Direct assembling of N-graphene, i.e. nitrogen doped graphene, in a controllable manner was achieved using microwave plasmas at atmospheric pressure conditions. The synthesis is accomplished via a single step using ethanol and ammonia as carbon and nitrogen precursors. Tailoring of the high-energy density plasma environment results in a selective synthesis of N-graphene (~0.4% doping level) in a narrow range of externally controlled operational conditions, i.e. precursor and background gas fluxes, plasma reactor design and microwave power. Applying infrared (IR) and ultraviolet (UV) irradiation to the flow of free-standing sheets in the post-plasma zone carries out changes in the percentage of sp², the N doping type and the oxygen functionalities. X-ray photoelectron spectroscopy (XPS) revealed the relative extension of the graphene sheets π-system and the type of nitrogen chemical functions present in the lattice structure. Scanning Electron microscopy (SEM), Transmission Electron microscopy (TEM) and Raman spectroscopy were applied to determine morphological and structural characteristics of the sheets. Optical emission and FT-IR spectroscopy were applied for characterization of the high-energy density plasma environment and outlet gas stream. Electrochemical measurements were also performed to elucidate the electrochemical behavior of NG for supercapacitor applications.

Self-standing graphene sheets were synthesized using microwave plasmas driven by surface waves at 2.45 GHz stimulating frequency and atmospheric pressure. The method is based on injecting ethanol molecules through a microwave argon plasma environment, where decomposition of ethanol molecules takes place. The evolution of the ethanol decomposition was studied in situ by plasma emission spectroscopy. Free gas-phase carbon atoms created in the plasma diffuse into colder zones, both in radial and axial directions, and aggregate into solid carbon nuclei. The main part of the solid carbon is gradually withdrawn from the hot region of the plasma in the outlet plasma stream where nanostructures assemble and grow. Externally forced heating in the assembly zone of the plasma reactor has been applied to engineer the structural qualities of the assembled nanostructures. The synthesized graphene sheets have been analysed by Raman spectroscopy, scanning electron microscopy, high-resolution transmission electron microscopy and x-ray photoelectron spectroscopy. The presence of sp3 carbons is reduced by increasing the gas temperature in the assembly zone of the plasma reactor. As a general trend, the number of mono-layers decreases when the wall temperature increases from 60 to 100 °C. The synthesized graphene sheets are stable and highly ordered.

One of the greatest challenges in the commercialization of graphene and derivatives is production of high quality material in bulk quantities at low price and in a reproducible manner. The very limited control, or even lack of, over the synthesis process is one of the main problems of conventional approaches. Herein, we present a microwave plasma-enabled scalable route for continuous, large-scale fabrication of free-standing graphene and nitrogen doped graphene sheets. The method’s crucial advantage relies on harnessing unique plasma mechanisms to control the material and energy fluxes of the main building units at the atomic scale. By tailoring the high energy density plasma environment and complementarily applying in situ IR and soft UV radiation, a controllable selective synthesis of high quality graphene sheets at 2 mg/min yield with prescribed structural qualities was achieved. Raman spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy, X-ray photoelectron spectroscopy and Near Edge X-ray-absorption fine-structure spectroscopy were used to probe the morphological, chemical and microstructural features of the produced material. The method described here is scalable and show a potential for controllable, large-scale fabrication of other graphene derivatives and promotes microwave plasmas as a competitive, green, and cost-effective alternative to presently used chemical methods.

A theoretical model for a low pressure surface wave driven ${\mathrm{N}}_2–\mathrm{Ar}$ discharge accounting in a self-consistent way for electron and heavy particle kinetics, gas thermal balance, and wave electrodynamics is developed. The inhomogeneous wave power transfer along the discharge and the concentrations of active species as a function of the spatial position and mixture composition are investigated. ${\mathrm{N}}_2^{+}$ are the dominant ions over a wide range of Ar percentages in the mixture due to the contributions of charge transfer processes between ${\mathrm{Ar}}^{+}$ and ${\mathrm{N}}_2$ and an effective associative ionization from ${\mathrm{N}}_2{\mathrm{(A }}^3{\Sigma }_u^{+}\mathrm{).}$ Dissociative recombination of ${\mathrm{N}}_2^{+}$ with electrons provides an increase in the dissociation degree of nitrogen molecules at high Ar fractional concentration.