Mössbauer analysis of iron phases in brown coal ash and fireside deposits

The iron phases present in an electrostatic precipitator ash, an uncooled ash deposit and a cooled superheater ash deposit from Hazelwood Power Station, Australia, burning Morwell brown coal has been examined using Mössbauer spectroscopy. The principal iron phase in the precipitator ash and the uncooled ash deposit from a hot gas offtake was calcium aluminoferrite (Ca₂Fe_{2 ? x}Al_xO₅). Minor amounts of hematite (α-Fe₂O₃) and magnetite (Fe₃O₄) were also detected in the precipitator ash. The cooled superheater ash deposit contained a (Mg, Fe, Al) oxide spinel as the primary iron phase; small quantities of hematite were also detected in this deposit close to the heat exchanger interface. The formation of these iron phases has been rationalized on the basis of the average composition of coal delivered to the power station and supplementary ash chemistry data obtained from other techniques. The evidence suggests that the calcium aluminoferrite in the precipitator ash is derived from inorganic constituents (distributed throughout the coal organic matrix) and the hematite and magnetite are of mineral origin (discrete particles).     

Oxidation of pyrite in coal to magnetite

When bituminous coal is heated in an inert atmosphere (He) containing small amounts of oxygen at 393–455 °C, pyrite (FeS₂) in coal is partially converted to magnetite (Fe₃0₄). The maximum amount of Fe₃0₄ formed during the time of heating corresponds to 5–20% of the total pyrite present, depending on the coal sample. The magnetite forms as an outer crust on the pyrite grains. The fact that the magnetic properties of the pyrite grains are substantially increased by the magnetite crust suggests that pyrite can be separated from coal by use of a low magnetic field. In a laboratory test, 75% removal is obtained by means of a 500 Oe magnet on three samples, and 60% on a fourth sample.     

Dehydrogenation activities of coal liquefaction catalysts on various ranks of coals

The amount of hydrogen evolved from a coal during pyrolysis at atmospheric pressure in the presence of coal hydroliquefaction catalysts can be used to compare the activity of different catalysts for the highpressure hydrogenation of coals. This technique has now been used to compare the variation in the effectiveness of MoO₃-TiO₂, and Fe₂O₃-SO^2?₄, as hydroliquefaction catalysts with change in coal rank. It is indicated that coals with carbon contents of ≈ 82 wt% are the most amenable to hydroliquefaction at high pressure.     

Magnetic and sterilizing properties of Ag(II)O–Fe3O4 hybrids synthesized via mechano-chemistry

Ag(II)O–Fe₃O₄ hybrids with good magnetic and bactericidal activity were synthesized via mechano-chemistry. The resulted products were characterized by transmission electronic microscope, X-ray diffraction, X-ray photoelectron and Fourier transform infrared spectroscopy, atomic absorption spectrophotometer, vibrating sample magnetometry and the shake-flask method. The results indicated that magnetite nanoparticles were effectively grafted onto the surface of Ag(II)O submicron particles. The functionalized particles remained dispersed and superparamagnetic. The saturation magnetization increased with the amount of magnetite in the hybrids. Element Ag was released from Ag(II)O–Fe₃O₄ hybrids with a slow dissolution speed. Ag(II)O–Fe₃O₄ hybrids had strong antibacterial properties. When the concentrations of the two hybrids with the mass ratio of Ag(II)O to Fe₃O₄ of 1:2 and 2:1 were 10 mg/L, more than 99.9% of the Staphylococcus aureus or Escherichia coli bacteria were killed.     

