An efficient method of producing stable graphene suspensions with less toxicity using dimethyl ketoxime

A highly stable graphene suspension has been prepared using dimethyl ketoxime (DMKO) as reductant. Nitrogen was doped into the graphene plane at the same time as the graphene oxide (GO) sheets were reduced. X-ray photoelectron spectroscopy indicated that the C/O ratio of graphene was significantly increased after GO was treated with DMKO and the quantity of nitrogen incorporated into the graphene lattice was 3.67 at.%. The electrical conductivity of the graphene paper was found to be ～10² S m^?1, which was 5 orders of magnitude better than that of GO, and this demonstrated the effective chemical reduction of GO. The mechanism of the chemical reaction of GO with DMKO was also discussed. The as-produced graphene material showed good capacitive behavior and long cycle life with a specific capacitance of ～140 F g^?1.     

Tubular graphene nanoribbons with attached manganese oxide nanoparticles for use as electrodes in high-performance supercapacitors

Graphene nanoribbons (GNRs) with tubular shaped thin graphene layers were prepared by partially longitudinal unzipping of vapor-grown carbon nanofibers (VGCFs) using a simple solution-based oxidative process. The GNR sample has a similar layered structure to graphene oxide (GO), which could be readily dispersed in isopropyl alcohol to facilitate electrophoretic deposition (EPD). GO could be converted to graphene after heat treatment at 300 °C. The multilayer GNR electrode pillared with open-ended graphene tubes showed a higher capacitance than graphene flake and pristine VGCF electrodes, primarily due to the significantly increased surface area accessible to electrolyte ions. A GNR electrode with attached MnO₂ nanoparticles was prepared by EPD method in the presence of hydrated manganese nitrate. The specific capacitance of GNR electrode with attached MnO₂ could reach 266 F g⁻¹, much higher than that of GNR electrode (88 F g⁻¹) at a discharge current of 1 A g⁻¹. The hydrophilic MnO₂ nanoparticles attached to GNRs could act as a redox center and nanospacer to allow the storage of extra capacitance.     

Conversion of pyrazoline to pyrazole in hydrazine treated N-substituted reduced graphene oxide films obtained by ion bombardment and their electrical properties

An efficient method for the conversion of pyrazoline to pyrazole in hydrazine treated N-substituted reduced graphene oxide (N-rGO) films at room temperature has been reported. This method comprises the Ar⁺ ion bombardment of the N-rGO films that are prepared by drop casting method. The X-ray photoelectron spectroscopy (XPS) data in association with the X-ray diffraction, Ultra-violet spectroscopy and Raman spectroscopy data reveal that the addition of hydrazine removes the epoxy and hydroxyl groups of graphite oxide largely, and the reaction of hydrazine with carbonyl groups at 1,3-position of GO yields the pyrazoline moiety at the edge of the exfoliated carbon network. Further, the XPS data of the bombarded N-rGO films at the threshold applied potential of ∼3 keV for 10 min show that the position of the N1s XPS peak shifts from 400.05 to 398.6 eV due to the bombardment, indicating a conversion occurs from non-aromatic pyrazoline to aromatic pyrazole moiety. The electrical results reveal that the conductivity of the N-rGO/pyrazole film (47,600 S/m) is higher than the N-rGO/pyrazoline film (25,000 S/m) by virtue of the enhancement in the length of the conjugation π bond. The conversion of pyrazoline to pyrazole is discussed based on the activation energy.     

Increased optical nonlinearities of graphene nanohybrids covalently functionalized by axially-coordinated porphyrins

Two graphene oxide (GO)-based nanohybrid materials possessing covalent linkages to axially-coordinated tetraphenylporphyrin (TPP), GO–TPP, were prepared and were characterized by Fourier transform infrared (FT-IR), Ultraviolet–visible (UV–Vis) absorption, steady state fluorescence, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), thermogravimetric analysis (TGA), elemental analysis and Raman spectroscopic techniques. The nonlinear optical properties and optical limiting performance of GO, GO–TPP nanohybrids and the free porphyrins dihydroxotin(IV) tetraphenylporphyrin (SnTPP) and the phosphorus-cored porphyrin (PTPP) were investigated using nanosecond and picosecond Z-scan measurements at 532 nm. At the identical mass concentration of 0.2 mg mL⁻¹, GO–TPP nanohybrids exhibited enhanced nonlinear optical properties and optical limiting performance, ascribed to a combination of nonlinear scattering and/or two-photon absorption with reverse saturable absorption, and the photo-induced electron or energy transfer from the electron-donor porphyrin moiety to the acceptor graphene.     

