Influence of parent graphite particle size on the electrochemistry of thermally reduced graphene oxide

Electrochemical applications of graphene are of very high importance. For electrochemistry, bulk quantities of materials are needed. The most common preparation of bulk quantities of graphene materials is based on oxidation of graphite to graphite oxide and subsequent thermal exfoliation of graphite oxide to thermally reduced graphene oxide (TR-GO). It is important to investigate to which extent a reaction condition, that is, composition of the oxidation mixture and size of graphite materials, influences the properties of the resulting materials. We characterised six graphite materials with a range of particle sizes (0.05, 11, 20, 32, 35 and 41 μm) and the TR-GO products prepared from them by use of scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. Cyclic voltammetric performance of the TR-GO samples was compared using ferro/ferricyanide and ascorbic acid. We observed no correlation between size of initial graphite and properties of the resultant TR-GO such as density of surface defects, amount of oxygen-containing groups, or rate of heterogeneous electron transfer (HET). A positive correspondence between HET rate and high defect density as well as low amounts of oxygen functionalities was noted. Our findings will have profound influence upon practical fabrication of graphene for applications in sensing and energy storage devices.     

Electrochemically exfoliating graphite into N-doped graphene and its use as a high efficient electrocatalyst for oxygen reduction reaction

N-doped graphene has been extensively explored because of their intriguing properties. However, most of the conventional heat-processed N-doped graphene (HNG) suffer from the poor hydrophilic property and low electric conductivity when using electrode materials. Herein, we present a facile solution-processed strategy to fabricate N-doped graphene through electrochemical exfoliation of graphite in inorganic electrolyte solution. The resulting electrochemically exfoliated N-doped graphene (ENG) has high level of nitrogen (7.9 at.%) and oxygen (16.5 at.%), moreover, excellent electric conductivity (19 s cm^?1). As a binder-free electrode material for oxygen reduction reaction (ORR), ENG exhibits much better electroactivity than HNG and electrochemically exfoliated graphene (EG), moreover, much better methanol tolerance and long-term durability than that commercial Pt/C catalyst. The results provide new sights into scalable production of noble metal-free catalyst towards ORR.     

PtPd-nanoparticles supported by new carbon materials

Nanocomposites based on PtPd nanoparticles with chemical ordering like disordered solid solution on surface of multilayer graphene have been prepared through thermal shock of mechanically obtained mixture of double complex salt [Pd(NH₃)₄][PtCl₆] and different carbon materials–exfoliated graphite, graphite oxide and graphite fluoride. An effect of original carbon precursors on formation of PtPd bimetallic nanoparticles was studied using X-ray absorption spectroscopy (XAFS), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). It was shown that the distribution of bimetallic nanoparticles over the multilayer graphene surface as well as the particles size distribution is controlled by the graphene precursors. For all nanocomposites, the surface of the nanoparticles was found to be Pd-enriched. In case when the thermal exfoliated graphite and graphite oxide were used as the graphene precursors a thin graphitized layer covered the nanoparticles surface. Such a graphitized layer was not observed in the nanocomposite, which used the fluorinated graphite as the precursor.     

Intercalation of few-layer graphite flakes with FeCl3: Raman determination of Fermi level, layer by layer decoupling, and stability

We use anhydrous ferric chloride (FeCl(3)) to intercalate graphite flakes consisting of 2-4 graphene layers and to dope graphene monolayers. The intercalant, staging, stability, and doping of the resulting intercalation compounds (ICs) are characterized by Raman scattering. The G peak of heavily doped monolayer graphene upshifts to ～1627 cm(-1). The 2-4 layer ICs have similar upshifts, and a Lorentzian line shape for the 2D band, indicating that each layer behaves as a decoupled heavily doped monolayer. By performing Raman measurements at different excitation energies, we show that, for a given doping level, the 2D peak can be suppressed by Pauli blocking for laser energy below the doping level. Thus, multiwavelength Raman spectroscopy allows a direct measurement of the Fermi level, complementary to that derived by performing measurements at fixed excitation energy significantly higher than the doping level. This allows us to estimate a Fermi level shift of up to ～0.9 eV. These ICs are thus ideal test-beds for the physical and chemical properties of heavily doped graphenes.     