Efficient visible light magnetic modified iron oxide photocatalysts

Magnetite iron oxide (Fe₃O₄) nanoparticles were synthesized via simple co-precipitation method using ferrous and ferric ions salts. Fe₃O₄ nanoparticles were modified by silica and titania. Pure and modified nanoparticles were employed for dye degradation under visible light. X-ray diffraction analysis indicated inverse spinel structure of Fe₃O₄ nanoparticles. The particle size of magnetite nanoparticles is decreased due to coating of silica and titania. Scanning and transmission electron microscopy indicated the spherical morphology for all samples. The synthesized Fe₃O₄ nanoparticles were ferromagnetic in nature with highest saturation magnetization value of 1.1034 emu as compared to silica and titania coated samples. Fourier transform infra-red spectra confirmed the incorporation of magnetite nanoparticles with silica and titania. Titania modified magnetite sample showed the highest photocatalytic activity as compared to silica modified magnetite nanoparticles and bare iron oxide under visible light irradiations.     

Structure,morphology and magnetic properties of Au/Fe3O4 nanocomposites fabricated by a soft aqueous route

Magnetic Fe₃O₄ (magnetite) nanoparticles are synthesized via a chemical precipitation route in different alkaline environments (NH₃ or NaOH) and subsequently functionalized with a (propynylcarbamate)triethoxysilane moiety, with the aim of promoting the nucleation and subsequent stabilization of gold nanoparticles. The propynylcarbamate group is able to capture the gold precursor (HAuCl₄), spontaneously reduce it, and stabilize the resulting Au nanoaggregates. The obtained results show that though the dimensions of the starting magnetite substrate depend on the base used in the preparation, they remain unaltered upon the subsequent modification. Conversely, the average Au nanoparticle dimensions can be conveniently tailored as a function of the base used in Fe₃O₄ preparation and the presence/absence of the organic functionalization. The smallest dimensions (15?nm) are obtained for AuNP supported on propynylcarbamate-functionalized Fe₃O₄ prepared in the presence of ammonia. Magnetization measurements highlight that all the Au/Fe₃O₄ nanocomposites display a superparamagnetic behavior and those obtained using ammonia showed consistently smaller Hc and Mr values (av. values of 7.4?Oe and 0.8?emu/g) than those prepared with sodium hydroxide (av. values of 28?Oe and 2.8?emu/g).     

12-Hydrothermal Synthesis and Characterization of Fe3O4 Nanorods

Oriented magnetite (Fe₃O₄) nanorods have been successfully synthesized using a simple ethylenediamine-assisted hydrothermal technique. The samples were characterized by X-ray diffractometer, transmission electron microscopy, Fourier transform infrared and vibrating sample magnetometer. The cubic spinel structure Fe₃O₄ nanorods show a good crystalline state and the diameter is ~5 nm with lengths up to 0.5 μm. Experimental results indicate that ethylenediamine plays a crucial role in determining morphological features. The Fe₃O₄ nanorods exhibit ferromagnetic behavior at room temperature with a magnetic saturation value of 72.94 emu g^?1. The growth mechanism based on the results of control experiments is also discussed.     

Structures of organic additives modified magnetite nanoparticles

Magnetite (Fe₃O₄) nanoparticles and magnetite-based inorganic–organic hybrids are attracting increasing attention in biomedicine, as thermoseeds for hyperthermia and contrast media in magnetic resonance imaging. Controlling the size of Fe₃O₄ thermoseeds is important, as particle size affects their heat generation under alternative magnetic fields. Fe₃O₄ is easily synthesized via aqueous processes. We previously demonstrated that adding organic polymers during synthesis affected the size and crystallinity of the resulting Fe₃O₄. However, the relationship of the chemical structure of the low-molecular-weight organic additive of its effect on the product has not been elucidated. In this study, organic compounds containing varying functional groups and surface charges were added to the precursor solution of Fe₃O₄. Crystalline Fe₃O₄ formed in the presence of neutral acetone, cationic ethylenediamine, and anionic acetic acid. These nanoparticles had slightly smaller particle sizes than those prepared in the absence of additives. The presence of oxalic acid and tris(hydroxymethyl)aminomethane inhibited Fe₃O₄ nucleation, instead yielding lepidocrosite- or akaganeite-type FeOOH. These differences were attributed to the ability to form complexes between iron ions and the organic additives. The saturation magnetizations of the products were consistent with Fe₃O₄. This indicated that the crystal phase of the iron oxide products differed, even when prepared in the presence of organic additives of the same functional group. It is concluded that state of ion-organic molecule complex in the solutions is a key factor governing nanostructure of the resultant iron oxide.     

