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.

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The formation of a segregated network structure (wittingly uneven distribution of a filler) is one of the most promising strategies for the fabrication of electrically conductive polymer composites at present. However, the simultaneous achievement of high values of electrical conductivity with the retention of well mechanical properties within this approach remains a great challenge. Here, by means of X-ray photoelectron spectra (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectra, scanning electron microscopy (SEM), dielectric spectroscopy, and compression engineering stress–strain curve analysis, we have studied the effect of a segregated network structure on the electrical conductivity and mechanical properties of a set of polymer composites. The composites were prepared by applying graphene oxide (GO) with ultralarge basal plane size (up to 150 μm) onto the surface of polymer powder particles, namely, poly(vinyl chloride) (PVC), poly(vinylidene fluoride- co -tetrafluoroethylene) (P(VDF-TFE)), and ultrahigh-molecular-weight poly(ethylene) (UHMWPE) with the subsequent GO reduction and composite hot pressing. A strong dependence of the segregated network polymer composites’ physical properties on the polymer matrix was demonstrated. Particularly, 12 orders of magnitude rise of the polymers’ electrical conductivity up to 0.7 S/m was found upon the incorporation of the reduced GO (rGO). A 17% increase in the P(VDF-TFE) elastic modulus filled by 1 wt % of rGO was observed. Fracture strength of PVC/rGO at 0.5 wt % content of the filler was demonstrated to decrease by fourfold. At the same time, the change in strength was not significant for P(VDF-TFE) and UHMWPE composites in comparison with pure polymers. Our results show a promise to accelerate the development of new composites for energy applications, such as metal-free supercapacitor plates and current collectors of lithium-ion batteries, bipolar plates of proton-exchange membrane fuel cells, antistatic elements of various electronic devices, etc.

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.

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