Hydroboration of graphene oxide: towards stoichiometric graphol and hydroxygraphane.

Covalently functionalized graphene materials with well-defined stoichiometric composition are of a very high importance in the research of 2D carbon material family due to their well-defined properties. Unfortunately, most of the contemporary graphene-functionalized materials do not have this kind of defined composition and, usually, the amount of heteroatoms bonded to graphene framework is in the range of 1-10 at. %. Herein, we show that by a well-established hydroboration reaction chain, which introduces -BH2 groups into the graphene oxide structure, followed by H2O2 or CF3COOH treatment as source of -OH or -H, we can obtain highly hydroxylated compounds of precisely defined composition with a general formula (C1O0.78H0.75)n, which we named graphol and highly hydroxylated graphane (C1(OH)0.51H0.14)n, respectively. These highly functionalized materials with an accurately defined composition are highly important for the field of graphene derivatives. The enhanced electrochemical performance towards important biomarkers as well as hydrogen evolution reaction is demonstrated.

Definitive Insight into the Graphite Oxide Reduction Mechanism by Deuterium Labeling.

The reduction of graphite oxide is one of the most important reactions in the production of graphene in gram quantities. The mechanisms of these widely used reactions are poorly understood. The mechanism of the chemical reduction of two different graphite oxides prepared by the chlorate (Hofmann method) and permanganate methods (Hummers method) has been investigated. Three different reduction agents, lithium tetrahydridoaluminate, sodium tetrahydridoborate, and lithium tetrahydridoborate, as well as their deuterated counterparts, were used for the reduction of graphite oxide. Reduced graphite oxides were analyzed by scanning electron microscopy, energy-dispersive spectroscopy, elemental combustion analysis, Raman spectroscopy, high-resolution X-ray photoelectron spectroscopy, and simultaneous thermal analysis. The concentration of boron incorporated into graphene was measured by prompt gamma activation analysis. Rutherford back-scattering spectroscopy and elastic recoil detection analysis were used for the determination of the elemental composition, including deuterium concentration, as evidence of CH bond formation.

Chemical preparation of graphene materials results in extensive unintentional doping with heteroatoms and metals.

Chemical synthesis of graphene relies on the usage of various chemical reagents. The initial synthesis step, in which graphite is oxidized to graphite oxide, is achieved by a combination of chemical oxidants and acids. A subsequent chemical reduction step eliminates/reduces most oxygen functionalities to yield graphene. We demonstrate here that these chemical treatments significantly contaminate graphene with heteroatoms/metals, depending on the procedures followed. Contaminations with heteroatoms (N, B, Cl, S) or metals (Mn, Al) were present at relatively high concentrations (up to 3 at%), with their chemical states dependent on the procedures. Such unintentional contaminations (unwanted doping) during chemical synthesis are rarely anticipated and reported, although the heteroatoms/metals may alter the electronic and catalytic properties of graphene. In fact, the levels of unintentionally introduced contaminants on graphene are often higher than typical levels found on intentionally doped graphene. Our findings are important for scientists applying chemical methods to prepare graphene.