Facile synthesis of magnetic Fe3O4@Chitosan nanocomposite as environmentally green catalyst in multicomponent Knoevenagel-Michael domino reaction

Magnetic Fe₃O₄ has interesting characteristics such as large surface area, low toxicity, ferromagnetic, and biocompatible. The presence of magnetic properties in Fe₃O₄ provides an advantage in its application as a heterogeneous catalyst. This study highlights the synthesis of Fe₃O₄ modified chitosan composite and evaluates the catalytic ability in multicomponent Knoevenagel-Michael domino reaction. The synthesis and characterization of pristine Fe₃O₄ and Fe₃O₄@Chi samples were investigated. The XRD analysis combined with refinement technique indicates that the pristine Fe₃O₄ crystallized in a cubic structure with Fd-3mz symmetry and the presence of chitosan in Fe₃O₄ sample did not change its structure. The FTIR analysis also demonstrated the binding of chitosan to the Fe₃O₄ nanoparticles. TEM image reveals the presence of chitosan in the composite sample formed a core-shell interaction and covered the surface of Fe₃O₄ nanoparticles. The evaluation of Fe₃O₄@Chi catalytic ability in multicomponent Knoevenagel-Michael domino reaction demonstrated reliable catalyst performance with a yield of 92.3% at optimum conditions. Fe₃O₄@Chi could be classified as a green catalyst because it can be used repeatedly with high yield and easy separation.     

Magnetic and structural studies of Fe3O4 nanoparticles synthesized via coprecipitation and dispersed in different surfactants

We present a study of the structural characteristics and magnetic behavior of Fe₃O₄ nanoparticles synthesized via coprecipitation and dispersed in different surfactants, among which we include acid oleic acid (OA), sodiumdodecylsulfate (SDS), polyvinyl alcohol (PVA) and several olive oils with different acidity, especially 0.2° (O2) and 1.0° (O10). The obtained samples were characterized by thermal analysis, X-ray diffraction, transmission electron microscopy (TEM), Fourier transform infrared (FTIR) and Mössbauer spectroscopies as well as M vs. H measurements. X-ray diffraction shows single phases having cubic spinel crystal structure whose crystallite size ranges between 9.4–11.1 nm. These results are in good agreement with TEM images also revealing the existence of an organic shell around the Fe₃O₄ nanoparticles, more visible for olive oils and insignificant in the sample dispersed with SDS. FTIR spectra of all synthetized samples show the two main broad metal-oxygen bands corresponding to intrinsic stretching vibrations of the metal located in tetrahedral and octahedral sites and additional sets of bands due to the different organic chains of surfactants. Mössbauer data indicated non-stoichiometric magnetite for Fe₃O₄-AO, Fe₃O₄-O2/O10 and Fe₃O₄-PVA samples and a large presence of maghemite for Fe₃O₄-SDS sample. All the obtained samples present superparamagnetic behavior, finding the greatest magnetization for Fe₃O₄-AO. Olive oils show comparable results than oleic acid, confirming their suitability as coating agents for this kind of synthesis.     

