Martin Kormunda

TiO2-graphene oxide nanocomposite as advanced photocatalytic materials

BackgroundGraphene oxide composites with photocatalysts may exhibit better properties than pure photocatalysts via improvement of their textural and electronic properties.ResultsTiO2-Graphene Oxide (TiO2 - GO) nanocomposite was prepared by thermal hydrolysis of suspension with graphene oxide (GO) nanosheets and titania peroxo-complex. The characterization of graphene oxide nanosheets was provided by using an atomic force microscope and Raman spectroscopy. The prepared nanocomposites samples were characterized by Brunauer–Emmett–Teller surface area and Barrett–Joiner–Halenda porosity, X-ray Diffraction, Infrared Spectroscopy, Raman Spectroscopy and Transmission Electron Microscopy. UV/VIS diffuse reflectance spectroscopy was employed to estimate band-gap energies. From the TiO2 - GO samples, a 300 μm thin layer on a piece of glass 10×15 cm was created. The photocatalytic activity of the prepared layers was assessed from the kinetics of the photocatalytic degradation of butane in the gas phase.ConclusionsThe best photocatalytic activity under UV was observed for sample denoted TiGO_100 (k = 0.03012 h-1), while sample labeled TiGO_075 (k = 0.00774 h-1) demonstrated the best activity under visible light.

Cerium dioxide as a new reactive sorbent for fast degradation of parathion methyl and some other organophosphates

Abstract Cerium dioxide was used for the first time as reactive sorbent for the degradation of the organophosphate pesticides parathion methyl, chlorpyrifos, dichlofenthion, fenchlorphos, and prothiofos, as well as of some chemical warfare agents-nerve gases soman and O -ethyl S -[2-(diisopropylamino) ethyl] methylphosphonothioate (VX). CeO 2 specimens were prepared by calcination of basic cerous carbonate obtained by precipitation from an aqueous solution. The CeO 2 samples containing certain amounts (1 wt.%-5 wt.%) of the neighboring lanthanides (La, Pr, Nd) were prepared in a similar way from pure lanthanide salts. It was shown that ceria accelerated markedly the decomposition of parathion methyl causing the cleavage of the P-O-aryl bond in the pesticide molecule. A similar reaction mechanism was proposed for the degradation of other organophosphate pesticides and nerve agents. The degradation times (reaction half-times) were in an order of minutes in the presence of CeO 2 , compared to hours or days under common environmental conditions. The reaction in suitable organic solvents allowed conversions of about 90% for parathion methyl loading of 20 mg pesticide/g CeO 2 within 2 h with a reactant half-life in the order of 0.1 min. The key parameter governing the degradation efficiency of CeO 2 was the temperature during calcination. At optimum calcination temperature (about 773.15 K), the produced ceria retained a sufficiently high surface area, and attained an optimum degree of crystallinity (related to a number of crystal defects, and thus potential reactive sites). The presence of other lanthanides somewhat decreased the reaction rate, but this effect was not detrimental and permitted the possible use of chemically impure ceria as a reactive sorbent. A fast organophosphate degradation was demonstrated not only in non-polar solvents (such as heptane), but also in polar aprotic solvents (acetonitrile, acetone) that are miscible with water. This opens new possibilities for designing more versatile decontamination strategies. The cleavage of phosphate ester bonds is of a great importance not only for the degradation of dangerous chemicals (chemical weapons, pesticides), but also for interactions of ceria (especially the nano-sized one) in biologically relevant systems.

Plasma Treatment of Glass Surfaces Using Diffuse Coplanar Surface Barrier Discharge in Ambient Air

We report a study on the treatment of flat glass surfaces by ambient air atmospheric pressure plasma, generated by a dielectric barrier discharge of coplanar arrangement of the electrode system—the diffuse coplanar surface barrier discharge (DCSBD). The plasma treatment of glass was performed in both static and dynamic modes. With respect to wettability of the glass surface, treatment in static mode resulted in non-uniform surface properties, whereas dynamic mode provided a fully uniform treatment. A water contact angle measurement was used to determine the efficiency of plasma treatments in dynamic mode and also to investigate a hydrophobic recovery of plasma treated glass surfaces. The X-ray photoelectron spectroscopy measurements showed a decrease of overall carbon concentrations after plasma treatment. A deconvolution of C1s peak, showed that a short plasma treatment led to decrease of C–C bonds concentration and increases of C–O and O–C=O bond concentrations. An enhancing influence of the glass surface itself on DCSBD diffuse plasma was observed and explained by different discharge onsets and changes in the electric field distribution.

