Graphene oxide dispersions in organic solvents

The dispersion behavior of graphene oxide in different organic solvents has been investigated. As-prepared graphite oxide could be dispersed in N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, and ethylene glycol. In all of these solvents, full exfoliation of the graphite oxide material into individual, single-layer graphene oxide sheets was achieved by sonication. The graphene oxide dispersions exhibited long-term stability and were made of sheets between a few hundred nanometers and a few micrometers large, similar to the case of graphene oxide dispersions in water. These results should facilitate the manipulation and processing of graphene-based materials for different applications.     

Transition Metal (Mn,Fe, Co,Ni)‐Doped Graphene Hybrids for Electrocatalysis

The development of electrocatalysts is crucial for renewable energy applications. Metal‐doped graphene hybrid materials have been explored for this purpose, however, with much focus on noble metals, which are limited by their low availability and high costs. Transition metals may serve as promising alternatives. Here, transition metal‐doped graphene hybrids were synthesized by a simple and scalable method. Metal‐doped graphite oxide precursors were thermally exfoliated in either hydrogen or nitrogen atmosphere; by changing exfoliation atmospheres from inert to reductive, we produced materials with different degrees of oxidation. Effects of the presence of metal nanoparticles and exfoliation atmosphere on the morphology and electrocatalytic activity of the hybrid materials were investigated using electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray photoelectron spectroscopy, and cyclic voltammetry. Doping of graphene with transition metal nanoparticles of the 4th period significantly influenced the electrocatalysis of compounds important in energy production and storage applications, with hybrid materials exfoliated in nitrogen atmosphere displaying superior performance over those exfoliated in hydrogen atmosphere. Moreover, nickel‐doped graphene hybrids displayed outstanding electrocatalytic activities towards reduction of O₂ when compared to bare graphenes. These findings may be exploited in the research field of renewable energy.     

Aqueous Dispersions of Graphene from Electrochemically Exfoliated Graphite

A facile and environmentally friendly synthetic strategy for the production of stable and easily processable dispersions of graphene in water is presented. This strategy represents an alternative to classical chemical exfoliation methods (for example the Hummers method) that are more complex, harmful, and dangerous. The process is based on the electrochemical exfoliation of graphite and includes three simple steps: 1) the anodic exfoliation of graphite in (NH₄)₂SO₄, 2) sonication to separate the oxidized graphene sheets, and 3) reduction of oxidized graphene to graphene. The procedure makes it possible to convert around 30 wt % of the initial graphite into graphene with short processing times and high yields. The graphene sheets are well dispersed in water, have a carbon/oxygen atomic ratio of 11.7, a lateral size of about 0.5–1 μm, and contain only a few graphene layers, most of which are bilayer sheets. The processability of this type of aqueous dispersion has been demonstrated in the fabrication of macroscopic graphene structures, such as graphene aerogels and graphene films, which have been successfully employed as absorbents or as electrodes in supercapacitors, respectively.     

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.     

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.     

A facile way to large-scale production of few-layered graphene <Emphasis Type="Italic">via</Emphasis> planetary ball mill

In the field of polymer/graphene nanocomposites, massive production and commercial availability of graphene are essential. Exfoliation of graphite to obtain graphene is one of the most promising ways to large-scale production at extremely low cost. In this work we illustrate a facile strategy for mass production of few-layered (≤ 10) graphene (FLG) via the newly explored ball milling. The achieved FLG concentration was determined by UV/Vis spectroscopy. The formation of FLG was proved by measuring the flake thickness by atomic force microscopy (AFM). Further Raman spectral studies indicated that the crystal structure of exfoliated flakes was preserved satisfactorily during this shear-force dominating process. To increase the maximum concentration obtainable, it’s critical to make a good parameter assessment. N-methylpyrrolidone (NMP) was used as a dispersing medium and the effect of milling parameters was systematically and quantitatively investigated, thus providing a criterion to optimize the milling process. We established the optimal values for solvent volume and initial weight of graphite. As for milling time, the production of FLG was enhanced with continuous milling according to the power law, but not linearly with increasing milling time. Moreover, the possible mechanism involved in milling process was also explored. Our work provides a simple method for graphite exfoliation and has great potential for improving thermal and electrical conductivity of polymer composites in the fields of engineering.     

