionally, a remarkable smaller distance of adjacent mesogenic units was observed, which is attributed to the confinement of the polymer chains between 2D reduced graphene oxide sheets.     

One-step hydrothermal synthesis,characterization and visible-light catalytic property of Ag-reduced graphene oxide composite

In this paper, a nanocomposite consisting of Ag nanoparticles and reduced graphene oxide sheets was synthesized via a one-step hydrothermal method using glucose as a reducing agent. The as-prepared sample was characterized systematically, and the results indicated that the graphene oxide was reduced and an Ag-reduced graphene oxide hybrid material was formed. It was shown that the as-prepared Ag-reduced graphene oxide was in a layered structure stacked by reduced graphene oxide sheets. The Ag nanoparticles decorated on the reduced graphene oxide sheets. The analysis revealed that there was strong interaction between the Ag nanoparticles and reduced graphene oxide sheets. A photodegradation study was also performed on the Ag-reduced graphene oxide composite. It showed that the composite exhibited a high catalytic activity for the photodegradation of Rhodamine B pollutant under visible-light irradiation, which made Ag-reduced graphene oxide a promising candidate as photocatalyst for Rhodamine B.     

Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition

Integration of individual two-dimensional graphene sheets into macroscopic structures is essential for the application of graphene. A series of graphene-based composites and macroscopic structures have been recently fabricated using chemically derived graphene sheets. However, these composites and structures suffer from poor electrical conductivity because of the low quality and/or high inter-sheet junction contact resistance of the chemically derived graphene sheets. Here we report the direct synthesis of three-dimensional foam-like graphene macrostructures, which we call graphene foams (GFs), by template-directed chemical vapour deposition. A GF consists of an interconnected flexible network of graphene as the fast transport channel of charge carriers for high electrical conductivity. Even with a GF loading as low as ～0.5 wt%, GF/poly(dimethyl siloxane) composites show a very high electrical conductivity of ～10 S cm(-1), which is ～6 orders of magnitude higher than chemically derived graphene-based composites. Using this unique network structure and the outstanding electrical and mechanical properties of GFs, as an example, we demonstrate the great potential of GF/poly(dimethyl siloxane) composites for flexible, foldable and stretchable conductors.     

The synthesis and fluorescence quenching properties of well soluble hybrid graphene material covalently functionalized with indolizine

Chemically functionalized graphene-indolizine functionalized graphene (IMG) sheets, which can be well dispersed in different organic solvents over four months without obvious aggregation, are obtained through a 1,3-dipolar cycloaddition to graphene with pyridinium ylide. The properties of IMG sheets are investigated using a thorough set of measurements including UV-visible spectroscopy, Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), Raman spectroscopy, x-ray photoelectron spectroscopy (XPS), photoluminescence spectroscopy (PL), transmission electron microscopy (TEM), atomic force microscopy (AFM) and cyclic voltammetry (CV), and a tagging technique has exhibited the distribution of functional groups on the graphene surface. The IMG sheets show very strong quenching by a factor of ～ 93.4% to that of indolizine, which is attributed to the fluorescence resonance energy transfer (FRET) from indolizine molecules to few-layer graphene sheets. The CV method also proved the catalytic properties of IMG sheets in some redox systems.     

Growth of few layer graphene from commercial C2 hydrocarbons at low temperature and controlled surface functionalization

Graphene is mostly grown from methane on copper foils at a high temperature about 1000°C. In this research, a commercial ethylene-acetylene-ethane mixture was used as a clean precursor for graphene synthesis on nickel foils in a chemical vapor deposition reactor at 750°C. Furthermore, controlled functionalization of graphene sheets was achieved via hydrothermal oxidation at moderate pressure and temperature using nitric acid. Broadened 2D band and G band frequencies in Raman spectra indicated that pristine graphene (PG) was of high quality with low defects. X-ray diffraction results confirmed that PG has five layers. Transmission electron microscopy and N₂ adsorption-desorption analyses affirmed that the graphene is of a good quality, large surface area (562 m²/g) and small pore size. Fourier transform infrared spectroscopy confirmed functionalization process performance. Thermogravimetric analysis affirmed that the thermal stability of PG was drastically decreased after the functionalization process.     

High-throughput production of high-quality graphene by exfoliation of expanded graphite in simple liquid benzene derivatives

Graphene, a perfect one-atomic thick two-dimensional lattice carbon allotrope, has drawn extensive attention of scientific communities since it was found several years ago, for its excellent mechanical characteristics, unique electrical properties and remarkable optical properties. However, one of the biggest obstacles to graphene research and applications is to obtain single-layer graphene in large quantity. Here, we reported a solvent-exfoliation method to massively produce high quality graphene. We showed that the expanded graphite can be effectively dispersed and exfoliated in several common benzene derivatives including chlorobenzene, benzyl chloride, o-dichlorobenzene and nitrobenzene, to produce high-quality graphene sheets, with a yield of about 3.9%. The obtained thin graphene nanosheets have been characterized by TEM, SEM and Raman spectroscopy.