N. Bundaleska

Plasmas for environmental issues: from hydrogen production to 2D materials assembly

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, H2O2, 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.

Towards large-scale in free-standing graphene and N-graphene sheets

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.

Microwave plasma torches used for hydrogen production

A microwave plasma torch operating at 2.45 GHz and atmospheric pressure has been used as a medium and a tool for decomposition of alcohol in order to produce molecular hydrogen. Plasma in a gas mixture of argon and ethanol/methanol, with or without water, has been created using a waveguide surfatron launcher and a microwave generator delivering a power in the range 0.2-2.0 kW. Mass, Fourier Transform Infrared, and optical emission spectrometry have been applied as diagnostic tools. The decomposition yield of methanol was nearly 100 % with H2, CO, CO2, H2O, and solid carbon as the main reaction products. The influence of the fraction of Ar flow through the liquid ethanol/methanol on H2, CO, and CO2 partial pressures has been investigated, as well as the dependence of the produced H2 flow on the total flow and power. The optical emission spectrum in the range 250–700 nm has also been detected. There is a decrease of the OH(A-X) band intensity with the increase of methanol in the mixture. The emission of carbon atoms in the near UV range (240–300 nm) exhibits a significant increase as the amount of alcohol in the mixture grows. The obtained results clearly show that this microwave plasma torch at atmospheric pressure provides an efficient plasma environment for hydrogen production.

Instrumental contributions to the time-resolved optogalvanic signal in a hollow cathode discharge

Three light-induced galvanic contributions to the real optogalvanic (OG) signal were studied in a hollow cathode discharge (HCD). The photoelectron emission (PE) from the cathode surface with a sub-breakdown bias applied, and hence no discharge present, was measured within the framework of an OG experimental arrangement. The PE component in a real OG measurement was found to manifest itself as an instrumental effect along with the effect of nonresonant ionization. The convolution of these components was determined experimentally as an instrumental function, and a deconvolution procedure to determine the actual OG signal was developed. The transient characteristics of the OG circuit were analysed by time-deconvolution of the measured OG signal, and they turned out to be dependent on the operating HCD I–V point. In addition, the polarization of the light beam irradiating the HCD was found to influence the OG signal.

Large-scale synthesis of free-standing N-doped graphene using microwave plasma

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.