Cross‐sectional structural characterization of the surface of exfoliated HOPG using HRTEM‐EELS

We analyzed the surface atomic structure of highly oriented pyrolytic graphite (HOPG) substrate exfoliated with adhesive tape, using high‐resolution transmission electron microscopy and scanning transmission electron microscopy‐electron energy‐loss spectroscopy (STEM‐EELS). The surface step height of the exfoliated HOPG substrate was determined using high‐angle annular dark‐field‐scanning transmission electron microscopy (HAADF‐STEM) images and the depth profiles of the EELS spectra of a cross‐sectioned thin foil specimen prepared via focused ion beam milling. The exfoliated surface of the HOPG substrate presented disordered and curved graphene layers. The STEM‐EELS measurements indicated that upon exfoliation, the surface of the HOPG substrate reacted with atmospheric water and oxygen molecules.     

High‐Concentration Graphene Dispersions with Minimal Stabilizer: A Scaffold for Enzyme Immobilization for Glucose Oxidation

Modified acrylate polymers are able to effectively exfoliate and stabilize pristine graphene nanosheets in aqueous media. Starting with pre‐exfoliated graphite greatly promotes the exfoliation level. The graphene concentration is significantly increased up to 11 mg mL^?1 by vacuum evaporation of the solvent from the dispersions under ambient temperature. TEM shows that 75 % of the flakes have fewer than five layers with about 18 % of the flakes consisting of monolayers. Importantly, a successive centrifugation and redispersion strategy is developed to enable the formation of dispersions with exceptionally high graphene‐to‐stabilizer ratio. Characterization by high‐resolution transmission electron microscopy, X‐ray photoelectron spectroscopy, X‐ray diffraction, and Raman spectroscopy shows the flakes to be of high quality with very low levels of defects. These dispersions can act as a scaffold for the immobilization of enzymes applied, for example, in glucose oxidation. The electrochemical current density was significantly enhanced to be approximately six times higher than an electrode in the absence of graphene, thus showing potential applications in enzymatic biofuel cells.     

Unlocking the Electrocatalytic Activity of Antimony for CO2 Reduction by Two‐Dimensional Engineering of the Bulk Material

Two‐dimensional (2D) materials are known to be useful in catalysis. Engineering 3D bulk materials into the 2D form can enhance the exposure of the active edge sites, which are believed to be the origin of the high catalytic activity. Reported herein is the production of 2D “few‐layer” antimony (Sb) nanosheets by cathodic exfoliation. Application of this 2D engineering method turns Sb, an inactive material for CO₂ reduction in its bulk form, into an active 2D electrocatalyst for reduction of CO₂ to formate with high efficiency. The high activity is attributed to the exposure of a large number of catalytically active edge sites. Moreover, this cathodic exfoliation process can be coupled with the anodic exfoliation of graphite in a single‐compartment cell for in situ production of a few‐layer Sb nanosheets and graphene composite. The observed increased activity of this composite is attributed to the strong electronic interaction between graphene and Sb.     

2D/2D h‐BN/N‐doped MoS2 Heterostructure Catalyst with Enhanced Peroxidase‐like Performance for Visual Colorimetric Determination of H2O2

Recently, nanozymes have attracted extensive attention because of their advantages of combining nanomaterials with enzymes. Herein, hexagonal boron nitride (h‐BN) and nitride‐doped molybdenum disulfide (N?MoS₂) nano‐composites (h‐BN/N?MoS₂) were synthesized by facile and cost‐effective liquid exfoliation with a solvothermal method in nontoxic ethanol solution. The results show that h‐BN, as a co‐catalyst, can not only dope into the lattice of MoS₂ but also form a heterogeneous structure with MoS₂NSs. It expanded the layer spacing and specific surface area of MoS₂NSs, which was beneficial to the contact between the catalyst and the substrate, and resulted in a synergistic enhancement of the catalytic activity of hydrogen peroxide (H₂O₂) with MoS₂. A colorimetric determination platform of h‐BN/N?MoS₂‐TMB‐H₂O₂ was constructed. It exhibited a wide linear range of 1–1000 μM with a low limit of detection (LOD) of 0.4 μM under optimal conditions, high sensitivity and stability, as well as good reliability (99.4–110.0%) in practice, making the measurement system more widely applicable.1. Introduction     

