A theoretical and experimental study on atmospheric pressure microwave plasma-based assembly of free standing graphene sheets is presented. The synthesis method is based on introducing a carbon-containing precursor (C 2 H 5 OH) through a microwave (2.45 GHz) argon plasma environment, where decomposition of ethanol molecules takes place and carbon atoms and molecules are created and then converted into solid carbon nuclei in the 'colder' nucleation zones. A theoretical model previously developed has been further updated and refined to map the particle and thermal fluxes in the plasma reactor. Considering the nucleation process as a delicate interplay between thermodynamic and kinetic factors, the model is based on a set of non-linear differential equations describing plasma thermodynamics and chemical kinetics. The model predictions were validated by experimental results. Optical emission spectroscopy was applied to detect the plasma emission related to carbon species from the 'hot' plasma zone. Raman spectroscopy, scanning electron microscopy (SEM), and x-ray photoelectron spectroscopy (XPS) techniques have been applied to analyze the synthesized nanostructures. The microstructural features of the solid carbon nuclei collected from the colder zones of plasma reactor vary according to their location. A part of the solid carbon was deposited on the discharge tube wall. The solid assembled from the main stream, which was gradually withdrawn from the hot plasma region in the outlet plasma stream directed to a filter, was composed by 'flowing' graphene sheets. The influence of additional hydrogen, Ar flow rate and microwave power on the concentration of obtained stable species and carbon−dicarbon was evaluated. The ratio of sp 3 /sp 2 carbons in graphene sheets is presented. A correlation between changes in C 2 and C number densities and sp 3 /sp 2 ratio was found.

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.

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.

It is well recognized at present that the unique, high energy density plasma environment provides suitable conditions to dissociate/atomize molecules in remediation systems, to convert waste and biomass into sustainable energy sources, to purify water, to assemble nanostructures, etc. The remarkable plasma potential is based on its ability to supply simultaneously high fluxes of charged particles, chemically active molecules, radicals (e.g. O, H, OH), heat, highly energetic photons (UV and extreme UV radiation), and strong electric fields in intrinsic sheath domains. Due to this complexity, low-temperature plasma science and engineering is a huge, highly interdisciplinary field that spans many research disciplines and applications across many areas of our daily life and industrial activities. For this reason, this review deals only with some selected aspects of low-temperature plasma applications for a clean and sustainable environment. It is not intended to be a comprehensive survey, but just to highlight some important works and achievements in specific areas. The selected issues demonstrate the diversity of plasma-based applications associated with clean and sustainable ambiance and also show the unity of the underlying science. Fundamental plasma phenomena/processes/features are the common fibers that pass across all these areas and unify all these applications. Browsing through different topics, we try to emphasize these phenomena/processes/features and their uniqueness in an attempt to build a general overview. The presented survey of recently published works demonstrates that plasma processes show a significant potential as a solution for waste/biomass-to-energy recovery problems. The reforming technologies based on non-thermal plasma treatment of hydrocarbons show promising prospects for the production of hydrogen as a future clean energy carrier. It is also shown that plasmas can provide numerous agents that influence biological activity. The simultaneous generation in water discharges of intense UV radiation, shock waves and active radicals (OH, O, H 2 O 2 , etc), which are all effective agents against many biological pathogens and harmful chemicals, make these discharges suitable for decontamination, sterilization and purification processes. Moreover, plasmas appear as invaluable tools for the synthesis and engineering of new nanomaterials and in particular 2D materials. A brief overview on plasma-synthesized carbon nanostructures shows the high potential of such materials for energy conversion and storage applications.

An experimental and theoretical study on microwave (2.45 GHz) plasma enabled assembly of carbon nanostructures, such as multilayer graphene sheets and nanoparticles, was performed. The carbon nanostructures were fabricated at different Ar-CH4 gas mixture composition and flows at atmospheric pressure conditions. The synthesis method is based on decomposition of the carbon-containing precursor (CH4) in the "hot" microwave plasma environment into carbon atoms and molecules, which are further converted into solid carbon nuclei in the "colder" plasma zones. By tailoring of the plasma environment, a controlled synthesis of graphene sheets and diamond-like nanoparticles was achieved. Selective synthesis of graphene flakes was achieved at a microwave power of 1 kW, Ar and methane flow rates of 600 sccm and 2 sccm respectively, while the predominant synthesis of diamond-like nanoparticles was obtained at the same power, but with higher flow rates, i.e. 1000 and 7.5 sccm, respectively. Optical emission spectroscopy was applied to detect the plasma emission related to carbon species from the 'hot' plasma zone and to determine the main plasma parameters. Raman spectroscopy and scanning electron microscopy have been applied to characterize the synthesized nanostructures. A previously developed theoretical model was further updated and employed to understand the mechanism of CH4 decomposition and formation of the main building units, i.e. C and C2, of the carbon nanostructures. An insight into the physical chemistry of carbon nanostructure formation in a high energy density microwave plasma environment is presented.

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