On the interpretation of XPS spectra of metal (Pt,Pt–Sn) nanoparticle/graphene systems

This Letter discusses the X-ray photoelectron spectroscopy (XPS) results of an article on Pt and Pt–Sn nanoparticles dispersed on graphene nanosheets. I argue that the authors’ interpretation is largely unwarranted because it neglects the spin–orbit multiplicity and the branching ratio of XPS signals arising from electron levels with l > 0, and the fact that XPS peaks of given electron levels and given chemical species possess precise full with at half maximum (FWHM) values, and binding energy (BE) values. I suggest an interpretation which offers a more accurate insight into the chemical composition and the catalytic properties of these nanoparticle systems.     

Synthesis of high-density arrays of graphene nanoribbons by anisotropic metal-assisted etching

We demonstrate the synthesis of highly aligned dense arrays of graphene nanoribbons (GNRs) based on metal-assisted etching of chemical vapor deposition-grown single-layer graphene. In order to obtain GNR arrays, controlling the direction of the etching becomes an important task. Crystalline surfaces of r- and a-planes of sapphire (α-Al₂O₃) were found to induce anisotropic etching of the graphene along their specific crystallographic directions. In contrast, anisotropic surface of ST-cut quartz induced few etching lines. We found that the graphene etching is strongly dependent on the metal species; the order of the catalytic activity of metal nanoparticles is Ni > Fe > > Cu. Etching temperature and H₂ concentration also strongly influenced the density and quality of the etching lines. Our anisotropic graphene etching is expected to offer a new route toward the synthesis of high density GNR array in large area without relying on any lithographic techniques for future electronic devices.     

Low-cost preparation of a conductive and catalytic graphene film from chemical reduction with AlI3

AlI₃ synthesized by I₂ and Al in ethanol was used as reductive agent to directly obtain flexible reductive graphene oxide (RGO) films with high conductivity of 5320 S/m from graphene oxide (GO) films at a low temperature of 80 °C. This reductive method has provided a low-cost and effective route for large-scale production of graphene with high catalytic activity. Structural evolution during the reduction of GO was studied by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. The RGO films served as counter electrode exhibited high electrochemical activity.     

Bio-inspired cross-linking with borate for enhancing gas-barrier properties of poly(vinyl alcohol)/graphene oxide composite films

The demand for flexible and transparent barrier films in industries has been increasing. Learning from nature, borate ions were used to cross-link poly(vinyl alcohol) (PVA) and graphene oxide (GO) to produce flexible, transparent high-barrier composite films with a bio-inspired structure. PVA/GO films with only 0.1 wt% GO and 1 wt% cross-linker exhibited an O₂ transmission rate <0.005 cc m⁻² day⁻¹, an O₂ permeability <5.0 × 10⁻²⁰ cm³ cm cm⁻² Pa⁻¹ s⁻¹, and a transmittance at 550 nm >85%; thus, they can be used for flexible electronics. Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy indicated that the outstanding barrier properties are attributed to the formation of chemical cross-linking involving borate ions, GO sheets, and PVA, similar to the borate cross-links in high-order plants. Comparing our experimental data with the Cussler model, we found that the effective aspect ratio was significantly increased after cross-linking, suggesting that cross-linking networks connected GO with each other to form ultra-large impermeable regions. A feasible green technique, with potential for commercial production of barrier films for flexible electronics was presented.     