Engineered Recombinant Proteins for Aqueous Ultrasonic Exfoliation and Dispersion of Biofunctionalized 2D Materials

Aqueous ultrasonic exfoliation by using proteins as dispersants allows for the simultaneous production and biofunctionalization of single- or few-layered 2D materials for biomedical applications. However, the production yield and quality are always a concern. Here, the production of stable, low-defect, and biofunctionalized 2D flakes of graphene by using bifunctional chimeric polyproteins as dispersants is shown. The chimeric polyproteins contain an amphiphilic protein, hydrophobin (HFBI), to serve as the anchoring point that strongly binds to graphene layers and tandem repeats of a globular protein, GB1, to respond and transmit the ultrasonic force for efficient mechanical exfoliation. For this reason, the production yield is much higher than those obtained by using HFBI alone. Moreover, the yield, lateral size and number of layers can be fine-tuned by the number of GB1 repeats. Other 2D materials, such as MoS₂ and WS₂, can also be exfoliated in the same manner, demonstrating the versatility of this approach.     

Highly Efficient,Green, and Scalable β‐Cyclodextrin‐Assisted Aqueous Exfoliation of Transition‐Metal Dichalcogenides: MoS2 and ReS2 Nanoflakes

The β‐cyclodextrin‐assisted aqueous‐exfoliation method was used to prepare transition‐metal dichalcogenide (TMD) nanosheets, in a cheap, highly efficient, scalable and environmentally friendly manner. As study cases, MoS₂ and ReS₂ nanoflakes were prepared according to this method. Particularly, the effective exfoliation of ReS₂ crystals in an aqueous environment was observed for the first time. Moreover, exfoliated nanomaterials can be readily utilized in hydrogen evolution reactions (HERs) as noble‐metal‐free catalysts. This work provides new opportunities for highly efficient exfoliation of TMDs and other 2D nanomaterials into few‐layer nanosheets in aqueous media. Their production process showed high biocompatibility, broad applicability and excellent sustainability.     

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.

     

Nanocrystalline‐Graphene‐Tailored Hexagonal Boron Nitride Thin Films

Unintentionally formed nanocrystalline graphene (nc‐G) can act as a useful seed for the large‐area synthesis of a hexagonal boron nitride (h‐BN) thin film with an atomically flat surface that is comparable to that of exfoliated single‐crystal h‐BN. A wafer‐scale dielectric h‐BN thin film was successfully synthesized on a bare sapphire substrate by assistance of nc‐G, which prevented structural deformations in a chemical vapor deposition process. The growth mechanism of this nc‐G‐tailored h‐BN thin film was systematically analyzed. This approach provides a novel method for preparing high‐quality two‐dimensional materials on a large surface.     

Cleaning of pyrolytic hexagonal boron nitride surfaces

Hexagonal boron nitride (h‐BN) has recently garnered significant interest as a substrate and dielectric for two‐dimensional materials and devices based on graphene or transition metal dichalcogenides such as molybdenum disulfide (MoS₂). As substrate surface impurities and defects can negatively impact the structure and properties of two‐dimensional materials, h‐BN surface preparation and cleaning are a critical consideration. In this regard, we have utilized X‐ray photoelectron spectroscopy to investigate the influence of several ex situ wet chemical and in situ thermal desorption cleaning procedures on pyrolytic h‐BN surfaces. Of the various wet chemistries investigated, a 10 : 1 buffered HF solution was found to produce surfaces with the lowest amount of oxygen and carbon contamination. Ultraviolet/ozone oxidation was found to be the most effective ex situ treatment for reducing carbon contamination. Annealing at 1050 °C in vacuum or 10^?5 Torr NH₃ was found to further reduce oxygen and carbon contamination to the XPS detection limits. Copyright © 2015 John Wiley & Sons, Ltd.     