Cytotoxic effect of functionalized superparamagnetic samarium doped iron oxide nanoparticles for hyperthermia application

Magnetic Fluid Hyperthermia (MFH) is an emerging and safe technique for cancer treatment. Radiotherapy and Chemotherapy are widely adopted techniques for treating cancer but cause damage to the nearby healthy tissue. This paves the way for hyperthermia treatment for cancer. Since healthy cells are more heat-tolerant than malignant cells, magnetic nanoparticles with superparamagnetic properties were used in hyperthermia treatment. Surface modified magnetite (Fe₃O₄) iron oxide nanoparticles with enhanced stability, solubility, bio-compatibility and magnetic property were employed in hyperthermia treatment. In the present study, Superparamagnetic Samarium doped magnetite (Fe₃O₄:Sm) nanoparticles were functionalized with Oleylamine (OAm) and polyvinyl alcohol (PVA) by the sol-gel process. The obtained nanoparticles were characterized by X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), Transmission Electron Microscopy (TEM), and UV–Visible diffuse reflectance spectroscopy (UV-DRS), Thermogravimetric analysis (TGA) and Vibrating Sample Magnetometer (VSM). From XRD data, the crystallite size of oleylamine coated samarium doped magnetite (OAm–Fe₃O₄:Sm) and PVA-coated samarium doped Fe₃O₄ (PVA- Fe₃O₄:Sm) were found to be 9.5 nm and 10.9 nm, respectively. TEM images of the functionalized nanoparticles were visualized as a spherical structure with reduced agglomeration. UV-DRS gives the bandgap value of OAm–Fe₃O₄:Sm and PVA- Fe₃O₄:Sm coated samarium doped magnetite to be 2.3 eV and 2 eV respectively. VSM measurement of OAm-Fe₃O₄:Sm and PVA- Fe₃O₄:Sm coated, showed superparamagnetic behaviour. The cytotoxicity study on the L929 cell line shows that both oleylamine and PVA-coated samarium doped magnetite were less toxic and biocompatible compared to the uncoated Fe₃O₄:Sm. The hyperthermia study reveals a rise in temperature within a few seconds with a high Specific Absorption Rate (SAR) value, confirming that the functionalized Samarium doped Fe₃O₄ was an effective nanomaterial for hyperthermia application.     

Catalysis of coal hydroliquefaction by synthetic iron catalysts

The following synthetic iron catalyst precursors were investigated: FeOOH and FeOOH-Al₂O₃ (90:10 wt%) co-precipitated by ammonia, washed and dried either in an oven or by spray-drying, and Fe₂O₃ prepared by flame decomposition of FeCl₃ in the gas phase. These catalyst precursors were sulphided in situ by CS₂ during the hydroliquefaction of a highly volatile bituminous coal. An increasing catalytic activity of the iron sulphide was observed as its particle size decreases down to a very low value (0.05 μm), compared to 2–3 μm and to ? 5 μm. Al₂O₃ did not act as an efficient promoter, even if it gives rise to a decrease of the iron sulphide crystallite size. Diffusional limitations and/or plugging by carbonaceous or mineral solids could result in a low efficiency of the iron sulphide crystallites which lie inside one iron catalyst particle. The above cited flame method, allowing the preparation of pure or doped Fe₂O₃ with particle size even less than 0.05 μm, is worthwhile for further work in coal hydroliquefaction catalysis, where the catalyst acts as Fe_1?xS.     

Coal demineralization using sodium hydroxide and acid solutions

A coal product which exceeds the purity requirements for ash, iron and silicon in Hall Cell anode carbon was prepared by a unique leaching sequence involving caustic treatment, followed by treatments with sulphuric and nitric acids. The two acid leaching steps for the three-step process can also be combined with no adverse effect on the coal quality for anode purposes. In the process, the majority of the pyrite reacts with NaOH, forming Fe₂O₃ and Na₂S. Na₂S is dissolved in the leaching liquor and Fe₂O₃ is trapped in the coal matrix. The incorporation of sodium with organic sulphur increases the ash content and decreases the heating value of caustic leached coal on a dry basis. The silicon and aluminium contents are lowered by reactions with NaOH. While most of the reaction products are soluble sodium silicates and aluminates, the remaining silica and alumina form noselite. Dilute sulphuric acid dissolves nearly all of the sodium salts. The remaining iron compounds are dissolved by nitric acid.     