In situ SERS spectroscopy of Ag-modified pyrolytic graphite in organic electrolytes

Surface enhanced Raman scattering (SERS) has been applied to study the lithium intercalation/deintercalation process at the interface of a pyrolytic graphite electrode with propylene and ethylene carbonate containing organic solutions. We have focused on the lattice vibration of the most outer graphite surface layer simultaneously with cyclic voltammetric measurements. In situ Raman spectroscopy performed in this way allowed us to determine the La value that describes the size of graphitic microcrystallites along the a-axis. It was found that the La value decreases when the electrode is polarized to potentials between 0.02 and 1.0 V. This phenomenon can be correlated with the intercalation of lithium ions into the graphene structure. According to the spectral change, the size of the graphitic microcrystallites shows reversible behavior with potential cycling at the surface of the electrode. Electronic Publication     

Effect of graphite features on the properties of metal-organic framework/graphite hybrid materials prepared using an in situ process

Metal-organic framework (MOF)/graphite hybrid materials were prepared using an in situ process. Graphites with various chemical and physical features were used, and HKUST-1 was selected as the MOF component. The samples (parent materials and hybrid materials) were characterized by X-ray diffraction, nitrogen sorption, scanning electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Then they were tested as ammonia adsorbents in dynamic conditions. The results indicate that the functionalization of graphite is important to build the hybrid materials with synergistic properties. The lack of functional groups on graphite results in the formation of a simple physical mixture. Besides the surface chemistry of the graphitic component, the physical parameters (porosity and size of flakes) also seem to influence the formation of the hybrid materials. It is observed that the graphite particles disturb the formation of HKUST-1 and induce a different crystal morphology (more defects and increased surface roughness) than the one observed when MOF is formed in the absence of a substrate. The latter behavior causes less ammonia to be adsorbed on the hybrid materials than is expected for the simple physical mixture of HKUST-1 and graphite. The MOF structure collapses (in HKUST-1 and the hybrid materials) upon ammonia adsorption and leads to the formation of new species.     

Thermal conductivity of exfoliated graphite nanocomposites

Since the late 1990’s, research has been reported where intercalated, expanded, and/or exfoliated graphite nanoflakes could also be used as reinforcements in polymer systems. The key point to utilizing graphite as a platelet nanoreinforcement is in the ability to exfoliate graphite using Graphite Intercalated Compounds (GICs). Natural graphite is still abundant and its cost is quite low compared to the other nano–size carbon materials, the cost of producing graphite nanoplatelets is expected to be ~$5/lb. This is significantly less expensive than single wall nanotubes (SWNT) (>$45000/lb) or vapor grown carbon fiber (VGCF) ($40–50/lb), yet the mechanical, electrical, and thermal properties of crystalline graphite flakes are comparable to those of SWNT and VGCF. The use of exfoliated graphite flakes (xGnP) opens up many new applications where electromagnetic shielding, high thermal conductivity, gas barrier resistance or low flammability are required. A special thermal treatment was developed to exfoliate graphite flakes for the production of nylon and high density polypropylene nanocomposites. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the degree of exfoliation of the graphite platelets and the morphology of the nanocomposites. The thermal conductivity of these composites was investigated by three different methods, namely, by DSC, modified hot wire, and halogen flash lamp methods. The addition of small amounts of exfoliated graphite flakes showed a marked improvement in thermal and electrical conductivity of the composites.     

Graphene preparation and graphite exfoliation

The synthesis of Graphene is critical to achieving its functions in practical applications. Different methods have been used to synthesis graphene, but graphite exfoliation is considered the simplest way to produce graphene and graphene oxide. In general, controlling the synthesis conditions to achieving the optimum yield, keeping the pristine structure to realize on-demand properties, minimum layers with the smallest lateral size, and minimum oxygen content are the most obstacles experienced by researchers. Each application requires a specific graphene model, graphene oxides GO, or even graphene intercalated compounds (GIC) depending on synthesis conditions and approach. This paper reviewed and summarized the most researches in this field and focusing on exfoliation methods.     

