Oxidative wet-chemical delamination of graphene from graphite is expected to become a scalable production method. However, the formation process of the intermediate stage-1 graphite sulfate by sulfuric acid intercalation and its subsequent oxidation are poorly understood and lattice defect formation must be avoided. Here, we demonstrate film formation of micrometer-sized graphene flakes with lattice defects down to 0.02% and visualize the carbon lattice by transmission electron microscopy at atomic resolution. Interestingly, we find that only well-ordered, highly crystalline graphite delaminates into oxo-functionalized graphene, whereas other graphite grades do not form a proper stage-1 intercalate and revert back to graphite upon hydrolysis. Ab initio molecular dynamics simulations show that ideal stacking and electronic oxidation of the graphite layers significantly reduce the friction of the moving sulfuric acid molecules, thereby facilitating intercalation. Furthermore, the evaluation of the stability of oxo-species in graphite sulfate supports an oxidation mechanism that obviates intercalation of the oxidant. Scalable graphene production from graphite via an intercalation-oxidation-reduction process is still hampered by low reproducibility and many lattice defects. Here, the authors show that reducing molecular friction by using highly crystalline graphite and mild oxidizing conditions is the key to high quality graphene.

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Effect of friction on oxidative graphite intercalation and high-quality graphene formation

The chemical production of graphene as well as its controlled wet chemical modification is a challenge for synthetic chemists. Furthermore, the characterization of reaction products requires sophisticated analytical methods. In this Review we first describe the structure of graphene and graphene oxide and then outline the most important synthetic methods that are used for the production of these carbon-based nanomaterials. We summarize the state-of-the-art for their chemical functionalization by noncovalent and covalent approaches. We put special emphasis on the differentiation of the terms graphite, graphene, graphite oxide, and graphene oxide. An improved fundamental knowledge of the structure and the chemical properties of graphene and graphene oxide is an important prerequisite for the development of practical applications.

Chemistry with graphene and graphene oxide-challenges for synthetic chemists.

Despite intensive research, the mechanism of graphene oxide (GO) formation remains unclear. The role of interfacial interactions between solid graphite and the liquid reaction medium, and transport of the oxidizing agent into the graphite, has not been well-addressed. In this work, we show that formation of GO from graphite constitutes three distinct independent steps. The reaction can be stopped at each step, and the corresponding intermediate products can be isolated, characterized, and stored under appropriate conditions. The first step is conversion of graphite into a stage-1 graphite intercalation compound (GIC). The second step is conversion of the stage-1 GIC into oxidized graphite, which we define as pristine graphite oxide (PGO). This step involves diffusion of the oxidizing agent into the preoccupied graphite galleries. This rate-determining step makes the entire process diffusive-controlled. The third step is conversion of PGO into conventional GO after exposure to water, which involves hydroly...

Mechanism of graphene oxide formation.

Efficient exfoliation of graphite in solutions to obtain high-quality graphene flakes is desirable for printable electronics, catalysis, energy storage, and composites. Graphite oxide with large lateral dimensions has an exfoliation yield of ~100%, but it has not been possible to completely remove the oxygen functional groups so that the reduced form of graphene oxide (GO; reduced form: rGO) remains a highly disordered material. Here we report a simple, rapid method to reduce GO into pristine graphene using 1- to 2-second pulses of microwaves. The desirable structural properties are translated into mobility values of >1000 square centimeters per volt per second in field-effect transistors with microwave-reduced GO (MW-rGO) as the channel material and into particularly high activity for MW-rGO catalyst support toward oxygen evolution reactions.

http://science.sciencemag.org/content/sci/353/6306/1413.full.pdf

High-quality graphene via microwave reduction of solution-exfoliated graphene oxide

The chemical production of graphene as well as its controlled wet- chemical modification is a challenge for synthetic chemists and the characterization of reaction products requires sophisticated analytic methods. In this review we first describe the structure of graphene and graphene oxide. We then outline the most important synthetic methods which are used for the production of these carbon based nanomaterials. We summarize the state-of-the-art for their chemical functionalization by non-covalent and covalent approaches. We put special emphasis on the differentiation of the terms graphite, graphene, graphite oxide and graphene oxide. An improved fundamental knowledge about the structure and the chemical properties of graphene and graphene oxide is an important prerequisite for the development of practical applications.

Chemistry with Graphene and Graphene Oxide - Challenges for Synthetic Chemists

A suitable technology for the preparation of graphene based on versatile wet chemistry is presented for the first time. The protocol allows the wet chemical synthesis of graphene from a new form of graphene oxide that consists of an intact hexagonal σ-framework of C-atoms. Thus, it can be easily reduced to graphene that is no longer dominated by defects.

Wet Chemical Synthesis of Graphene

In this work, the authors focus on a method to fabricate arbitrary shaped free standing membranes with a thickness less than 20 nm, produced from different polymers with the help of low-energy ion irradiation. The authors analyze the thickness of the membranes and its dependence on the details of the irradiation process. In order to tune the properties of the suspended membranes, an additional ion irradiation step has been used. This step is applied to already suspended membranes and leads to several effects, such as heating, shape transformation, etc. These effects were analyzed for irradiation with Ar+ and He+ ions. The authors have found that He+ irradiation has a significant advantage over Ar+ irradiation providing strained, smooth, and homogeneous membranes. In order to measure the electrical properties of the suspended membranes, the authors invented a new method to contact the membranes. These low resistance contacts can be achieved as the authors describe in detail. The membranes electrical properties after He+ ion irradiation at different temperatures are presented. Finally, the authors analyze Raman spectra, and thermal and electrical conductivity of the highly conducting membranes. The authors conclude that after high temperature He+ ion irradiation the membranes consist of material similar in properties to the glassy carbon obtained by pyrolysis. However, this method does not require high temperature pyrolysis step, which makes integration with on-chip electronics more feasible.

Fabrication and characterization of glassy carbon membranes

The electrical and optical properties of surfaces of polyimide and AZ5214e graphitized by low-energy (1 keV) He+ irradiation at different polymer temperatures were investigated. The conductivity of the graphitized layers can be controlled with the irradiation temperature within a broad range and can reach values up to ∼1000 S/cm. We show that the electrical transport in low-conducting samples is governed by thermally activated hopping, while the samples with a high conductivity show a typical semimetallic behavior. The transition from thermally activated to semimetallic conductance governed by the irradiation temperature could also be observed in optical measurements. The semimetallic samples show an unusually high for graphitic materials carrier concentration, which results in a high extinction coefficient in the visible light range. By analyzing the temperature dependence of the conductance of the semimetallic samples, we conclude that the scattering of charge carriers is dominated by Coulomb interactions and can be described by a weak localization model. The transition from a three to two dimensional transport mechanism at low temperatures consistently explains the change in the temperature dependence of the conductance by cooling, observed in experiments.

Andreas Geworski

Papers

Wet Chemical Synthesis of Graphene

Fabrication and characterization of glassy carbon membranes

Polymer surfaces graphitization by low-energy He+ ions irradiation