Synthesis and encapsulation of magnetite nanoparticles in PLGA: effect of amount of PLGA on characteristics of encapsulated nanoparticles

Oleic acid-coated superparamagnetic iron oxide nanoparticles (Fe₃O₄) encapsulated within poly(d,l-lactide-co-glycolide) (PLGA) particles were prepared by the w/o/w emulsion technique using poly(vinyl alcohol) as a dispersant. The concentration of PLGA in the oil phase was varied (5, 15, 30, 45, and 60?mg/ml) at constant magnetite concentration in the oil phase (5?mg/ml) to study the properties of composite Fe₃O₄–PLGA nanoparticles. Even though PLGA concentration varied widely in the oil phase, the weight percent of 7–16?nm diameter magnetite in the particles varied only from 56 to 62?% (23–28?vol.%). The obtained composite nanoparticles were essentially spherical with magnetite spatially uniformly dispersed in individual PLGA particles, as measured by transmission electron microscopy (TEM). Also, the magnetite concentration in each particle did not vary widely as determined qualitatively via microscopy. Hydrodynamic diameters of the composite nanoparticles as measured by dynamic light scattering increased by approximately 10?% with added magnetite, with a smaller relative increase in diameter measured by TEM. The zeta potential of the particles was about ?26?mV, independent of Fe₃O₄ loading. Relatively high saturation magnetizations (36–45?emu/g) were measured for these highly loaded particles, with the latter value only 7?emu/g lower than the value measured for the oleic acid-coated particles alone.     

Hydrothermal synthesis of magnetite nanoparticles as MRI contrast agents

Magnetite (Fe₃O₄) nanoparticles prepared using hydrothermal approach were employed to study their potential application as magnetic resonance imaging (MRI) contrast agent. The hydrothermal process involves precursors FeCl₂·4H₂O and FeCl₃ with NaOH as reducing agent to initiate the precipitation of Fe₃O₄, followed by hydrothermal treatment to produce nano-sized Fe₃O₄. Chitosan (CTS) was coated onto the surface of the as-prepared Fe₃O₄ nanoparticles to enhance its stability and biocompatible properties. The size distribution of the obtained Fe₃O₄ nanoparticles was examined using transmission electron microscopy (TEM). The cubic inverse spinel structure of Fe₃O₄ nanoparticles was confirmed by X-ray diffraction technique (XRD). Fourier transform infrared (FTIR) spectrum indicated the presence of the chitosan on the surface of the Fe₃O₄ nanoparticles. The superparamagnetic behaviour of the produced Fe₃O₄ nanoparticles at room temperature was elucidated using a vibrating sample magnetometer (VSM). From the result of custom made phantom study of magnetic resonance (MR) imaging, coated Fe₃O₄ nanoparticles have been proved to be a promising contrast enhanced agent in MR imaging.     

Remarkable effect of Co and Mn on the activity of Fe3 − xMxO4 promoted oxidation of organic contaminants in aqueous medium with H2O2

In this work substituted magnetites Fe_3 − xMn_xO₄ (x=0.21, 0.26 and 0.53), Fe_3 − xCo_xO₄ (x=0;0.19;0.38;0.75) and Fe_3 − xNi_xO₄ (x=0;0.10;0.28;0.54) have been used to promote two different reactions involving H₂O₂: (i) the oxidation of organic molecules namely phenol, hydroquinone and methylene blue dye in aqueous medium and (ii) the peroxide decomposition to O₂. The presence of Co or Mn in the magnetite structure strongly increased the rate of H₂O₂ decomposition and the oxidation of the organic molecules whereas the presence of Ni inhibited both reactions. Kinetic data and CEMS Mössbauer spectroscopy suggest that the H₂O₂ decomposition and the organic oxidation are competitive reactions involving oxidizing species generated by surface M²⁺ (M=Fe, Co or Mn).     

