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.

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.

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.

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.

Topology-Driven Reductive Silylation of Synthetic Carbon Allotropes.

Herein, the combined application of characterization tools, such as Raman spectroscopy, thermal gravimetric analysis coupled with mass spectrometry, and optical and atomic force microscopy, confirms the reductive silylation of synthetic carbon allotropes as a new covalent functionalization strategy for the formation of heteroatom-carbon bonds. In particular, our study gives interesting insights into the topology-driven retrofunctionalization of nanotubide and graphenide derivatives.

Novel λ(3)-iodane-based functionalization of synthetic carbon allotropes (SCAs)-common concepts and quantification of the degree of addition.

The covalent functionalization of carbon allotropes represents a main topic in the growing field of nano materials. However, the development of functional architectures is impeded by the intrinsic polydispersibility of the respective starting material, the unequivocal characterization of the introduced functional moieties, and the exact determination of the degree of functionalization. Based on a novel carbon allotrope functionalization reaction, utilizing λ(3) -iodanes as radical precursor systems, we were able to demonstrate the feasibility to separate and to quantify thermally detached functional groups, formerly covalently linked to carbon nanotubes and graphene through thermogravimetric GC-MS.

New basic insight into reductive functionalization sequences of single walled carbon nanotubes (SWCNTs).

The reactivity of reduced single walled carbon nanotubes (SWCNTs) (carbon nanotubides), prepared under strict inert conditions in a glovebox with respect to the covalent functionalization with hexyl iodide and subsequent exposure to ambient conditions (air, moisture), was systematically investigated by Raman, absorption, fluorescence, and IR spectroscopy as well as by TG/MS measurements. We have discovered that the alkylation does not lead to a complete discharging of the tubes since follow-up reactions with moisture still take place leading to mixed functionalized carbon nanotube derivatives containing H- and OH-addends (but no carboxylates) next to the hexyl groups. This was confirmed by the exposure of carbon nanotubides to ambient conditions. The degree of hexylation determined both under strict inert (ic) and ambient (ac) conditions increases with an increasing K:C ratio of the reduced SWCNT starting material. The presence of OH-groups covalently attached to the nanotubes was also confirmed by postfunctionalization reactions with 2-thiophenecarbonyl chloride, leading to the corresponding esters. Control experiments with KO2 give rise to the formation of the same oxygen functionalities. These combined findings allowed for the suggestions of a plausible reaction mechanism, describing all the observed reactions on the SWCNTs side walls. The amount of subsequent side reactions after the treatment of reduced SWCNTs with electrophiles is strongly influenced by the reduction potential of the electrophile, which is responsible for the extent of reoxidation. Incomplete quenching of negative charges allows stronger oxidants/electrophile (e.g., O2) to perform follow-up reactions.

Sulfur species in graphene oxide.

The structure of graphene oxide (GO) is of crucial importance for its chemical functionalization. However, the sulfur content present in GO prepared by Hummers' method has only been addressed by a few authors so far. It has been reported that hydrolysis of sulfur species takes place and that stable sulfonic groups are present in graphite oxide. In this manuscript, in contrast to earlier reports, sulfate species are identified that are covalently bound to GO and still present after extensive aqueous work-up. Additionally, we exclude the possibility that sulfonic groups are present in GO as major species after aqueous work up. Our results are based on bulk characterization of graphene oxide by thermogravimetry and subsequent analysis of the decomposition products using mass spectroscopy and infrared spectroscopy. Up to now, the combustion temperature between 200 and 300 °C remained almost unaddressed. In a temperature dependant experiment we reveal two main decomposition steps that differ in temperature and that are closely related to the sulfur species in GO. While the decomposition, between 200 and 300 °C, is related to the degradation of organosulfate, the other one, between 700 and 800 °C, is assigned to the pyrolysis of inorganic sulfate. Furthermore, organosulfate is to some extent responsible for the reactivity of GO. Therefore, the structural model of GO was extended by adding organosulfate in addition to epoxy and hydroxyl groups, which are predominantly covalently bound above and below the carbon skeleton. Furthermore, the identification of organosulfate groups beneath epoxy groups makes new molecular architectures feasible and can be used to explain the properties of GO in various applications.

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.

Selective polycarboxylation of semiconducting single-walled carbon nanotubes by reductive sidewall functionalization.

The efficient and controllable synthesis, the detailed characterization, and the chemical postfunctionalization of polycarboxylated single-walled carbon nanotubes SWCNT(COOH)(n) are reported. This innovative covalent sidewall functionalization method is characterized by (a) the preservation of the integrity of the entire σ-framework of SWCNTs; (b) the possibility of achieving very high degrees of addition; (c) control of the functionalization degrees by the variation of the reaction conditions (reaction time, ultrasonic treatment, pressure); (d) the identification of conditions for the selective functionalization of semiconducting carbon nanotubes, leaving unfunctionalized metallic tubes behind; (e) the proof that the introduced carboxylic acid functionalities can serve as versatile anchor points for the coupling to functional molecules; and (f) the application of a subsequent thermal degradation step of the functionalized semiconducting tubes leaving behind intact metallic SWCNTs. Functional derivatives have been characterized in detail by means of Raman, UV-vis/nIR, IR, and fluorescence spectroscopy as well as by thermogravimetric analysis combined with mass spectrometry, atomic force microscopy, and zeta-potential measurements.

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.

Brominated single walled carbon nanotubes as versatile precursors for covalent sidewall functionalization.

Herein we report on the facile preparation of brominated SWCNTs based on two complementary reductive activation routes. The respective brominated SWCNTs are highly reactive and can be used in nucleophilic substitution reactions and represent versatile starting materials for the generation of sidewall functionalized SWCNTs with a high density of functional moieties.