Reduction of graphite oxide to graphene with laser irradiation

Reduction of graphite oxide (GO) to graphene induced by picosecond pulsed laser irradiation has been studied by Raman spectroscopy, scanning electron microscopy together with modeling of temperature dynamics in the materials. Dependence of the D, G, and 2D Raman band parameters on the laser pulse energy and the irradiation dose was evaluated. The exponential decline of the full width at half maximum of the Raman lines with increasing product of the pulse energy and irradiation dose was observed indicating ordering in the film and reduction in the number of graphene layers during the laser treatment. The minimum concentration of structural defects and the largest relative intensity of the 2D peak were found for the 50 mW mean laser power and the 30 mm/s scanning speed. Modeling of temperature dynamics revealed that the temperature of the GO film irradiated with a single laser pulse at a fluence of 0.04 J/cm² (50 mW) increased up to 1400 °C for a few nanoseconds, which was sufficient for the effective reduction of GO to graphene with successive laser pulses.     

Controllable growth of single-layer graphene on a Pd(1 1 1) substrate

Using a surface segregation technique, single-layer graphene can be grown on a carbon-doped Pd(1 1 1) substrate. The growth was monitored and visualized using Auger electron spectroscopy, X-ray photoelectron spectroscopy, Raman microscopy, atomic force microscopy and scanning tunneling microscopy. Appropriate adjustment of annealing parameters enables controllable growth of single-layer graphene islands and homogeneous, wafer-scale, single-layer graphene. The chemical state of the C 1s peak from X-ray photoelectron spectroscopy indicates there is almost no charge transfer between graphene and the Pd(1 1 1) substrate, suggesting weak graphene–substrate interaction. These findings show surface segregation to be an effective method for synthesizing large-scale graphene for fundamental research as well as potential applications.     

Reduced graphene oxide for Li–air batteries: The effect of oxidation time and reduction conditions for graphene oxide

Reduced graphene oxide (rGO) has shown great promise as an air-cathode for Li–air batteries with high capacity. In this article we demonstrate how the oxidation time of graphene oxide (GO) affects the ratio of different functional groups and how trends of these in GO are extended to chemically and thermally reduced GO. We investigate how differences in functional groups and synthesis may affect the performance of Li–O₂ batteries. The oxidation timescale of the GO was varied between 30 min and 3 days before reduction. Powder X-ray diffraction, micro-Raman, FE-SEM, BET analysis, and XPS were used to characterize the GO’s and rGO’s. Selected samples of GO and rGO were analyzed by solid state ¹³C MAS NMR. These methods highlighted the difference between the two types of rGO’s, and XPS indicated how the chemical trends in GO are extended to rGO. A comparison between XPS and ¹³C MAS NMR showed that both techniques can enhance the structural understanding of rGO. Different rGO cathodes were tested in Li–O₂ batteries which revealed a difference in overpotentials and discharge capacities for the different rGO’s. We report the highest Li–O₂ battery discharge capacity recorded of approximately 60,000 mAh/g_carbon achieved with a thermally reduced GO cathode.     

Multiscale patterning of graphene oxide and reduced graphene oxide for flexible supercapacitors

A simple and facile method for multiscale, in-plane patterning of graphene oxide and reduced graphene oxide (GO–rGO) was developed by region-specific reduction of graphene oxide (GO) under a mild irradiation. The UV-induced reduction of graphene oxide was monitored by various spectroscopic techniques, including optical absorption, X-ray photoelectron spectroscopy (XPS), Raman, and X-ray diffraction (XRD), while the resultant GO–rGO patterned film morphology was studied on optical microscope, scanning electron microscope (SEM), and atomic force microscope (AFM). Flexible symmetric and in-plane supercapacitors were fabricated from the GO–rGO patterned polyethylene terephthalate (PET) electrodes to show capacitances up to 141.2 F/g.     

