The chemical reduction of graphene oxide is a promising route towards the large scale production of graphene for commercial applications. The current state-of-the-art in graphene oxide reduction, consisting of more than 50 types of reducing agent, will be reviewed from a synthetic chemistry point of view. Emphasis is placed on the techniques, reaction mechanisms and the quality of the produced graphene. The reducing agents are reviewed under two major categories: (i) those which function according to well-supported mechanisms and (ii) those which function according to proposed mechanisms based on knowledge of organic chemistry. This review will serve as a valuable platform to understand the efficiency of these reducing agents for the reduction of graphene oxide.

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The recent growth in graphene has witnessed the utilization of graphene as promising materials in a plethora of applications. The potential of graphene could be improved exponentially provided that the processability and band gap could be finely controlled. To this aim, chemical functionalization of graphene remains an important and fundamental approach. This tutorial review aims to provide a broad-based coverage on the recent solution-based functionalization methods of graphene in a concise and mechanistic manner. We focus on the reactions of the graphene sp(2) backbone, such as nucleophilic addition, cycloaddition, free radical additions, substitutions and rearrangements.

The electrochemistry of graphene and its derivatives has been extensively researched in recent years. In the aspect of graphene preparation methods, the efficiencies of the top-down electrochemical exfoliation of graphite, the electrochemical reduction of graphene oxide and the electrochemical delamination of CVD grown graphene, are currently on par with conventional procedures. Electrochemical analysis of graphene oxide has revealed an unexpected inherent redox activity with, in some cases, an astonishing chemical reversibility. Furthermore, graphene modified with p-block elements has shown impressive electrocatalytic performances in processes which have been historically dominated by metal-based catalysts. Further progress has also been achieved in the practical usage of graphene in sensing and biosensing applications. This review is an update of our previous article in Chem. Soc. Rev. 2010, 39, 4146-4157, with special focus on the developments over the past two years.

Graphene-related materials are in the forefront of nanomaterial research. One of the most common ways to prepare graphenes is to oxidize graphite (natural or synthetic) to graphite oxide and exfoliate it to graphene oxide with consequent chemical reduction to chemically reduced graphene. Here, we show that both natural and synthetic graphite contain a large amount of metallic impurities that persist in the samples of graphite oxide after the oxidative treatment, and chemically reduced graphene after the chemical reduction. We demonstrate that, despite a substantial elimination during the oxidative treatment of graphite samples, a significant amount of impurities associated to the chemically reduced graphene materials still remain and alter their electrochemical properties dramatically. We propose a method for the purification of graphenes based on thermal treatment at 1,000°C in chlorine atmosphere to reduce the effect of such impurities on the electrochemical properties. Our findings have important implications on the whole field of graphene research.electrochemistry | synthesis G raphene and graphene-derived materials have recently attracted enormous attention from the scientific community because of their extraordinary physical, chemical, and mechanical features (1, 2). Graphene materials can be used in several applications-including electronics (3), composite materials (4, 5), sensing (6), energy storage (7,8), and medicine (9)-with expected or known advantages over conventional materials.In general, there are two routes leading to the production of graphene: (i) a bottom-up approach, consisting of growing single/ bilayered graphene onto a catalytic surface through chemical vapor deposition (CVD) technique (10, 11); and (ii) a top-down approach, starting from graphite to obtain single/few-layered graphene sheets by an exfoliation procedure (12, 13). Because exfoliation in the liquid phase is hardly achieved directly on graphitic materials because of the highly cohesive van der Waals forces between the graphene sheets (14), a chemical treatment is generally performed to oxidize graphite to graphite oxide (GO). The oxidation helps to increase the graphene interlayer distance for an easy exfoliation, which is then followed by the removal of the oxygen functionalities to give single/few-layered graphene (12). The second approach received particularly huge attention because it is suitable for large-scale production of graphene materials and is cost-effective, although the graphene produced presents significant structural defects and lower carrier mobility properties (12). Natural graphite is the preferred starting material for this method of preparation because it is available in great quantities and at a low cost. Alternatively, synthetic graphite is also widely adopted as a starting material. It is important to highlight the differences between these two graphitic materials with particular focus on the content of metallic impurities and possible sources of contamination.Natural graphite is mined using standard ...

Research on graphene materials has refocused on graphite oxides (GOs) in recent years. The fabrication of GO is commonly accomplished by using concentrated sulfuric acid in conjunction with: a) fuming nitric acid and KClO(3) oxidant (Staudenmaier); b) concentrated nitric acid and KClO(3) oxidant (Hofmann); c) sodium nitrate for in situ production of nitric acid in the presence of KMnO(4) (Hummers); or d) concentrated phosphoric acid with KMnO(4) (Tour). These methods have been used interchangeably in the graphene community, since the properties of GOs produced by these different methods were assumed as almost similar. In light of the wide applicability of GOs in nanotechnology applications, in which presence of certain oxygen functional groups are specifically important, the qualities and functionalities of the GOs produced by using these four different methods, side-by-side, was investigated. The structural characterizations of the GOs would be probed by using high resolution X-ray photoelectron spectroscopy, nuclear magnetic resonance, Fourier transform infrared spectroscopy, and Raman spectroscopy. Further electrochemical applicability would be evaluated by using electrochemical impedance spectroscopy and cyclic voltammetry techniques. Our analyses highlighted that the oxidation methods based on permanganate oxidant (Hummers and Tour methods) gave GOs with lower heterogeneous electron-transfer rates and a higher amount of carbonyl and carboxyl functionalities compared with when using chlorate oxidant (Staudenmaier and Hofmann methods). These observations indicated large disparities between the GOs obtained from different oxidation methods. Such insights would provide fundamental knowledge for fine tuning GO for future applications.

Graphene quantum dots is a class of graphene nanomaterials with exceptional luminescence properties. Precise dimension control of graphene quantum dots produced by chemical synthesis methods is currently difficult to achieve and usually provides a range of sizes from 3 to 25 nm. In this work, fullerene C60 is used as starting material, due to its well-defined dimension, to produce very small graphene quantum dots (∼2-3 nm). Treatment of fullerene C60 with a mixture of strong acid and chemical oxidant induced the oxidation, cage-opening, and fragmentation processes of fullerene C60. The synthesized quantum dots were characterized and supported by LDI-TOF MS, TEM, XRD, XPS, AFM, STM, FTIR, DLS, Raman spectroscopy, and luminescence analyses. The quantum dots remained fully dispersed in aqueous suspension and exhibited strong luminescence properties, with the highest intensity at 460 nm under a 340 nm excitation wavelength. Further chemical treatments with hydrazine hydrate and hydroxylamine resulted in red- and blue-shift of the luminescence, respectively.

Chemical reduction of graphene oxide is one of the main routes of preparation for large quantities of graphenes. A wide range of reducing agents was described for this task, such as hydroquinone, ascorbic acid, saccharides, proteins, hydrazine, or sodium borohydride. With exception of sodium borohydride and hydrazine, no "standard" organic chemistry agents have been described for reduction of graphene oxides. Lithium aluminum hydride (LAH) is a very powerful reducing agent frequently used in organic synthetic methodologies to convert several types of oxygen containing carbon moieties with a well-known reduction mechanism. Here, we describe, for the first time, the use of LAH toward the reduction of graphene oxide and compare its reduction strength to that of hydrazine and sodium borohydride, which are generally adopted in such application. We show that LAH is far more efficient in reducing oxygen functionalities present on graphene oxide. This is a step forward toward applicability of "standard" organic chemistry reducing agents for reduction of graphene oxides.