Reactivity with hydrogen of pure iron oxide and of iron oxides doped with oxides of Mn, Co, Ni and Cu

Using dynamic TG in H2, X-ray powder diffraction and Mössbauer Spectroscopy the reactivities fot hydrogen reduction of Fe2O3 prepared at different temperatures, Fe2O3 doped with oxides of Mn, Co, Ni and Cu prepared at 300DaggerC from nitrate precursors and intermediate spinels derived from above samples during reduction have been explored. The reactivity is higher for finely divided Fe2O3 prepared at 250DaggerC. The reduction is retarded by Mn, marginally affected by Co and accelerated by Ni and Cu, especially at higher (5 at.%) dopant concentration. These reactivities confirmed also by isothermal experiments, are ascribed to the nature of disorder in the metastable intermediate spinels and to hydrogen rsquospill overrsquo effects.

Form, Content, and Magnetism in Iron Oxide Nanocrystals

Monodisperse iron oxide nanocrystals with spherical and cubic morphologies, of comparable dimensions, have been prepared by the thermal decomposition of FeOOH. The lattice spacings of both forms agree with that of magnetite, Fe(3)O(4). The two, however, exhibit very different blocking temperatures. Nanocrystals of cubic morphology are superparamagnetic above 190 K while the spherical nanocrystals at a lower temperature, 142 K. The higher blocking temperatures in particles of cubic morphology are shown to be a consequence of exchange bias fields. We show that in the present iron oxide nanocrystals the exchange bias fields originate from the presence of trace amounts of wustite, FeO. A Reitveld refinement analysis of the X-ray diffraction patterns shows that nanocrystals of cubic morphology have a higher FeO content. The higher FeO content is responsible for the larger exchange bias fields that in turn lead to a higher blocking temperature for nanocrystals with cubic morphology.

Cyclodextrin functionalized magnetic iron oxide nanocrystals: a host-carrier for magnetic separation of non-polar molecules and arsenic from aqueous media

A single-step magnetic separation procedure that can remove both organic pollutants and arsenic from contaminated water is clearly a desirable goal. Here we show that water dispersible magnetite nanoparticles prepared by anchoring carboxymethyl-beta-cyclodextrin (CMCD) cavities to the surface of magnetic nanoparticles are suitable host carriers for such a process. Monodisperse, 10 nm, spherical magnetite, Fe3O4, nanocrystals were prepared by the thermal decomposition of FeOOH. Trace amounts of antiferromagnet, FeO, present in the particles provides an exchange bias field that results in a high superparamagnetic blocking temperature and appreciable magnetization values that facilitate easy separation of the nanocrystals from aqueous dispersions on application of modest magnetic fields. We show here that small molecules like naphthalene and naphthol can be removed from aqueous media by forming inclusion complexes with the anchored cavities of the CMCD-Fe3O4 nanocrystals followed by separation of the nanocrystals by application of a magnetic field. The adsorption properties of the iron oxide surface towards As ions are unaffected by the CMCD capping so it too can be simultaneously removed in the separation process. The CMCD-Fe3O4 nanocrystals provide a versatile platform for magnetic separation with potential applications in water remediation.

Single-step synthesis of carbon nanotubes/iron/iron oxide composite films through inert-ambient CVD using ferric acetylacetonate as a precursor

We have developed a unique single-step chemical vapor deposition (CVD) route for the synthesis of composite thin films containing carbon nanotubes (CNTs). CVD was carried out in an inert ambient using only iron(III) acetylacetonate as the precursor. Depositions were conducted at 700 degrees C on stainless steel substrates in argon ambient in the absence of any reactive gases (such as oxygen, hydrogen). By changing the deposition parameters, especially the pressure in the CVD reactor, the form of carbon deposited could be changed from amorphous to carbon nanotubes, the latter resulting in Fe-Fe3O4-CNT films. X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and electron microscopy together confirm the formation of the three-component composite and illustrate the nanoscale mixing of the components. Elemental iron formed in this process was protected from oxidation by the co-deposited carbon surrounding it. Irrespective of the substrate used, a composite coating with CNTs was formed under optimum conditions, as verified by analyses of the film formed on polycrystalline alumina and silicon substrates.

The electronic, chemical and electrocatalytic processes and intermediates on iron oxide surfaces during photoelectrochemical water splitting

We re-assess experimental soft X-ray absorption spectra of the oxygen K-shell which we recorded operando from iron oxide during photoelectrochemical water splitting in KOH electrolyte. In particular, we refer to recently reported transitional electron hole states which originate within the charge carrier depletion layer of the iron oxide and on the iron oxide surface. For the latter we find that an intermediate oxy-peroxo species is formed on the iron oxide with increasing bias potential, which disappears upon further polarization of the electrode, concomitantly with the evolution and disappearance of the aforementioned surface state. The oxygen spectra contain also the spectroscopic signatures of the electrolyte water, the position of which changes with increasing bias potential towards lower X-ray energies, revealing the breaking and formation of hydrogen bonds in the water during the experiment. Combined with potential dependent impedance spectroscopy data we are able to sketch the molecular structure of chemical intermediates and their charge carrier dynamics. (C) 2015 Elsevier B.V. All rights reserved.