Low-temperature exfoliation of multilayer-graphene material from FeCl3 and CH3NO2 co-intercalated graphite compound

Microwave induced rapid decomposition of nitromethane at low temperature exfoliates the graphene sheets from the FeCl(3) and CH(3)NO(2) co-intercalated graphite compound without creating many defects and functional groups. This approach provides a scalable method for high-quality graphene materials via low-temperature exfoliation of graphite under mild chemical conditions.     

Low contents of graphite improving general properties of poly(vinylidene fluoride)

Studies on graphite flakes with a lateral size greater than 50 μm, having a large number of stacked collapse blocks, are neglected and replaced by graphene nanosheets or by powdered graphite, which can be obtained from graphite through chemical or physical exfoliation, as filler in polymer composites. Besides, the production of graphene nanosheets or the purification of powdered graphite uses a high concentration of strong and toxic acids that pollutes the environment. These processes are extremely time-consuming and generate an expensive product. Composites of poly(vinylidene fluoride) (PVDF) were prepared via extrusion with graphite flakes with up to 60 μm thick and 700 μm lateral size, in the range from 0.1 to 5% m/m. The quality of graphite flakes was analyzed by thermogravimetric analysis, x-ray diffraction (XRD), Raman spectroscopy, Fourier-transform infrared spectroscopy, and scanning electron microscopy. The increase in the graphite content in the PVDF matrix improved thermal resistance while showed an increase in the degree of crystallinity up to 25% by XRD and 43% by differential scanning calorimetry, approximately. Although the graphite acted as a nucleating agent, the content of the PVDF beta phase did not change. In the composites with up to 2.0% of graphite, a significant increase in mechanical properties, 13% modulus, and 36% in the storage modulus, evaluated by thermodynamic-mechanical analysis and tensile tests. In the analyses of time-domain nuclear magnetic resonance and oscillatory rheology in parallel plates, it was noticed that the increase of mechanical properties is due to the reinforcing effect along with the lubricant protection of stacked graphene sheets, attenuating the stress and friction between the polymer chains. Therefore, even though graphite flakes are inexpensive, that filler without any treatment at low contents are capable of significantly improving the performance of PVDF. This work suggests that these composites could be employed in applications such as electrical insulator with less energy dissipation, and also in oil pipelines, specifically to replace PVDF-based terpolymers or mixtures thereof, and polyamide-11 in flexible risers as a barrier layer, improving their performance.     

The formation of vibrationally excited HD from atomic recombination on cold graphite surfaces

HD molecules formed in v"=3 and v"=4 have been detected by laser spectroscopy when a cold (15 K) graphite surface is irradiated with H and D atoms. Population of the v"=3, J"=0-6 and v"=4, J"=0-6 levels has been detected and the average rotational temperatures of the nascent HD were determined. These results are compared with previous data collected for the formation of HD in v"=1 and 2 under similar conditions. This comparison indicates that the nascent HD flux increases with increasing vibrational quantum number for v"=1-4.     

A Review on Graphene Oxide Two-dimensional Macromolecules: from Single Molecules to Macro-assembly

Graphene oxide(GO), which consists of two-dimensional(2 D) sp2 carbon hexagonal networks and oxygen-contained functional groups, has laid the foundation of mass production and applications of graphene materials. Made by chemical oxidation of graphite, GO is highly dispersible or even solubilized in water and polar organic solvents, which resolves the hard problem of graphene processing and opens a door to wet-processing of graphene. Despite its defects, GO is easy to functionalize, dope, punch h...     

Efficient and Scalable Production of 2D Material Dispersions using Hexahydroxytriphenylene as a Versatile Exfoliant and Dispersant