On the chemical nature of thermally reduced graphene oxide and its electrochemical Li intake capacity

Graphene oxide (GO) presents a unique chemical complexity due to the number of defect sites and chemical groups introduced by the harsh oxidative treatment. In this work, we elucidate the chemical nature of GO and thermally-reduced GO at different temperatures. These materials were characterized by a variety of techniques such as FT-IR, Raman spectroscopy, TGA, SEM, XRD, XPS, TEM, surface area, and elemental analysis. Furthermore, galvanostatic experiments demonstrate that the electrochemical performance of reduced-GOs for Li intake is optimal when GO is reduced at a relatively mild temperature of 250 °C regardless of the chemical environment. Mildly reduced-GOs show a high first cycle specific capacity of over 2000 mAh/g (charge) and 1000 mAh/g (discharge), at a large current density of 500 mA/g. After 100 cycles, the reversible capacity remains stabilized at 500 mAh/g. Our characterization results combined with density functional theory calculations suggest that the presence of specific ketone groups at the edge sites rather than their gross morphology is responsible for the enhanced performance of the material as anode electrodes.     

Preparation and characterization of graphene and Ni-decorated graphene using flower petals as the precursor material

A simple method is reported for preparing graphene and nickel-decorated graphene from the petals of lotus and hibiscus flowers by heating the original petals and petals soaked in a nickel(II) chloride solution ranging 800–1600 °C under a flowing argon atmosphere for 0.5 h. The products have been characterized by scanning and transmission electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. Graphene prepared at high temperature (>1200 °C) is purer than that obtained at a lower temperature (800 °C). The presence of nickel has been found to have improved the quality of the graphene and electron density near the Fermi energy level.     

Preparation and characterisation of calcined Mg/Al hydrotalcites impregnated with alkaline nitrate and their activities in the combustion of particulate matter

The effect of incorporating alkaline nitrates in hydrotalcites for use in the combustion of particulate matter from diesel emissions has been studied. The catalysts were characterised by X-ray diffraction (XRD), N₂ adsorption, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), elemental analysis (EA), atomic absorption spectrophotometry (AAS) temperature programmed reduction (TPR) and Fourier transform infrared spectroscopy (FTIR). Activity measurements were carried out using a thermobalance in air and using a fixed-bed reactor with a NO/O₂ flow. The observed activities decreased in the following order: HTMgAlcCs > HTMgAlcK > HTMgAlcLi > HTMgAlc.     

Evolution of epitaxial graphene layers on 3C SiC/Si (1 1 1) as a function of annealing temperature in UHV

The growth of graphene on SiC/Si substrates is an appealing alternative to the growth on bulk SiC for cost reduction and to better integrate the material with Si based electronic devices. In this paper, we present a thorough in situ study of the growth of epitaxial graphene on 3C SiC (1 1 1)/Si (1 1 1) substrates via high temperature annealing (ranging from 1125 to 1375 °C) in ultra high vacuum (UHV). The quality and number of graphene layers have been investigated by using X-ray Photoelectron Spectroscopy (XPS), while the surface characterization have been studied by Scanning Tunnelling Microscopy (STM). Ex-situ Raman spectroscopy measurements confirm our findings, which demonstrate the exponential dependence of the number of graphene layers on the annealing temperature.     

Gelation of graphene oxides induced by different types of amino acids

We have investigated gelation of graphene oxide (GO) sheets induced by amino acids. For gelation of single layer GO sheets, six different types of amino acids were added to GO suspension as gelators. To understand gelation mechanism, we varied the concentration and type of amino acids as well as the pH of suspension, and monitored the morphology and rheological properties of reaction mixtures. Gelation was observed in acidic pH only with three types of amino acids (arginine, tryptophan, and cysteine) whereas no gel was formed at other pH values (neutral and basic). As the type of amino acid was varied, both the binding strength between amino acid and GO and the moduli (G′ and G′′) of reaction mixtures followed the same order, arginine > cysteine > tryptophan > asparagine > aspartic acid > glycine. To rationalize these results, we considered interactions between amino acid side chains and GO sheets (i.e., electrostatic interaction, π–π stacking, and hydrogen bonding), and found that the hydrogel formed by electrostatic attraction with arginine exhibited shorter gel time and larger moduli than the other samples. Finally, synthesis of GO hydrogel at physiological pH was demonstrated by increasing the concentration of GO sheets.     

