Influence of Defects and Charges on the Colloidal Stabilization of Graphene in Water.

Mastering graphene preparation is an essential step to its integration into practical applications. For large-scale purposes, full graphite exfoliation appears as a suitable route for graphene production. However, it requires overpowering attractive van der Waals forces demanding large energy input, with the risk of introducing defects in the material. This difficulty can be overcome by using graphite intercalation compounds (GICs) as starting material. The greater inter-sheet separation in GICs (compared with graphite) allows the gentler exfoliation of soluble graphenide (reduced graphene) flakes. A solvent exchange strategy, accompanied by the oxidation of graphenide to graphene, can be implemented to produce stable aqueous graphene dispersions (Eau de graphene, EdG), which can be readily incorporated into many processes or materials. In this work, we prove that electrostatic forces are responsible for the stability of fully exfoliated graphene in water, and explore the influence of the oxidation and solvent exchange procedures on the quality and stability of EdG. We show that the amount of defects in graphene is limited if graphenide oxidation is carried out before exposing the material to water, and that gas removal of water before the incorporation of pre-oxidized graphene is advantageous for the long-term stability of EdG.

Burning Graphite Faster than Carbon Black: A Case of Diffusion Control.

External diffusion may be exploited as a tool to purify materials in a way thought to be inaccessible from a chemical reactivity point of view. A mixture of two carbonaceous materials, graphite and carbon black, are thermally oxidized in either i) outside total diffusion-limited regime or ii) total diffusion-limited regime. Depending on the treatment applied it is possible to purify either graphite, a trivial task, or carbon black, a task thought impossible. Introducing geometrical selectivity, controlled total diffusion-limited chemistry exceeds by far the field of carbon materials and can be used as an engineering tool for many materials purification, original synthesis, or to introduce asymmetry in a system. Several examples for direct applications of the findings are mentioned.

An Introduction to the Combustion of Carbon Materials.

Combustion is arguably as old as homo sapiens ability to observe and use fire. Despite the long tradition of using carbon combustion for energy production, this reaction is still not fully understood. This can be related to several facts that are intertwined and complicate the investigation, such as the large variety of possible carbon structures, the actual surface structure, porosity, the solid-gas nature of this reaction, diffusion limitation and fundamental reaction steps. In this review, a brief history of carbon combustion science is given, followed by a detailed discussion of the most important aspects of carbon combustion. Special attention is given to limitations for example diffusion. In carbon combustion, kinetic control can rarely be observed. The literature of the fundamental reaction steps actually occurring on the carbon framework is reviewed and it becomes apparent that the reaction is occurring primarily on defects on the basal plane. Thus, the reaction between oxygen and carbon may be used as an analytical tool to provide further insights into novel materials, for example synthetic carbon materials, fibres and graphene type materials. Mastering the combustion reaction in all its complexity may prove to be very valuable in the future.

Magnetic Ordering in Ultrasmall Potassium Ferrite Nanoparticles Grown on Graphene Nanoflakes.

Magnetic nanoparticles are central to the development of efficient hyperthermia treatments, magnetic drug carriers, and multimodal contrast agents. While the magnetic properties of small crystalline iron oxide nanoparticles are well understood, the superparamagnetic size limit constitutes a significant barrier for further size reduction. Iron (oxy)hydroxide phases, albeit very common in the natural world, are far less studied, generally due to their poor crystallinity. Templating ultrasmall nanoparticles on substrates such as graphene is a promising method to prevent aggregation, typically an issue for both material characterization and applications. We generate ultrasmall nanoparticles, directly on the carbon framework by the reaction of a graphenide potassium solution, charged graphene flakes, with iron(II) salts. After mild water oxidation, the obtained composite material consists of ultrasmall potassium ferrite nanoparticles bound to the graphene nanoflakes. Magnetic properties as evidenced by magnetometry and X-ray magnetic circular dichroism, with open magnetic hysteresis loops near room temperature, are widely different from classical ultrasmall superparamagnetic iron oxide nanoparticles. The large value obtained for the effective magnetic anisotropy energy density Keff accounts for the presence of magnetic ordering at rather high temperatures. The synthesis of ultrasmall potassium ferrite nanoparticles under such mild conditions is remarkable given the harsh conditions used for the classical syntheses of bulk potassium ferrites. Moreover, the potassium incorporation in the crystal lattice occurs in the presence of potassium cations under mild conditions. A transfer of this method to related reactions would be of great interest, which underlines the synthetic value of this study. These findings also give another view on the previously reported electrocatalytic properties of these nanocomposite materials, especially for the sought-after oxygen reduction/evolution reaction. Finally, their longitudinal and transverse proton NMR relaxivities when dispersed in water were assessed at 37 °C under a magnetic field of 1.41 T, allowing potential applications in biological imaging.