Highly Concentrated Aqueous Dispersions of Graphene Exfoliated by Sodium Taurodeoxycholate: Dispersion Behavior and Potential Application as a Catalyst Support for the Oxygen‐Reduction Reaction

A high‐yielding exfoliation of graphene at high concentrations in aqueous solutions is critical for both fundamental study and future applications. Herein, we demonstrate the formation of stable aqueous dispersions of pristine graphene by using the surfactant sodium taurodeoxycholate under tip sonication at concentrations of up to 7.1 mg mL^?1. TEM showed that about 8 % of the graphene flakes consisted of monolayers and 82 % of the flakes consisted of less than five layers. The dispersions were stable regardless of freezing (?20 °C) or heat treatment (80 °C) for 24 h. The concentration could be significantly improved to about 12 mg mL^?1 by vacuum‐evaporation of the dispersions at ambient temperature. The as‐prepared graphene dispersions were readily cast into conductive films and were also processed to prepare Pt/graphene nanocomposites that were used as highly active electrocatalysts for the oxygen‐reduction reaction.     

Electrochemically Exfoliated Graphene and Graphene Oxide for Energy Storage and Electrochemistry Applications

Top‐down methods are of key importance for large‐scale graphene and graphene oxide preparation. Electrochemical exfoliation of graphite has lately gained much interest because of the simplicity of execution, the short process time, and the good quality of graphene that can be obtained. Here, we test three different electrolytes, that is, H₂SO₄, Na₂SO₄, and LiClO₄, with a common exfoliation procedure to evaluate the difference in structural and chemical properties that result for the graphene. The properties are analyzed by means of scanning transmission electron microscopy (STEM), Raman spectroscopy, and X‐ray photoelectron spectroscopy. We then tested the graphene materials for electrochemical applications, measuring the heterogeneous electron transfer (HET) rates with a Fe(CN)₆^3?/4? redox probe, and their capacitive behavior in alkaline solutions. We correlate the electrochemical features with the presence of structural defects and oxygen functionalities on the graphene materials. In particular, the use of LiClO₄ during the electrochemical exfoliation of graphite allowed the formation of highly oxidized graphene with a C/O ratio close to 4.0 and represents a possible avenue for the mass production of graphene oxide as valid alternative to the current laborious and dangerous chemical procedures, which also have limited scalability.     

Single‐Step Functionalization and Exfoliation of Graphene with Polymers under Mild Conditions

The simultaneous polymer functionalization and exfoliation of graphene sheets by using mild bath sonication and heat treatment at low temperature is described. In particular, free‐radical polymerization of three different vinyl monomers takes place in the presence of graphite flakes. The polymerization procedure leads to the exfoliation of graphene sheets and at the same time the growing polymer chains are attached onto the graphene lattice, which gives solubility and stability to the final graphene‐based hybrid material. The polymer‐functionalized graphene sheets possess fewer defects as compared with previously reported polymer‐functionalized graphene. The success of the covalent functionalization and exfoliation of graphene was confirmed by using a variety of complementary spectroscopic, thermal, and microscopy techniques, including Raman, IR and UV/Vis spectroscopy, thermogravimetric analysis, and transmission electron microscopy.     

Exfoliation of graphite by dry ball milling with cellulose

Dry ball milling of graphite with cellulose and related polysaccharides was found effective for exfoliation-dispersion of graphene-like carbon. The exfoliation behavior was found to depend strongly on the polymer species; namely, polysaccharides are much more effective than thermoplastic polymers. The compression-molded slabs from co-milled powder with cellulose and carboxymethylcellulose showed an electrical percolation threshold of 1.0 % (w/w) or lower. The carbon fraction isolated from milling with carboxymethylcellulose was water-dispersible, containing single- to few-layer graphenes. This method can provide facile and solventless graphene exfoliation and mechanical alloying with polymers.     

Comparison of sample preparation methods for determination of free carbon in boron carbide by X-ray powder diffraction

Several sample preparation methods were evaluated for determination of free carbon in boron carbide powders by quantitative X-ray diffraction method, including ultrasonication, wet ball milling and dry ball milling–wet mixing. Quantitation was based on measuring the integral peak area ratio of the diffraction lines of graphite (002) to boron carbide (012) in samples spiked with pure graphite. The dry milling–wet mixing method provided the best precision and accuracy in all the measurements as well as in determination of free carbon in a boron carbide reference material. There was a linear relationship between the integral peak area ratios and graphite added to boron carbide samples which were purified from their free carbon content. The method provided a low detection limit of 0.05 wt% free carbon.