Simultaneous Synthesis and Nitrogen Doping of Free-Standing Graphene Applying Microwave Plasma.

An experimental and theoretical investigation on microwave plasma-based synthesis of free-standing N-graphene, i.e., nitrogen-doped graphene, was further extended using ethanol and nitrogen gas as precursors. The in situ assembly of N-graphene is a single-step method, based on the introduction of N-containing precursor together with carbon precursor in the reactive microwave plasma environment at atmospheric pressure conditions. A previously developed theoretical model was updated to account for the new reactor geometry and the nitrogen precursor employed. The theoretical predictions of the model are in good agreement with all experimental data and assist in deeper understanding of the complicated physical and chemical process in microwave plasma. Optical Emission Spectroscopy was used to detect the emission of plasma-generated ''building units'' and to determine the gas temperature. The outlet gas was analyzed by Fourier-Transform Infrared Spectroscopy to detect the generated gaseous by-products. The synthesized N-graphene was characterized by Scanning Electron Microscopy, Raman, and X-ray photoelectron spectroscopies.

Prospects for microwave plasma synthesized N-graphene in secondary electron emission mitigation applications.

The ability to change the secondary electron emission properties of nitrogen-doped graphene (N-graphene) has been demonstrated. To this end, a novel microwave plasma-enabled scalable route for continuous and controllable fabrication of free-standing N-graphene sheets was developed. High-quality N-graphene with prescribed structural qualities was produced at a rate of 0.5 mg/min by tailoring the high energy density plasma environment. Up to 8% of nitrogen doping levels were achieved while keeping the oxygen content at residual amounts (~ 1%). The synthesis is accomplished via a single step, at atmospheric conditions, using ethanol/methane and ammonia/methylamine as carbon and nitrogen precursors. The type and level of doping is affected by the position where the N-precursor is injected in the plasma environment and by the type of precursors used. Importantly, N atoms incorporated predominantly in pyridinic/pyrrolic functional groups alter the performance of the collective electronic oscillations, i.e. plasmons, of graphene. For the first time it has been demonstrated that the synergistic effect between the electronic structure changes and the reduction of graphene π-plasmons caused by N doping, along with the peculiar "crumpled" morphology, leads to sub-unitary (< 1) secondary electron yields. N-graphene can be considered as a prospective low secondary electron emission and plasmonic material.

Microwave plasma-based direct synthesis of free-standing N-graphene.

Free-standing N-graphene was synthesized using a microwave plasma-based method at atmospheric pressure conditions through a single step and in a controllable manner. Using ethanol and ammonia as precursors, N-graphene with low relative amount of bonded oxygen and low level of saturated sp3 carbon bonds was produced. Adjusting the injection position of the nitrogen precursor in the plasma medium leads to selectivity in terms of doping level, nitrogen configuration and production yield. A previously developed theoretical model, based on plasma thermodynamics and chemical kinetics, was further updated to account for the presence of nitrogen precursor. The important role of HCN attachment to the graphene sheets as the main process of N-graphene formation is elucidated. The model predictions were validated by experimental results. Optical Emission Spectroscopy was used to detect the emission of plasma generated "building units" and to determine the gas temperature. The plasma outlet gas was analyzed by Fourier-Transform Infrared Spectroscopy to detect the generated gaseous by-products. The synthesized N-graphene was characterized by Scanning Electron Microscopy, Raman and X-ray photoelectron spectroscopies.

Microwave plasma enabled synthesis of free standing carbon nanostructures at atmospheric pressure conditions.

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.

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.

Applying weight gain in Pomacea lineata (Spix 1824) (Mollusca: Prosobranchia) as a measure of herbicide toxicity

Pomacea lineata, um molusco amplamente distribuído e considerado como peste em plantações de arroz no Oriente, pode ser considerado como um valioso recurso para monitorar a qualidade da água no Nordeste do Brasil. Neste trabalho, apresentamos dados que demonstram que o incremento de peso em moluscos neonatos é uma medida consistente que responde eficientemente ao estresse imposto por concentrações tóxicas subletais dos herbicidas Paraquat e Round-up. Os resultados de crescimento para avaliar a toxicidade crônica foram obtidos em experimentos de quatro e quatro, oito, doze e dezesseis dias para Paraquat e Round-up, respectivamente. A maior concentração de efeito não observado (NOEC) e a menor concentração de efeito observado (LOEC) para Paraquat, após 96 horas, foram respectivamente de 0,12 e 0,25 mg/L. Para o Round-up, os valores de NOEC e LOEC estimados foram respectivamente de 0,25 e 0,5 mg/L. Todas as concentrações de Round-up testadas após 192 horas de exposição provocaram diminuições nas taxas de crescimento, sendo significativamente diferentes do controle. Conseqüentemente não pode ser estimado o valor de NOEC. O valor de LOEC foi menor do que 0,12 mg/L. Além disso, não houve nenhuma mortalidade durante o teste. Por conseguinte, nenhum NOEC pôde ser derivado e o LOEC era < 0,12 mg/L. Para as mais baixas concentrações de Paraquat testadas (0,005 mg/L), houve um aumento do crescimento que foi significativamente maior que o controle, sugerindo a ocorrência de um efeito hormético.

Applying weight gain in Pomacea lineata (SPIX 1824) (Mollusca: Prosobranchia) as a measure of herbicide toxicity.

Pomacea lineata, an extremely ubiquitous snail and pest to rice farmers throughout Asia, holds promise as a valuable resource for monitoring water quality in northeast Brazil. In this paper, we present data demonstrating the rate of weight gain in P. lineata neonates as a consistent measure of the stress imposed by sublethal concentrations of the herbicides Paraquat and Round-up. Our secondary agenda is to demonstrate the feasibility of incorporating bioassay into the standard municipal and state procedure of monitoring water quality. Growth data to assess chronic toxicity were generated in experiments of four and four, eight, twelve and sixteen days for Paraquat and Round-up, respectively. We estimated a 96 h no observed effect concentration (NOEC) and lowest observed effect concentration (LOEC) for Paraquat of 0.12 and 0.25 mg/L. The 96 h Round-up data yielded NOEC and LOEC values, respectively, of 0.25 and 0.5 mg/L. All concentrations of Round-up tested for the 192 h exposure yielded significantly lower growth than the control. Consequently, no NOEC could be derived. The LOEC was < 0.12 mg/L. Furthermore, there was no mortality during the test. At the lowest concentrations of Paraquat tested (0.005 mg/L) there was a significant increase in growth compared with the controls, suggesting a hormetic effect.