Intense Raman D Band without Disorder in Flattened Carbon Nanotubes.

Above a critical diameter, single- or few-walled carbon nanotubes spontaneously collapse as flattened carbon nanotubes. Raman spectra of isolated flattened and cylindrical carbon nanotubes have been recorded. The collapse provokes an intense and narrow D band, despite the absence of any lattice disorder. The curvature change near the edge cavities activates a D band, despite framework continuity. Theoretical calculations based on Placzek approximation fully corroborate this experimental finding. Usually used as a tool to quantify defect density in graphenic structures, the D band cannot be used as such in the presence of a graphene fold. This conclusion should serve as a basis to revisit materials comprising structural distortion where poor carbon organization was concluded on a Raman basis. Our finding also emphasizes the different visions of a defect between chemists and physicists, a possible source of confusion for researchers working in nanotechnologies.

Carbon supported noble metal nanoparticles as efficient catalysts for electrochemical water splitting.

Due to an increasing requirement of clean and sustainable hydrogen energy economy, it is significant to develop new highly effective catalysts for electrochemical water splitting. In alkaline electrolyte, Platinum (Pt) shows a much slower hydrogen evolution reaction (HER) kinetics relative to acidic condition. Here, we show a versatile synthetic approach for combining different noble metals, such as Rhodium (Rh), RhPt and Pt nanoparticles, with carbon forming noble metal nanoparticles/nanocarbon composites, denoted as Rh(nP)/nC, RhPt(nP)/nC and Pt(nP)/nC, respectively. It was found that in alkaline media these composites exhibited higher performance for the HER than the commercial Pt/C. In particular, Rh(nP)/nC displayed a small overpotential of 44 mV at a current density of 5 mA cm-2 and a low Tafel slope of 50 mV dec-1. Meanwhile, it also showed a comparable activity for the oxygen evolution reaction (OER) to the benchmarking catalyst RuO2. The superior HER and OER performance benefits from the very small size of nanoparticles and synergy between carbon support and nanoparticles.

Thermal Oxidation of Carbonaceous Nanomaterials Revisited: Evidence of Mechanism Changes.

Kinetic data, for example, activation energy and reaction order, are crucial for the understanding of chemical reactions and processes. Here, we describe a novel method for obtaining kinetic data based on thermogravimetric measurements (TGA) that exploits in each measurement multiple successive isothermal steps (SIS). We applied this method to the notoriously challenging carbon combustion process for vastly different carbons for oxygen molar fractions between 1.4 % and 90 %. Our obtained apparent EA values are within the wide range of results in the literature and vary in a systematic way with the oxygen partial pressure. The improved accuracy and large amount of obtainable data allowed us to show that the majority of experimentally obtained apparent data for apparent EA are neither in a kinetic regime nor in a diffusion-controlled one but rather in a transition regime.

Hydroxide Ions Stabilize Open Carbon Nanotubes in Degassed Water.

The main hurdle preventing the widespread use of single-walled carbon nanotubes remains the lack of methods with which to produce formulations of pristine, unshortened, unfunctionalized, individualized single-walled carbon nanotubes, thus preserving their extraordinary properties. In particular, sonication leads to shortening, which is detrimental to percolation properties (electrical, thermal, mechanical, etc.). Using reductive dissolution and transfer into degassed water, open-ended, water-filled nanotubes can be dispersed as individualized nanotubes in water-dimethyl sulfoxide mixtures, avoiding the use of sonication and surfactant. Closed nanotubes, however, aggregate immediately upon contact with water. Photoluminescence and absorption spectroscopy both point out a very high degree of individualization while retaining lengths of several microns. The resulting transparent conducting films are 1 order of magnitude more conductive than surfactant-based blanks at equal transmittance.

Graphenide Solutions: A Chemical Platform for Nanoparticle-Nanocarbon Composites.