Thin‐layer 2D materials have been attracting enormous interest, and various processes have been investigated to obtain these materials efficiently. In view of their practical applications, the most desirable source for the preparation of these thin‐layer materials is the pristine bulk materials with stacked layers, such as pristine graphite. There are many options in terms of conditions for the exfoliation of thin‐layer materials, and these include wet and dry processes, with or without additives, and the kind of solvent. In this context, we found that the versatile exfoliant hexahydroxytriphenylene works efficiently for the exfoliation of typical 2D materials such as graphene, MoS₂, and hexagonal boron nitride (h‐BN) by both wet and dry processes by using sonication and ball milling, respectively, in aqueous and organic solvents. As for graphene, stable dispersions with relatively high concentrations (up to 0.28 mg mL^?1) in water and tetrahydrofuran were obtained from graphite in the presence of hexahydroxytriphenylene by a wet process with the use of bath sonication and by a dry process involving ball milling. Especially, most of the graphite was exfoliated and dispersed as thin‐layer graphene in both aqueous and organic solvents through ball milling, even on a large scale (47–86 % yield). In addition, the exfoliant was easily removed from the precipitated composite by heat treatment without disturbing the graphene structure. Bulk MoS₂ and h‐BN were also exfoliated by both wet and dry processes. Similar to graphene, dispersions of MoS₂ and h‐BN of high concentrations in water and DMF were produced in high yields through ball milling.     

One Pot Synthesis of Graphene through Microwave Assisted Liquid Exfoliation of Graphite in Different Solvents

This study presents an easy and quick method for the synthesis of graphene from graphite in a set of solvents, including n-Hexadecane (n-Hexa), dimethylsulfoxide (DMSO), sodium hydroxide (NaOH), 1-octanol (OCTA), perchloric acid (PA), N,N-Dimethylformamide (DMF), ethylene glycol (EG), and ethylene diamine (ED), via microwave (MW) energy. The properties of final products were determined by X-ray diffraction spectroscopy (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) spectroscopy, and the four-point probe technique. The XRD spectra of most of the MW-assisted graphene products showed peaks at 2θ = 26.5° and 54°. Layer numbers extend from 2 and 25, and the leading comes about were gotten by having two-layered products, named as graphene synthesized in dimethylsulfoxide (G-DMSO), graphene synthesized in ethylene glycol (G-EG), and graphene synthesized in 1-octanol (G-OCTA). G-DMF has the highest electrical conductivity with 22 S/m. The electrical conductivity is higher when the dipole moment of the used solvent is between 2 and 4 Debye (D). The FTIR spectra of most of the MW-assisted graphene products are in line with commercial graphene (CG). The UV-Vis spectra of all MW-assisted graphene products showed a peak at 223 nm referring to characteristic sp2 C=C bonds and 273 nm relating to the n → π * transition of C-O bonds.     

The role of interfacial compatibilization upon the microstructure and electrical conductivity threshold in polypropylene/expanded graphite nanocomposites

Attempts have been made to evaluate the effect of interface and degree of interfacial interaction upon electrical conductivity threshold in polypropylene/expanded graphite (PP/EG) nanocomposites, and dispersion state of graphite nanosheets. For this purpose, maleic anhydride grafted polypropylene (PPgMA) and maleic anhydride grafted EPDM (EPDMgMA) were used as compatibilizer. Nanocomposite samples containing 1–5 vol% of EG were prepared by melt mixing method using laboratory scale internal mixer. Characterization was carried out by using X‐ray diffraction (XRD), differential scanning calorimeter (DSC), thermo‐gravimetric analysis (TGA), scanning electron microscope (SEM), transmission electron microscope (TEM), and rheo‐mechanical spectroscopy (RMS). The conductivity measurements were carried out by using four point probe method according to ASTM D991. Results showed that the conductivity threshold is controlled by the extent of interfacial interaction between PP and EG. So, better conductivity was obtained using PPgMA as compatibilizer which causes higher level of interaction between PP and EG, and therefore better dispersion of the EG nanolayers in the polymer matrix. On the other hand, high levels of compatibilizers, especially EPDMgMA, caused formation of separated aggregates of EG shelled with the compatibilizer, which results in the reduction of conductivity of the nanocomposites. This finding has been verified by SEM, RMS, and conductivity measurements. Effects of EG nanolayers on crystalline structure and thermal decomposition temperature of the nanocomposites have also been investigated by DSC and TGA, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of the graphite oxide composition on the structure of products obtained by sulfuric acid treatment at elevated temperatures

The electronic structure and functional composition of products of the graphite oxide (GO) interaction with concentrated sulfuric acid (H₂SO₄) are studied, depending on the oxygen content in the precursor and the treatment temperature. X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) measured at the CK edge, and infrared spectroscopy are used to show the recovery of the π electron system of graphene planes at a temperature of 200 °C. Aggregation of functional groups in GO containing more than 40% of oxygen causes the formation of vacancy defects in the planes with treatment. When the GO treatment temperature rises to 280 °C, the oxidation of the basal plane π-regions occurs. The results can underlie the control of the functional composition, vacancy number, and size in graphite materials.     

