Tuning of magnetization in vertical graphenes by plasma-enabled chemical conversion of organic precursors with different oxygen content

Different magnetization in vertical graphenes fabricated by plasma-enabled chemical conversion of organic precursors with various oxygen atom contents and bonding energies was achieved. The graphenes grown from fat-like precursors exhibit magnetization up to 8 emu g−1, whereas the use of sugar-containing precursors results in much lower numbers. A relatively high Curie temperature exceeding 600 K was also demonstrated.

Control of morphology and nucleation density of iron oxide nanostructures by electric conditions on iron surfaces exposed to reactive oxygen plasmas

The possibility to control the morphology and nucleation density of quasi-one-dimensional, single-crystalline α -Fe2 O3 nanostructures by varying the electric potential of iron surfaces exposed to reactive oxygen plasmas is demonstrated experimentally. A systematic increase in the oxygen ion flux through rf biasing of otherwise floating substrates and then an additional increase of the ion/neutral density resulted in remarkable structural transformations of straight nanoneedles into nanowires with controlled tapering/aspect ratio and also in larger nucleation densities. Multiscale numerical simulations relate the microscopic ion flux topographies to the nanostructure nucleation and morphological evolution. This approach is applicable to other metal-oxide nanostructures.

The roles of adsorption in hydrate precipitation

It has been well established that organic compounds with adjacent hydroxyl groups in Bayer process liquor can inhibit gibbsite precipitation by acting as seed poisons. The degree of inhibition is a function of the number and stereochemistry of the hydroxyl groups. Seed poisons generally adsorb strongly onto hydrate surfaces, implying that surface coverage is the mechanism for yield inhibition. There are examples however of organics that strongly adsorb but do not lead to yield inhibition. There is a possibility that this apparent contradiction may be an artifact of differences in conditions between the adsorption and precipitation experiments. The present work investigates the adsorption and inhibition effects of a range of compounds under strictly similar conditions to clarify the role of adsorption on yield inhibition.

Reactive oxygen plasma-enabled synthesis of nanostructured CdO : tailoring nanostructures through plasma–surface interactions

Plasma-assisted synthesis of nanostructures is one of the most precise and effective approaches used in nanodevice fabrication. Here we report on the innovative approach of synthesizing nanostructured cadmium oxide films on Cd substrates using a reactive oxygen plasma-based process. Under certain conditions, the surface morphology features arrays of crystalline CdO nano/micropyramids. These nanostructures grow via unconventional plasma-assisted oxidation of a cadmium foil exposed to inductively coupled plasmas with a narrow range of process parameters. The growth of the CdO pyramidal nanostructures takes place in the solid-liquid-solid phase, with the rates determined by the interaction of plasma-produced oxygen atoms and ions with the surface. It is shown that the size of the pyramidal structures can be effectively controlled by the fluxes of oxygen atoms and ions impinging on the cadmium surface. The unique role of the reactive plasma environment in the controlled synthesis of CdO nanopyramidal structures is discussed as well.

Reactive Oxygen Species and Reactive Nitrogen Species in Epigenetic Modifications

For the normal homeostasis of a cell, there must be a balance between radical oxygen species/radical nitrogen species (ROS/RNS) production and the neutralization of these species by antioxidant scavenging. In times of stress, this balance is not maintained, and the result is oxidative stress. This stress can affect many pathways in the body and result in pathological consequences. Recent evidence suggests that ROS/RNS can affect the epigenetic regulation of genes by affecting the function of histone and DNA modifying enzymes, thus affecting phenotypic changes within the cellular environment. In the following chapter, we provide a broad overview of how oxidative stress induced by ROS/RNS can affect epigenetics, and using lung disease as our model we link the connection between these processes.