Graphenide solutions, comprising charged graphene layers in aprotic organic solutions, are exploited as a chemical platform to graft transition-metal oxide nanoparticles, namely nickel, manganese, copper, and cobalt oxide, onto the carbon framework. The reduction process is driven and controlled by the graphenide solution yielding nanoparticles with comparable sizes for all studied metal salts, well below 10 nm. The synthesis is generic and is not limited by the type of metal salt, because the reduced graphene layers serve simultaneously as both substrates and reducing agents. This reaction is reliable, reproducible, and versatile, generating materials for catalytic purposes without requiring any kind of stabilization or capping agents.

Degradation of Single-Layer and Few-Layer Graphene by Neutrophil Myeloperoxidase.

Biodegradability of graphene is one of the fundamental parameters determining the fate of this material in vivo. Two types of aqueous dispersible graphene, corresponding to single-layer (SLG) and few-layer graphene (FLG), devoid of either chemical functionalization or stabilizing surfactants, were subjected to biodegradation by human myeloperoxidase (hMPO) mediated catalysis. Graphene biodegradation was also studied in the presence of activated, degranulating human neutrophils. The degradation of both FLG and SLG sheets was confirmed by Raman spectroscopy and electron microscopy analyses, leading to the conclusion that highly dispersed pristine graphene is not biopersistent.

Highly Conducting, Sustainable, Nanographitic Rubber Composites.

Environmentally friendly multifunctional rubber composites are reported. Graphitic nanocarbon (NC) deriving from cracking of biogas (methane/carbon dioxide) and natural rubber extracted directly from the Hevea brasiliensis tree are the two components of these composites produced via latex technology. While maintaining and enhancing the intrinsic thermal and mechanical characteristics of rubber, the presence of NC shows a significant improvement on the electrical response. For a 10 wt % NC content, a 1010-fold increase in conductivity has been achieved with a conductivity value of 7.5 S·m-1, placing these composites among the best obtained using other carbon fillers. In addition, the piezoresistive behavior has also been verified. These promising green composites have a potential use in a variety of applications such as sealing of electronic devices and sensors.

From Food Waste to Efficient Bifunctional Nonprecious Electrocatalyst.

Synergy between graphitic nanocarbon, obtainable from food waste through cracking of biomethane, and iron oxide nanoparticles provides access to efficient bifunctional electro catalysts. Dissolution of potassium-intercalated graphitic nanocarbons yields graphenide solutions with calibrated, small lateral size-reduced graphenes that are used subsequently as reducing agents of iron metal salts. This results in the strong binding of small size (2-5 nm) nanoparticles on the carbon framework homogeneously within the composite material, accessibility of the catalytic centers, and good conductivity provided by the underlying carbon framework. The iron oxide nanocarbon electrocatalyst performances are highlighted by the overall overpotential of approximately 1 V needed to reach the benchmark threshold of 10 mA cm-2 for the oxygen reduction reaction and the particular activity towards oxygen evolution reaction (η≈0.4 V at 10 mA cm-2 ), comparable to that of the precious RuO2 and IrO2 catalysts. This iron oxide/nanocarbon electrocatalyst is versatile, remarkably active, stable, and truly sustainable.

Surfactant-free single-layer graphene in water.

Dispersing graphite in water to obtain true (single-layer) graphene in bulk quantity in a liquid has been an unreachable goal for materials scientists in the past decade. Similarly, a diagnostic tool to identify solubilized graphene in situ has been long awaited. Here we show that homogeneous stable dispersions of single-layer graphene (SLG) in water can be obtained by mixing graphenide (negatively charged graphene) solutions in tetrahydrofuran with degassed water and evaporating the organic solvent. In situ Raman spectroscopy of these aqueous dispersions shows all the expected characteristics of SLG. Transmission electron and atomic force microscopies on deposits confirm the single-layer character. The resulting additive-free stable water dispersions contain 400 m2 l-1 of developed graphene surface. Films prepared from these dispersions exhibit a conductivity of up to 32 kS m-1.

Simultaneous Graphite Exfoliation and N Doping in Supercritical Ammonia.