Selective Removal of Hydroxyl Groups from Graphene Oxide

Graphene has a wide range of potential applications, thus tremendous efforts have been put into ensuring that the most direct and effective methods for its large‐scale production are developed. The formation of graphene materials from graphene oxide through a chemical reduction method is still one of the most preferred routes. Numerous methods starting from various reducing agents have been developed to obtain near‐pristine graphene sheets. However, most of the reducing agents are not mechanistically supported by classical organic chemistry knowledge and of those that are supported, they are only theoretically capable of, at most, reducing oxygen‐containing groups on graphene oxide to hydroxyl groups. Herein, we present a mechanistically proven method for the selective defunctionalisation of hydroxyl groups from graphene oxide that is based on ethanethiol–aluminium chloride complexes and provides a graphene material with improved properties. The structural, morphological and electrochemical properties of the graphene materials have been fully characterised based on high‐resolution X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry techniques. Our analyses showed that the obtained graphene materials exhibited high heterogeneous electron‐transfer rates, low charge‐transfer resistance and high conductivity as compared to the parent graphene oxide. Moreover, the selective defunctionalisation of hydroxyl groups could potentially allow for the tailoring of graphene properties for various applications.     

Electrical conductivity of poly(ethylene terephthalate)/expanded graphite nanocomposites prepared by in situ polymerization

Nanocomposites based on poly(ethylene terephthalate) (PET) and expanded graphite (EG) have been prepared by in situ polymerization. Morphology of the nanocomposites has been examined by electronic microscopy. The relationship between the preparation method, morphology, and electrical conductivity was studied. Electronic microscopy images reveal that the nanocomposites exhibit well dispersed graphene platelets. The incorporation of EG to the PET results in a sharp insulator‐to‐conductor transition with a percolation threshold (?_c) as low as 0.05 wt %. An electrical conductivity of 10^?3 S/cm was achieved for 0.4 wt % of EG. The low percolation threshold and relatively high electrical conductivity are attributed to the high aspect ratio, large surface area, and uniform dispersion of the EG sheets in PET matrix. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Thermal exfoliation of electrochemically synthesized graphite intercalation compound with perrhenic acid

In present work, we describe the synthesis of graphite intercalation compounds with perrhenic acid (HReO₄-GIC) through the anodic oxidation of graphite in aqueous perrhenic acid solution and their thermal exfoliation. Due to electrochemical treatment of graphite in perrhenic acid solution, ReO₄⁻ ions are intercalated into interlayer spaces of graphite. Anodic oxidation of graphite in HReO₄ solution leads to the formation of 3-stage GIC. Simultaneously, some amount of perrhenic acid becomes deposited on the graphite surface and edges. In the next step, thermal treatment of the previously synthesized GIC was performed, causing both the exfoliation of graphitic structure and transformation of perrhenic acid into rhenium oxides on the surface of graphene layers. The yielded product was exfoliated graphite-ReO₂/ReO₃ composite. The obtained composite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy. Additionally, specific surface area of the exfoliated materials was measured.

     

石墨烯导热研究进展

石墨烯具有目前已知材料中最高的热导率,在电子器件、信息技术、国防军工等领域具有良好的应用前景。石墨烯导热的理论和实验研究具有重要意义,在最近十年间取得了长足的发展。本文综述了石墨烯本征热导率的研究进展及应用现状。首先介绍应用于石墨烯热导率测量的微纳尺度传热技术,包括拉曼光谱法、悬空热桥法和时域热反射法。然后展示了石墨烯热导率的理论研究成果,并总结了石墨烯本征热导率的影响因素。随后介绍石墨烯在导热材料中的应用,包括高导热石墨烯膜、石墨烯纤维及石墨烯在热界面材料中的应用。最后对石墨烯导热研究的成果进行总结,提出目前石墨烯热传导研究中存在的机遇与挑战,并展望未来可能的发展方向。