Synthesis of magnetite powder from iron ore tailings

Iron ore tailing—a waste material of mineral beneficiation plants, is used as a source of iron for synthesizing magnetite powder. Iron ore tailings containing 15.98% Fe₂O₃, 83.36% SiO₂ and 0.44% Al₂O₃ have been subjected to HCl digestion on a hot plate to extract the entire amount of Fe₂O₃ as FeCl₃. A portion of extracted FeCl₃ solution has been used to convert it to FeCl₂ via metallic iron formation by using NaBH₄ as a reducing reagent. Then, the left out FeCl₃ solution and derived FeCl₂ solutions (from FeCl₃) are mixed in an appropriate molar ratio (2:1) for synthesizing magnetite powder by the addition of alkali solution. The magnetite powder samples have been characterized by means of powder XRD, SEM, vibrating sample magnetometer and laser particle size analyzer. XRD study confirms the formation of magnetite phase. The magnetite particles synthesized in different ways show varying degrees of magnetization behavior which is attributed to the change in their particle size induced by the use of different precipitating reagents.     

Synthesis of nanocrystalline TiO<Subscript>2</Subscript>-coated coal fly ash for photocatalyst

In order to more easily separate TiO₂ photocatalyst from treated wastewater, TiO₂ photocatalyst is immobilized on coal fly ash by precipitation method. The titanium hydroxide precipitated on coal fly ash by neutralization of titanium chloride is transformed into titanium dioxide by heat treatment in the temperature range of 300–700 ‡C. The crystalline structure of the titanium dioxide shows anatase type in all ranges of heat treatment temperature. The crystal size of anatase increases with increasing heat treatment temperature, with the drawback being the lower removal ability of NO gas. When the coal fly ash coated with 10 wt% of TiO₂ was calcined at 300 and 400 ‡C for 2 hrs, the average crystal size of anatase appeared about 9 nm, and the removal rates of NO gas were 63 and 67.5%, respectively. The major iron oxide, existing in coal fly ash as impurity, is magnetite (Fe₃O₄). Phase transformation of magnetite into hematite (Fe₂O₃) by heat treatment improves the removal rate of NO gas for TiO₂-coated coal fly ash.     

The macromolecular nature of bituminous coal

Considerable insight into the macromolecular state of coal has been obtained by examining the optical anisotropy of untreated solvent-swollen, and chemically derivatized thin sections of coal. From the effect of pressure on the optical anisotropy, and from the rate and degree of recovery after release of pressure, it was found possible to determine whether the coal is in a plastic or rubbery state, whether a rubbery state is cross-linked and how mobile the macromolecular chain segments are. The experimental technique utilized for this work was transmission optical microscopy in polarized light of uncontaminated thin sections of vitrinite from a bituminous coal. The study included in-situ microscopic examination of swollen coal immersed in pyridine, THF, toluene and several other solvents. Some samples were O-methylated to assess the impact of hydrogen bonding. New results and conclusions derived from this study include: (1) the vitrinite of raw bituminous coal is a plastic macromolecular substance; (2) coal swollen in pyridine (and some other ‘specific’ solvents) is a cross-linked rubber and its macromolecular chain segments have substantial mobility; (3) when pyridine-extracted coal dries, it reverts to a plastic; (4) the large discrepancies previously found between values of M_c (molecular weight between crosslinks) measured by solvent-swelling and by stress-strain techniques is caused by differences in secondary interactions; (5) various solvents can, by their effect on secondary interactions, create appreciably different macromolecular structures in the coal; (6) different solvents, depending on their effect on secondary interactions in the coal, can be expected to extract chemically different molecules from a coal - rates of extraction and the ability of solvents to extract larger molecules should also differ; (7) O-methylated coal is a plastic, and thus, in addition to hydrogen bonding, other secondary interactions are of great importance; (8) it is likely that in their dry condition, solvent-treated coal and O-alkylated coal, as well as untreated coal, are in glassy states; (9) pyridine by itself appears to relax substantially all secondary interactions which are weakened by O-methylation, only permanent bonds are not relaxed; (10) previous measurements of M_c can now be reassessed in view of these results.