Amperometric acetylcholinesterase biosensor for pesticides monitoring utilising iron oxide nanoparticles and poly(indole-5-carboxylic acid)

A new electrochemical sensing device was constructed for determination of pesticides. In this report, acetylcholinesterase was bioconjugated onto hybrid nanocomposite, i.e. iron oxide nanoparticles and poly(indole-5-carboxylic acid) (Fe(3)O(4)NPs/Pin5COOH) was deposited electrochemically on glassy carbon electrode. Fe(3)O(4)NPs was showed as an amplified sensing interface at lower voltage which makes the sensor more sensitive and specific. The enzyme inhibition by pesticides was detected within concentrations ranges between 0.1-60 and 1.5-70 nM for malathion and chlorpyrifos, respectively, under optimal experimental conditions (sodium phosphate buffer, pH 7.0 and 25 degrees C). Biosensor determined the pesticides level in water samples (spiked) with satisfactory accuracy (96%-100%). Sensor showed good storage stability and retained 50% of its initial activity within 70 days at 4 degrees C.

Studies on interaction of Paenibacillus polymyxa with iron ore minerals in relation to beneficiation

Interaction between Paenibacillus polymyxa with minerals such as hematite, corundum, quartz and kaolinite brought about significant surface chemical changes on all the minerals. Quartz and kaolinite were rendered more hydrophobic, while hematite and corundum, became more hydrophilic after biotreatment. The predominance of bacterial polysaccharides on interacted hematite and corundum and of proteins on quartz and kaolinite was responsible for the above surface-chemical changes. Bio-pretreatment of the above iron ore mineral mixtures resulted in the selective separation of silica and alumina from iron oxide, through bioflotation and bioflocculation. The utility of bioprocessing in the beneficiation of iron ores is demonstrated.

Developments in Biotechnology for Environmentally Benign Iron Ore Beneficiation

Biomineralization and biogenesis of iron ore deposits are illustrated in relation to indigenous microorganisms inhabiting iron ore mines. Aerobic and anaerobic microorganisms indigenous to iron oxide mineralization are analyzed. Microbially-induced flotation and flocculation of iron ore minerals such as hematite, alumina, calcite and quartz are discussed with respect to use of four types of microorganisms, namely, Paenibacillus polymyxa, Bacillus subtilis, Saccharomyces cerevisiae and Desulfovibrio desulfuricans. The role of the above organisms in the removal of silica, alumina, clays and apatite from hematite is illustrated with respect to mineral-specific bioreagents, surface chemical changes and microbe-mineral interaction mechanisms. Silica and alumina removal from real iron ores through biobeneficiation is outlined. Environmental benefits of biobeneficiation are demonstrated with respect to biodegradation of toxic reagents and environmentally-safe waste disposal and processing.

Collapse Behavior of an Artificially Cemented Clayey Silt

The present study examines the role of interparticle cementation in the collapse behavior of two partly saturated (S-r = 4 to 12%) and very highly porous (initial void ratio = 1.5 to 2) laboratory-desiccated clayey silt specimens containing varying amounts (5 and 15% by dry weight of the respective specimens) of the cementitious iron oxides hematite and goethite, which are generally encountered in tropical residual soils. Kaolinite is the representative clay mineral of the soil matrix used for this research. Interparticle cementation by the crystalline iron oxides was generated in the laboratory by repeated (six times) wetting and drying of the iron-hydroxide-admixed clayey silt specimens under ambient conditions of temperature and humidity. Results showed that, for a given laboratory-desiccated clayey silt specimen (i.e., a specimen containing 5 or 15% of iron oxide on a dry weight basis), the amount of collapse (represented by Delta epsilon, the change in vertical strain upon wetting under constant pressure) increases with an increase in the experimental loading under which the specimen is inundated. The laboratory results also show that the desiccated specimen with a higher iron oxide content (containing 15% iron oxide by dry weight of the desiccated specimen) in spite of a lower dry unit weight (gamma(d) = 8.8 kN/m(3)) undergoes a lesser amount of collapse on soaking under a constant external stress (50 or 100 kPa) than the desiccated specimen with a lower iron oxide content (i.e., containing 5% iron oxide by dry weight of the desiccated specimen, gamma(d) = 10.4 KN/m(3)). Based on the X-ray diffraction results and the stress-strain relationships obtained from isotropically consolidated undrained triaxial tests, it is suggested that the laboratory-desiccated specimens are characterized by a metastable bonding provided by capillary suction and the crystalline iron oxides. On soaking under load owing to the loss of the metastable bonding, collapse of the laboratory-desiccated specimens occurs. Also, in the case of the laboratory-desiccated specimen with a higher iron oxide content, the presence of a stronger interparticle cementation (due to a greater abundance of crystalline iron oxides) and a higher initial moisture content are considered responsible for the specimen exhibiting a lower amount of collapse in comparison to that exhibited by the desiccated specimen with a lesser iron oxide content.