Preparation, characterization of surfactants modified clay minerals and nitrate adsorption

Organic surfactants modified clay minerals are usually used as adsorbents for hydrophobic organic contaminants remediation; this work however has shown organoclays can also work as adsorbents for hydrophilic anionic contaminant immobilization. Organoclays were prepared based on halloysite, kaolinite and bentonite and used for nitrate adsorption, which are significant for providing mechanism for the adsorption of anionic contaminants from waste water. XRD was used to characterize unmodified and surfactants modified clay minerals. Thermogravimetric analysis (TG) was used to determine the thermal stability and actual loading of surfactant molecules. Ion chromatography (IC) was used to determine changes of nitrate concentration before and after adsorption by these organoclays. These organoclays showed different removal capacities for anionic ions from water and adsorption mechanism was investigated.

Adsorption of the herbicide 2,4-D on organo-palygorskite

Among the clay minerals, montmorillonite is the most extensively studied material using as adsorbents, but palygorskite and its organically modified products have been least explored for their potential use in contaminated water remediation. In this study, an Australian palygorskite was modified with cationic surfactants octadecyl trimethylammonium bromide and dioctadecyl dimethylammonium bromide at different doses. A full structural characterization of prepared organo-palygorskite by X-ray diffraction, infrared spectroscopy, surface analysis and thermogravimetric analysis was performed. The morphological changes of palygorskite before and after modification were recorded using scanning electron microscopy, which showed the surfactant molecules can attach on the surface of rod-like crystals and thus can weaken the interactions between palygorskite single crystals. Real surfactants loadings on organo-palygorskites were also calculated based on thermogravimetric analysis. 1 CEC, 2 CEC octadecyl trimethylammonium bromide modified palygorskites, 1 CEC and 2 CEC dioctadecyl dimethylammonium bromide modified palygorskites absorbed as much as 12 mg/g, 42 mg/g, 9 mg/g and 25 mg/g of 2,4- dichlorophenoxyacetic acid respectively. This study has shown a potential on organo-palygorskites for organic herbicide adsorption especially anionic ones from waste water. In addition, equilibration time effects and the Langmuir and Freundlich models fitting were also investigated in details.

Reduction and adsorption of Pb2+ in aqueous solution by nano zero-valent iron : a SEM, TEM and XPS study

This study reports the synthesis, characterization and application of nano zero-valent iron (nZVI). The nZVI was produced by a reduction method and compared with commercial available ZVI powder for Pb2+ removal from aqueous phase. Comparing with commercial ZVI, the laboratory made nZVI powder has a much higher specific surface area. XRD patterns have revealed zero valent iron phases in two ZVI materials. Different morphologies have been observed using SEM and TEM techniques. EDX spectrums revealed even distribution of Pb on surface after reaction. The XPS analysis has confirmed that immobilized lead was present in its zero-valent and bivalent forms. ‘Core-shell’ structure of prepared ZVI was revealed based on combination of XRD and XPS characterizations. In addition, comparing with Fluka ZVI, this lab made nZVI has much higher reactivity towards Pb2+ and within just 15 mins 99.9% removal can be reached. This synthesized nano ZVI material has shown great potential for heavy metal immobilization from waste water.

Calculation of the oxygen isotope discrimination factor for studying plant respiration

Measurement of discrimination against 18O during dark respiration in plants is currently accepted as the only reliable method of estimating the partitioning of electrons between the cytochrome and alternative pathways. In this paper, we review the theory of the technique and its application to a gas-phase system. We extend it to include sampling effects and show that the isotope discrimination factor, D, is calculated as –dln(1 + δ)/dlnO*, where δ is isotopic composition of the substrate oxygen and O*=[O2]/[N2] in a closed chamber containing tissue respiring in the dark. It is not necessary to integrate the expression but, if the integrated form is used, the resultant regression should not be constrained through the origin. This is important since any error in D will have significant effects on the estimation of the flux of electrons through the two pathways.