Cerium oxide for the destruction of chemical warfare agents: A comparison of synthetic routes

Four different synthetic routes were used to prepare active forms of cerium oxide that are capable of destroying toxic organophosphates: a sol-gel process (via a citrate precursor), homogeneous hydrolysis and a precipitation/calcination procedure (via carbonate and oxalate precursors). The samples prepared via homogeneous hydrolysis with urea and the samples prepared via precipitation with ammonium bicarbonate (with subsequent calcination at 500°C in both cases) exhibited the highest degradation efficiencies towards the extremely dangerous nerve agents soman (O-pinacolyl methylphosphonofluoridate) and VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate) and the organophosphate pesticide parathion methyl. These samples were able to destroy more than 90% of the toxic compounds in less than 10 min. The high degradation efficiency of cerium oxide is related to its complex surface chemistry (presence of surface OH groups and surface non-stoichiometry) and to its nanocrystalline nature, which promotes the formation of crystal defects on which the decomposition of organophosphates proceeds through a nucleophilic substitution mechanism that is not dissimilar to the mechanism of enzymatic hydrolysis of organic phosphates by phosphotriesterase.

Thermal Treatment of Cerium Oxide and Its Properties: Adsorption Ability versus Degradation Efficiency

Cerium oxide belongs to the most important heterogeneous catalysts, but its applicability as so-called reactive sorbent for the degradation of toxic chemicals was only recently discovered. For these purposes, cerium oxide is prepared by precipitation of insoluble cerium salts (carbonates) with a subsequent thermal decomposition. Properties of cerium oxide prepared from the carbonate precursor are strongly affected by the temperature during the calcination. Main physicochemical properties of cerium oxide (specific surface area, crystallinity, and surface chemistry) were examined in dependence on the calcination temperature. As the adsorptive properties of CeO2 are undoubtedly of great importance in the abovementioned applications, the adsorption ability was studied using an azo dye Acid Orange 7 (AO7) as a model compound. The highest sorption efficiency towards AO7 exhibited sorbents prepared at temperatures below 700°C, which was attributed mainly to the presence of hydroxyl groups on the oxide surface. A strong correlation was found between an adsorption efficiency of cerium oxides and their degradation efficiency for organophosphate pesticide parathion methyl. The >Ce–OH groups on the sorbent surface are responsible for the dye binding by the surface-complexation mechanism, and probably also for the nucleophilic cleavage of the P–O–aryl bond in the pesticide molecule.

Shape-controlled synthesis of Sn-doped CuO nanoparticles for catalytic degradation of Rhodamine B

The uniform Sn-doped CuO nanoparticles were synthesized by a simple solution method at a low temperature. The prepared samples were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron microscopy techniques (HRSEM, HRTEM, SAED, STEM and EDS elemental mapping), atomic force microscopy (AFM), UV/Vis spectroscopy, nitrogen physisorption (BET) and by evaluation of the catalytic activity on the degradation of Rhodamine B. The tin doping had a considerable influence on the morphology of CuO. The gradual narrowing of the particles morphology in the crystallographic [010] direction was observed with increasing the dopant concentration. The plate-like, rectangularsquare and rod-like CuO nanoparticles were obtained. The mechanism of a crystal growth of CuO associated with doping is proposed. The tin doping also affected the structural and optical properties of CuO. Increasing the amount of a dopant led to a red-shift of a band gap from 1.33 to 1.18eV. The incorporation of tin into the structure of copper oxide was confirmed by XRD and distribution of tin mapped by EDS analysis. The good catalytic properties of the as-prepared doped material were demonstrated by the enhanced catalytic removal of Rhodamine B in the presence of H2O2. The undoped CuO nanosheets reached only 24% efficiency in the removal of Rhodamine B within two hours. The best result exhibited CuO_050Sn sample containing 4at.% of tin and the degradation of Rhodamine B reached 99% within the same time. We have demonstrated a simple, scalable process for the preparation of catalytically very active Sn-doped CuO nanoparticles with varying properties.