We report the exfoliation of graphite and simultaneous N doping of graphene by two methods: supercritical ammonia treatment and liquid-phase exfoliation with NH4OH. While the supercritical ammonia allowed N doping at a level of 6.4 atom % in 2 h, the liquid-phase exfoliation with NH4OH allowed N doping at a level of 2.7 atom % in 6 h. The N doped graphene obtained via the supercritical ammonia route had few layers (<5) and showed large lateral flake size (∼8 µm) and low defect density (ID/IG < 0.6) in spite of their high level of N doping. This work is the first demonstration of supercritical ammonia as an exfoliation agent and N doping precursor for graphene. Notably, the N doped graphene showed electrocatalytic activity toward oxygen reduction reaction with high durability and good methanol tolerance compared to those of commercial Pt/C catalyst.

High Yield Synthesis of Aspect Ratio Controlled Graphenic Materials from Anthracite Coal in Supercritical Fluids.

This paper rationalizes the green and scalable synthesis of graphenic materials of different aspect ratios using anthracite coal as a single source material under different supercritical environments. Single layer, monodisperse graphene oxide quantum dots (GQDs) are obtained at high yield (55 wt %) from anthracite coal in supercritical water. The obtained GQDs are ∼3 nm in lateral size and display a high fluorescence quantum yield of 28%. They show high cell viability and are readily used for imaging cancer cells. In an analogous experiment, high aspect ratio graphenic materials with ribbon-like morphology (GRs) are synthesized from the same source material in supercritical ethanol at a yield of 6.4 wt %. A thin film of GRs with 68% transparency shows a surface resistance of 9.3 kΩ/sq. This is apparently the demonstration of anthracite coal as a source for electrically conductive graphenic materials.

Single layer nano graphene platelets derived from graphite nanofibres.

Solutions of calibrated nanographenides (negatively charged nanographenes) are obtained by dissolution of graphite nanofibre intercalation compounds (GNFICs). Deposits show homogeneous unfolded nanographene platelets of 1 to 2 layers thickness and 10 nm lateral size, evidenced by atomic force microscopy and Raman spectroscopy. Upon oxidation, nanographenide solutions exhibit strong photoluminescence.

Transparent carbon nanotube network for efficient electrochemiluminescence devices.

A carbon nanotube-based electrode that combines transparency and good conductivity was used for the first time to develop an electrochemiluminescence (ECL) device. It resulted in an excellent material for ECL applications thanks to the very favorable overpotential of amine oxidation that represents the rate-determining step for the signal generation in both research systems and commercial instrumentation. The use of carbon nanotubes resulted in a ten times higher emission efficiency compared with commercial transparent indium tin oxide (ITO) electrodes. Moreover, application of this material for proof-of-principle ECL imaging was demonstrated, in which micro-beads were used to mimic a real biological sample in order to prove the possibility of obtaining single cell visualization.

Graphene/nickel nanoparticles composites from graphenide solutions.

Nanocomposites between nickel nanoparticles and graphene were obtained starting from nickel cations and graphenide solutions (negatively charged graphene layers) as both reducing agent to nickel cations and graphene source. Different nanomaterials were obtained in two different solvents, N-methyl-2-pyrrolidone (NMP) and tetrahydrofuran (THF), with different nickel/graphene ratios. The nanomaterials were characterized by UV-Vis spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). All the samples consist of large graphene layers highly decorated with crystalline nickel nanoparticles, of size ranging from 2 to 10 nm. Thin films of the samples were deposited on indium-tin oxide (ITO) substrates and electrochemically characterized in alkaline medium, leading to Ni(OH)2/NiOOH redox pair, where the increase of the nickel proportion in the nanocomposites resulted in higher peak currents. The samples obtained in NMP showed the best performance with a fivefold increase of the peak currents, consistent with the lower charge transfer resistance as seen by electrochemical impedance spectroscopy (EIS).

Reductive dismantling and functionalization of carbon nanohorns.

Reduction of carbon nanohorn (CNH) aggregates with potassium naphthalenide resulted in their dismantling and individualization. Furthermore, the reduced CNHs were functionalized via addition of electrophiles.

Solubilization of fullerenes, carbon nanotubes, and graphene.

Processing of novel carbon forms, i.e. fullerenes, nanotubes and graphene, in solution is described. C60 and higher fullerenes appear to be the only truly soluble forms of pure carbon. Ways to disperse carbon nanotubes and graphene are reviewed. True solutions of carbon nanotubes and graphene can be obtained by reductive dissolution, leading to solution of polyelectrolyte nanocarbons of high concentrations without damaging the nanocarbon. Finally it is shown that these solutions allow to obtain high performing materials such as highly conducting transparent electrodes.