Synthesis and supercapacitor performance studies of N-doped graphene materials using o-phenylenediamine as the double-N precursor

N-doped graphene (NG) materials have been prepared through a one-step solvothermal reaction by using o-phenylenediamine as a double-N precursor. N-doping and reduction of graphene oxide (GO) are both achieved simultaneously during the solvothermal reaction. The results of scanning electron microscopy and high resolution transmission electron microscopy measurements indicate that NG is highly crumpled. And the N-doping is confirmed by elemental analysis, X-ray photoelectron spectroscopy, Raman spectroscopy, Fourier transformed infrared spectroscopy and ultraviolet–visible spectroscopy. The doping level of nitrogen reaches up to 7.7 atom% and the types in NG are benzimidazole-N and phenazine-N. The NG materials exhibit excellent electrochemical performance for symmetric supercapacitors with a high specific capacitance of 301 F g⁻¹ at a current density of 0.1 A g⁻¹ in 6 M KOH electrolyte, which is remarkably higher than the solvothermal products of pristine GO (210 F g⁻¹ at 0.1 A g⁻¹). The NG materials also exhibit superior cycling stability (97.1% retention) and coulombic efficiency (99.2%) after 4000 cycles, due to the high content of nitrogen atoms, unique types of nitrogen and improved electronic conductivity.     

Adsorption characteristics of 1,2,4-trichlorobenzene, 2,4,6-trichlorophenol, 2-naphthol and naphthalene on graphene and graphene oxide

Adsorption of 1,2,4-trichlorobenzene (TCB), 2,4,6-trichlorophenol (TCP), 2-naphthol and naphthalene (NAPH) on graphene (G) and graphene oxide (GO) was investigated using a batch equilibration method and micro-Fourier transform infrared spectroscopy. All adsorption isotherms of four aromatics on G and GO were nonlinear, indicating that except for hydrophobic interaction, some specific interactions were involved in adsorption. For G, four aromatics had similar adsorption capacity at pH 5.0 in despite of their different chemical properties. A series of pH-dependent experimental results showed that 2-naphthol had higher adsorption capacity on G at alkaline pH than that at acidic pH. Theoretical calculation ascribed this to higher π-electron density of anionic 2-naphthol than that of neutral 2-naphthol, which facilitated the π–π interaction formation with G. For GO, the adsorption affinity of four aromatics increased in the order: NAPH < TCB < TCP < 2-naphthol. FTIR results revealed that TCB, TCP and 2-naphthol were adsorbed on G mainly via π–π interaction. In contrast, high adsorption of TCP and 2-naphthol on GO was attributed to the formation of H-bonding between hydroxyl groups of TCP and 2-naphthol and O-containing functional groups on GO.     

Structural,magnetic, and textural properties of iron oxide-reduced graphene oxide hybrids and their use for the electrochemical detection of chromium

Superparamagnetic Fe₃O₄ nanoparticles were anchored on reduced graphene oxide (RGO) nanosheets by co-precipitation of iron salts in the presence of different amounts of graphene oxide (GO). A pH dependent zeta potential and good aqueous dispersions were observed for the three hybrids of Fe₃O₄ and RGO. The structure, morphology and microstructure of the hybrids were examined by X-ray diffraction, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy, Raman and X-ray photoelectron spectroscopy. TEM images reveal lattice fringes (d₃₁₁ = 0.26 nm) of Fe₃O₄ nanoparticles with clear stacked layers of RGO nanosheets. The textural properties including the pore size distribution and loading of Fe₃O₄ nanoparticles to form Fe₃O₄–RGO hybrids have been controlled by changing the concentration of GO. An observed maximum (～10 nm) in pore size distribution for the sample with 0.25 mg ml^?1 of GO is different from that prepared using 1.0 mg ml^?1 GO. The superparamagnetic behavior is also lost in the latter and it exhibits a ferrimagnetic nature. The electrochemical behavior of the hybrids towards chromium ion was assessed and a novel electrode system using cyclic voltammetry for the preparation of an electrochemical sensor platform is proposed. The textural properties seem to influence the electrochemical and magnetic behavior of the hybrids.