Adsorption thermodynamics and kinetics study for the self-assembly of 1,8,15,22-tetraaminophthalocyanatocobalt(II) on glassy carbon surface

Spontaneous adsorption of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-CoIITAPc) on glassy carbon (GC) electrode leads to the formation of a stable self-assembled monolayer (SAM). Since the SAM of 4α-CoIITAPc is redox active, its adsorption on GC electrode was followed by cyclic voltammetry. SAM of 4α-CoIITAPc on GC electrode shows two pairs of well-defined redox peaks corresponding to CoIII/CoII and CoIIIPc−1/CoIIIPc−2. The surface coverage (Γ) value, calculated by integrating the charge under CoII oxidation, was used to study the adsorption thermodynamics and kinetics of 4α-CoIITAPc on GC surface. Cyclic voltammetric studies show that the adsorption of 4α-CoIITAPc on GC electrode has reached the saturation coverage (Γs) within 3 h. The Γs value for the SAM of 4α-CoIITAPc on GC electrode was found to be 2.37 × 10−10 mol cm−2. Gibbs free energy (ΔGads) and adsorption rate constant (kad) for the adsorption of 4α-CoIITAPc on GC surface were found to be −16.76 kJ mol−1 and 7.1 M−1 s−1, respectively. The possible mechanism for the self-assembly of 4α-CoIITAPc on GC surface is through the addition of nucleophilic amines to the olefinic bond on the GC surface in addition to a meager contribution from π stacking. The contribution of π stacking was confirmed from the adsorption of unsubstituted phthalocyanatocobalt(II) (CoPc) on GC electrode. Raman spectra for the SAM of 4α-CoIITAPc on carbon surface shows strong stretching and breathing bands of Pc macrocycle, pyrrole ring and isoindole ring. Raman and CV studies suggest that 4α-CoIITAPc is adopting nearly a flat orientation or little bit tilted orientation.

Porous fuel injection with oxygen enrichment in a viable scramjet engine

Oxygen enriched, porous fuel injection has been numerically investigated in this study with the aim of understanding mixing and combustion enhancements achievable in a viable scramjet engine. Four injection configurations were studied: a fuel only case, a pre-mixed case and two staged injection cases where fuel and oxidiser were injected independently. All simulations were performed on a flight scale vehicle at Mach 8 flow conditions. Results show that the addition of oxygen with the fuel increases the mixing efficiency of the engine, however, is less sensitive to the method of oxygen addition: premixed versus staged. When the fuel-oxidiser-air mixture was allowed to combust, the method of additional oxygen delivery had a more significant impact. For pre-mixed fuel and oxidiser, the engine was found to choke, whereas in contrast, in the staged enrichment cases the engine failed to ignite. This result indicates that there exists an optimised configuration between pre-mixed and staged oxygen enrichment which results in a started, and combusting engine.

Adsorption and mobility of metals in build-up on road surfaces

The study investigated the adsorption and bioavailability characteristics of traffic generated metals common to urban land uses, in road deposited solids particles. To validate the outcomes derived from the analysis of field samples, adsorption and desorption experiments were undertaken. The analysis of field samples revealed that metals are selectively adsorbed to different charge sites on solids. Zinc, copper, lead and nickel are adsorbed preferentially to oxides of manganese, iron and aluminium. Lead is adsorbed to organic matter through chemisorption. Cadmium and chromium form weak bonding through cation exchange with most of the particle sizes. Adsorption and desorption experiments revealed that at high metal concentrations, chromium, copper and lead form relatively strong bonds with solids particles while zinc is adsorbed through cation exchange with high likelihood of being released back into solution. Outcomes from this study provide specific guidance for the removal of metals from stormwater based on solids removal.

In-plane graphene/boron-nitride heterostructure as efficient metal-free electrocatalyst for the oxygen reduction reaction

Exploiting metal-free catalysts for the oxygen reduction reaction (ORR) and understanding their catalytic mechanisms are vital for the development of fuel cells (FCs). Our study has demonstrated that in-plane heterostructures of graphene and boron nitride (G/BN) can serve as an efficient metal-free catalyst for the ORR, in which the C-N interfaces of G/BN heterostructures act as reactive sites. The formation of water at the heterointerface is both energetically and kinetically favorable via a fourelectron pathway. Moreover, the water formed can be easily released from the heterointerface, and the catalytically active sites can be regenerated for the next reaction. Since G/BN heterostructures with controlled domain sizes have been successfully synthesized in recent reports (e.g. Nat. Nanotechnol., 2013, 8, 119), our results highlight the great potential of such heterostructures as a promising metal-free catalyst for ORR in FCs.