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.

Cotton functionalized with nanostructured TiO2-Ag-AgBr layer for solar photocatalytic degradation of dyes and toxic organophosphates.

The functionalization of cotton fabric with photoactive TiO2-Ag-AgBr nanostructured layer has been successfully developed using a low temperature non-aqueous sol-gel route and aqueous suspension of AgBr. Evidence for the growth of TiO2 layer and the immobilization of AgBr nanoparticles have been confirmed by Raman, XRD and XPS. GSDR analysis revealed a strong absorption in the visible region brought by surface Plasmon resonance (SPR) of Ag nanocrystals generated at the surface of AgBr. The XPS evidenced the presence of Ag+, Ag0 and bromine, suggesting that Ag0 formed a shell around the deposited AgBr. The immobilized TiO2-Ag-AgBr heterostructured layer imparts a strong photocatalytic activity under visible light for the degradation of dyes in aqueous solution as well as of dimethyl methylphosphonate (DMMP), a chemical warfare agent simulant. These new catalytically active functionalized fabrics, with self-detoxification properties, have great potential for application in chemical protective clothes and might offer new opportunities for the design of functional materials for toxic chemical protection.

Chitosan-Ag-TiO2 films: An effective photocatalyst under visible light.

Aiming the degradation of harmful molecules under visible light, new photocatalytic systems were created. For this purpose, the surface of chitosan thin films was modified in heterogeneous phase via a simple and straightforward mild chemical process: chemisorption of silver ions followed by the synthesis in situ of TiO2 at low temperature (100 °C). A high photocatalytic activity under visible light was observed, leading to the degradation and/or mineralization of different organic products such as o-toluidine, salicylic acid and 4-aminomethyl benzoic acid. This efficiency is partly attributed to the formation of Ag NPs and also to the unexpected appearance of AgCl NPs, likely formed from the residual chlorine contained in the chitosan. The resulting TiO2/Ag/AgCl/Chitosan system is easy to prepare under mild conditions, avoiding calcination treatments and opens new perspectives for the production of visible light-driven photocatalysts. Samples were analysed by different techniques: XRD, Raman, FE-SEM, XPS, TGA, GSDR, LIF and LIP.

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.

P-type Cuox thin films by rf-plasma enhanced reactive thermal evaporation: influence of rf-power density.

Copper oxide is a well known p-type semiconductor material, usually obtained by thermal oxidation of copper thin-films within few minutes, at atmospheric pressure. In this paper, thin films of copper oxide that were deposited by radio-frequency plasma enhanced reactive thermal evaporation of copper at room temperature, without any post-deposition annealing treatment, are studied. The deposition of good quality p-type semiconductor oxide to be used in the fabrication of p-TFTs is the purpose of this work. The thickness of the films varies from 97 up to 160 nm. The influence of rf power density on chemical, electrical and optical properties of the films was studied. Samples present conductivity within the range of 6 x 10(-5) to 4 x 10(2) omega(-1) x cm(-1) (thermal activation energy in the interval 0.46 to 0.01 eV). The p-type conductivity of the films was confirmed by Seebeck effect in the more conductive samples. Surface composition obtained by XPS analysis was correlated with optical and electrical properties, showing that rf-power plays a main role in changes of material characteristics.

Surface photochemistry: alloxazine within nanochannels of Na+ and H + ZSM-5 zeolites.

This work reports the surface photochemistry study of alloxazine adsorbed within nanochannels of MFI zeolites, namely in a series of Na+ and H+ ZSM-5 zeolites where the hydrophobic and hydrophilic character of the host varies systematically. Laser-induced room temperature and 77 K luminescence of air-equilibrated solid powdered samples of alloxazine adsorbed onto the two sets of zeolites, which we will name NaZSM-5 and HZSM-5, revealed the existence of a single emission of alloxazine as a broad band centred at about 450 nm in some cases, while in others an emission with a maximum at about 510 nm was detected. The decay times of the alloxazine emission vary greatly going from solution to entrapment within the nanochannels of the ZSM-5 zeolites. In the latter case a lifetime distribution analysis has shown that the longest lifetime for the alloxazine fluorescence emission exists in the case where an isoalloxazine-type emission was detected, i.e. whenever the hydrophobic character of the host increases. Alloxazine entrapped in the more acidic zeolites exists in the form of emissive monomers. However, alloxazine emits both from monomeric and aggregated emissive forms in the case of the hydrophobic zeolites. These data indicate the formation of planar dimers of alloxazine whenever the number of active sites in the zeolite decreases. These dimers have to be formed at the intersections of the zig-zag and linear nanochannels of the zeolite since there is no space available for their formation inside the zeolite channels. The isoalloxazine tautomers are formed due to the existence of alloxazine dimers which may undergo double proton transfer in the excited state, following laser excitation. Delayed fluorescence of alloxazine was also detected for the HZSM-5 and NaZSM-5 entrapment both at room temperature and at 77 K. The present study is paradigmatic as regards the host influence on the photochemistry of the guest.