A green method of graphene preparation in an alkaline environment

We present a new, simple, quick and ecologically friendly method of exfoliating graphite to produce graphene. The method is based on the intercalation of a permanganate M2MnO4 (M=K, Na, Li), which is formed by the reaction of a manganate MMnO4 with an alkali metal hydroxide MOH. The quality of exfoliation and the morphology were determined using X-ray photoelectron spectroscopy, X-ray diffraction and microscopic techniques, including transmission electron microscopy and atomic force microscopy. We observed that a stable graphene suspension could be prepared under strongly alkaline conditions in the presence of permanganate and ultrasound assistance. The use of only an alkaline environment for the direct preparation of graphene from graphite structures has not been previously described or applied. It was found that such a method of preparation leads to surprisingly high yields and a stable product for hydrophilic graphene applications.

Role of bismuth in nano-structured doped TiO2 photocatalyst prepared by environmentally benign soft synthesis

An environmentally benign synthesis method was used to prepare a nearly uniform dispersion of TiO2 nanoparticles modified by bismuth for photocatalytic purposes. The role of bismuth in the catalyst structure was evaluated using numerous methods such as XRPD, HTXRPD, TEM and HRTEM, and XPS, as well as Raman, FTIR, and UV–Vis spectroscopy. The bismuth doping significantly improved the photocatalytic performance of azo dye RB5 discoloration due to the formation of surface Bi3+ species and the abundant hydroxylation of the catalyst surface. The great advantage of this procedure lies in the low temperature preparation under ambient pressure without use of the titanium organometallic precursors. Therefore, this developed synthesis procedure could be easily adapted to the industrial scale.

Composite Fe3O4/Humic Acid Magnetic Sorbent and its Sorption Ability for Chlorophenols and some other Aromatic Compounds

A composite magnetic sorbent with a relatively high content of humic substances (above 35% of organic carbon) was prepared by co-precipitation of Fe2+/Fe3+ salts with commercially available alkaline humate concentrate. Magnetite (Fe3O4) was identified as the main crystalline phase bearing the magnetic properties of the sorbent. Scanning electron microscope (SEM) images revealed the presence of uniform sub-micron structures on the surface of the sorbent grains. Due to the presence of humic substances, the sorbent exhibited good sorption ability towards low-polarity organic pollutants, namely chlorophenols. The sorption efficiency increased in the order of 4-mono- < 2,4-di- < 2,4,5-trichlorophenol in accordance with growing hydrophobicity of these compounds, confirming a hydrophobic nature of the interactions involved in the sorption process. Similar trends were found in the desorption study utilizing water and methanol as leachants. Some polycyclic aromatic hydrocarbons (naphthalene, anthracene, phenanthrene, fluoranthene, pyrene) were also retained on the sorbent. The chemical composition as well as the main physical characteristics (surface area, phase composition) of the sorbent remained virtually unchanged during the sorption process. The sorbent retained its magnetic properties during the sorption of organic substances from aqueous solutions, which provides an opportunity for its regeneration.

Phase composition and surface properties of nylon-6 nanofibers prepared by nanospider technology at various electrode distances

Phase composition, morphology and surface properties of nylon-6 nanofibers prepared by Nanospider technology have been studied for dependence on spinning distance using a combination of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electrokinetic analysis, and scanning electron and transmission electron microscopy (SEM, TEM). The effect of the electric field strength on the nanofiber phase composition was investigated via the variable distance of the electrodes. Quantitative XRD phase analysis revealed the dependence of the phase composition on the electrode distance, which in the case of roller electrospinning, differs from that by melt spinning. A combination of XRD, XPS, and TEM suggested a core-shell structure model of the nanofibers. The XPS and electrokinetic analysis revealed the difference in surface chemistry and zeta potential at the face and reverse side of the nanofiber textile adjacent to a polypropylene (PP) antistatic spunbond, which may be important in subsequent chemical modification of nanofiber textiles and in its use for tissue engineering.