Reduction of electric are furnace slags in stainless steelmaking - Part 1 Observations

Simultaneous reduction of iron and chromium oxides from synthetic electric are furnace stainless steelmaking slag in a graphite crucible has been studied. Above the melting point of iron the reduction of iron oxide leads to a carbon saturated Fe-C melt, but below the melting point of iron initially solid iron or iron carbide forms on the crucible surface. Only when a certain number of Fe-C droplets are formed does the reduction of chromium oxide start to form an Fe-Cr-C alloy. The reaction proceeds with pronounced foaming which depends on the basicity, temperature, and iron oxide content of the slag. IS/1352a (C) 1998 The Institute of Materials.

``Clickable'', Trifunctional Magnetite Nanoparticles and Their Chemoselective Biofunctionalization

A multifunctional iron oxide based nanoformulation for combined cancer-targeted therapy and multimodal imaging has been meticulously designed and synthesized using a chemoselective ligation approach. Novel superparamagnetic magnetite nanoparticles simultaneously functionalized with amine, carboxyl, and azide groups were fabricated through a sequence of stoichiometrically controllable partial succinylation and Cu (II) catalyzed diazo transfer on the reactive amine termini of 2-aminoethylphosphonate grafted magnetite nanoparticles (MNPs). Functional moieties associated with MNP surface were chemoselectively conjugated with rhodamine B isothiocyanate (RITC), propargyl folate (FA), and paclitaxel (PTX) via tandem nucleophic addition of amine to isothithiocyanates, Cu (I) catalyzed azide-alkyne click chemistry and carbodiimide-promoted esterification. An extensive in vitro study established that the bioactives chemoselectively appended to the magnetite core bequeathed multifunctionality to the nanoparticles without any loss of activity of the functional molecules. Multifunctional nanoparticles, developed in the course of the study, could selectively target and induce apoptosis to folate-receptor (FR) overexpressing cancer cells with enhanced efficacy as compared to the free drug. In addition, the dual optical and magnetic properties of the synthesized nanoparticles aided in the real-time tracking of their intracellular pathways also as apoptotic events through dual fluorescence and MR-based imaging.

Electrochemical aspects of leaching of ocean nodules in the presence and absence of microorganisms

instead of using chemical-reducing agents to facilitate the reduction and dissolution of manganese and iron oxide in the ocean nodule, electrochemical reduction based on two approaches, namely, cathodic polarization and galvanic interaction, can also be considered as attractive alternatives. Galvanic leaching of ocean nodules in the presence of pyrite and pyrolusite for complete recovery of Cu, Ni and Co has been discussed. The key for successful and efficient dissolution of copper, nickel and cobalt from ocean nodules depends on prior reduction of the manganese and ferric oxides with which the above valuable nonferrous metals are interlocked. Polarization studies using a slurry electrode system indicated that maximum dissolution of iron and manganese due to electrochemical reduction occurred at negative DC potentials of -600 mV (SCE) and -1400 mV (SCE). The present work is also relevant to galvanic bioleaching of ocean nodules using autotrophic microorganisms, such as Thiobacillus ferrooxidans and T thiooxidans, which resulted in significant dissolution of copper, nickel and cobalt at the expense of microbiologically generated acids. Various electrochemical and biochemical mechanisms are outlined and the electroleaching and galvanic processes so developed are shown to yield almost complete dissolution of all metal values. (C) 2002 Elsevier Science B.V. All rights reserved.

Synthesis and characterization of porous flowerlike alpha-Fe2O3 nanostructures for supercapacitor application

Porous flower-like alpha-Fe2O3 nanostructures synthesized by an ethylene glycol mediated self-assembly process are crystalline and porous with BET surface area of 64.6 m(2) g(-1). The discharge capacitance is 127 F g(-1) when the electrodes are cycled in 0.5 M Na2SO3 at a current density of 1 A g(-1). Capacitance retention after 1000 cycles is about 80% of the initial capacitance. The high discharge capacitance and its retention are attributed to high surface area and porosity of the iron oxide. As the iron oxides are inexpensive, the nano alpha-Fe2O3 is expected to be of potential use for supercapacitor application.

Between photocatalysis and photosynthesis: Synchrotron spectroscopy methods on molecules and materials for solar hydrogen generation

Energy research is to a large extent materials research, encompassing the physics and chemistry of materials, including their synthesis, processing toward components and design toward architectures, allowing for their functionality as energy devices, extending toward their operation parameters and environment, including also their degradation, limited life, ultimate failure and potential recycling. In all these stages, X-ray and electron spectroscopy are helpful methods for analysis, characterization and diagnostics for the engineer and for the researcher working in basic science.This paper gives a short overview of experiments with X-ray and electron spectroscopy for solar energy and water splitting materials and addresses also the issue of solar fuel, a relatively new topic in energy research. The featured systems are iron oxide and tungsten oxide as photoanodes, and hydrogenases as molecular systems. We present surface and subsurface studies with ambient pressure XPS and hard X-ray XPS, resonant photoemission, light induced effects in resonant photoemission experiments and a photo-electrochemical in situ/operando NEXAFS experiment in a liquid cell, and nuclear resonant vibrational spectroscopy (NRVS). (C) 2012 Elsevier B.V. All rights reserved.