In this paper we present a facile method for the synthesis of aminated graphene derivative through simultaneous reduction and amination of graphene oxide via two-step liquid phase treatment with hydrobromic acid and ammonia solution in mild conditions. The amination degree of the obtained aminated reduced graphene oxide is of about 4 at.%, whereas C/O ratio is up to 8.8 as determined by means of X-ray photoelectron spectroscopy. The chemical reactivity of the introduced amine groups is further verified by successful test covalent bonding of the obtained aminated graphene with 3-Chlorobenzoyl chloride. The morphological features and electronic properties, namely conductivity, valence band structure and work function are studied as well, illustrating the influence of amine groups on graphene structure and physical properties. Particularly, the increase of the electrical conductivity, reduction of the work function value and tendency to form wrinkled and corrugated graphene layers are observed in the aminated graphene derivative compared to the pristine reduced graphene oxide. As obtained aminated graphene could be used for photovoltaic, biosensing and catalysis application as well as a starting material for further chemical modifications.

In this paper, we for the first time demonstrate efficient nitrogen doping of graphene oxide (GO) with nitrogen concentration of up to almost 5 at.% and desired type of the nitrogen species via modified Hummers’ method. Using x-ray photoelectron spectroscopy (XPS), x-ray absorption spectroscopy (XAS) and Fourier transform infrared spectroscopy (FTIR) techniques, we have found out graphitic nitrogen to be the dominant type of the implemented nitrogen species. At the same time, the subsequent GO thermal reduction to graphene appears to result in a transformation of the graphitic nitrogen into pyridines and pyrroles. The mechanisms of the observed GO nitrogen doping and conversion of the nitrogen species are proposed, providing an opportunity to control the type and concentration of the implemented nitrogen within the developed approach. A two-time increase of the graphenes’ conductivity is observed due to the performed nitrogen doping. Further comprehensive electrical studies combined with the transmission electron microscopy (TEM) and density functional theory (DFT) modeling have allowed us to estimate the conductivity mechanism and the impact of the implemented nitrogen. As a net result, a simple method to synthesize GO and graphene layers doped with specific nitrogen species is developed, which leads to new perspective applications for graphene, i.e. supercapacitors, catalysis, and sensors.

The derivatization of graphene to engineer its band structure is a subject of significant attention nowadays, extending the frames of graphene material applications in the fields of catalysis, sensing, and energy harvesting. Yet, the accurate identification of a certain group and its effect on graphene’s electronic structure is an intricate question. Herein, we propose the advanced fingerprinting of the epoxide and hydroxyl groups on the graphene layers via core-level methods and reveal the modification of their valence band (VB) upon the introduction of these oxygen functionalities. The distinctive contribution of epoxide and hydroxyl groups to the C 1s X-ray photoelectron spectra was indicated experimentally, allowing the quantitative characterization of each group, not just their sum. The appearance of a set of localized states in graphene’s VB related to the molecular orbitals of the introduced functionalities was signified both experimentally and theoretically. Applying the density functional theory calculations, the impact of the localized states corresponding to the molecular orbitals of the hydroxyl and epoxide groups was decomposed. Altogether, these findings unveiled the particular contribution of the epoxide and hydroxyl groups to the core-level spectra and band structure of graphene derivatives, advancing graphene functionalization as a tool to engineer its physical properties.