Prussian blue as a single precursor for synthesis of Fe/Fe3C encapsulated N-doped graphitic nanostructures as bi-functional catalysts

We report a unique, single source precursor Prussian blue (iron(III) ferrocyanide (Fe-4(III)Fe-II(CN)(6)](3))) for the synthesis of Fe/Fe3C nanoparticle encapsulated N-doped graphitic layers and bamboo-like graphitic nanotubes. Hollow N-doped graphite (N-HG) nanostructures are obtained when the encapsulated nanostructures are treated with an acid. Both the encapsulated nanostructures and N-HG are shown to be applicable as bi-functional electrocatalysts for oxygen reduction (ORR) and oxygen evolution reactions (OER). The ORR activity is shown to be improved for N-HG and is comparable to commercial Pt/C. On the other hand, encapsulated nanostructures exhibit OER activity with long-term stability comparable to commercial RuO2.

Prussian blue as a single precursor for synthesis of Fe/Fe3C encapsulated N-doped graphitic nanostructures as bi-functional catalysts

We report a unique, single source precursor Prussian blue (iron(III) ferrocyanide (Fe-4(III)Fe-II(CN)(6)](3))) for the synthesis of Fe/Fe3C nanoparticle encapsulated N-doped graphitic layers and bamboo-like graphitic nanotubes. Hollow N-doped graphite (N-HG) nanostructures are obtained when the encapsulated nanostructures are treated with an acid. Both the encapsulated nanostructures and N-HG are shown to be applicable as bi-functional electrocatalysts for oxygen reduction (ORR) and oxygen evolution reactions (OER). The ORR activity is shown to be improved for N-HG and is comparable to commercial Pt/C. On the other hand, encapsulated nanostructures exhibit OER activity with long-term stability comparable to commercial RuO2.

Synthesis of zero valent iron nanoparticles and application to removal of arsenic(III) and arsenic(V) from water

Recently nano scale zero valent iron particles (nZVI) have been considered as smart adsorbent for environmental and groundwater remediation. Although several synthetic methods are available for the preparation of nZVI, air stable nZVI are not available for remediation works. Further, challenges demand synthesis of nZVI without stabilizers and capping agents. A modified methodology for the synthesis of air stable nZVI has been developed without any capping agents and characterized by powder X-Ray Diffraction (XRD), Scanning Electron Microscopy Energy-dispersive X-Ray (SEM-EDS), Transmission Electron Microscopy (TEM) and X-Ray Photoelectron Spectroscopy (XPS). The results of the present study suggest that the synthetic nZVI are air-stable over a period of one year and consists of particles of 30-40 nm in diameter. Although a layer of less than 3 am thick oxide/hydroxide is observed by TEM and XPS, it appears to be due to oxidation of outer surface during analysis. Adsorption study has shown that the synthetic nZVI are more effective adsorbent than the commercial nZVI and can remove simultaneously arsenite As-III] and arsenate As-V] from water without prior reduction of As-V to As-III. The removal process is adsorptive rather than precipitative and the removal of As-III is greater than that of As-V.

Magnetic Properties of Iron Particles Embedded in Multiwall Carbon Nanotubes

Iron nanoparticles are embedded in multiwall carbon nanotubes by the chemical vapor deposition, where benzene and ferrocene are taken as precursor materials. Varying quantity of iron particles are embedded in these tubes by taking different amount of ferrocene. These particles exhibit a magnetic moment up to 98 emu/g and an enhanced coercivity in the range of 500-2000 Oe. Negative magnetoresistance similar to 10% is observed in the presence of magnetic field up to 11 T applied at various temperatures in the range of 1.3 K-300 K. It is argued that the enhanced coercivity is due to the shape anisotropy. The negative magnetoresistance is believed to be due to the weak localization and spin dependent scattering of electrons by the ferromagnetic particles. In addition we also observe a dependence of the magnetoresistance on the direction of applied field and this is correlated with the shape anisotropy of the Fe particles.

Effect of carbon equivalent and inoculation on residual stresses in grey iron castings

It is virtually impossible to produce castings free from internal stresses using conventional methods of founding. Castings with appreciable stresses distort during storage, transportation, machining and service. Though composition and melt treatment are known to affect the magnitude of residual stress in castings, the data on the effect of carbon equivalent and inoculation on the magnitude of residual stress in castings are limited. In the present investigation, an attempt is made to study (i) the effect of carbon equivalent on residual stress in cast iron castings, and (ii) the effect of inoculants such as calcium silicide and ferrosilicon on residual stress in iron castings in the carbon equivalent range 3.0–4.0%. The results of the investigation indicate the following: (i) the residual strains decrease linearly with increase in carbon equivalent in the uninoculated and inoculated irons; (ii) the tensile residual stresses decrease linearly with increase in carbon equivalent value of the uninoculated, calcium silicide-inoculated and ferrosilicon-inoculated cast iron castings; (iii) the ratio of UTS to residual stress increased on inoculating the grid castings. This increase is higher for calcium silicide-inoculated grids than for ferrosilicon-inoculated grid castings. This implies that from the residual stress point of view, inoculation of the iron with calcium silicide is beneficial.

Dependence of pH and surfactant effect in the synthesis of magnetite(Fe3O4) nanoparticles and its properties

Nanoparticles of Fe3O4 were synthesized by co-precipitation in an aqueous solution containing ferrous and ferric salts (1:2) at varying pH with ammonia as a base. It was found that the value of pH influences the reaction mechanism for the formation of Fe3O4. Furthermore, the addition of mercaptoethanol significantly reduced the crystalline size of Fe3O4 nanoparticles from 15.03 to 8.02 nm. X-ray diffraction (XRD) spectra revealed that the synthesized nanoparticles were epsilon-Fe2O3 or Fe3O4 phase. To further prove the composition of the product, as-prepared Fe3O4 were examined by X-rayphotoelectron spectroscopy (XPS). Magnetic properties of the obtained particles were determined by vibrating sample magnetometer (VSM). Further analysis of the X-ray studies shows that while maintaining a pH value of 6 and 9 in a solution containing iron salts II and III ions produces epsilon-Fe2O3. Whereas a pH value of 11 produces magnetite (Fe3O4) phase. All of these results show that the pH has a major role in the observed phase formation of (Fe3O4) nanoparticles.

Fe-Cr/Al2O3 metal-ceramic composites: Nature and size of the metal particles formed during hydrogen reduction

Fe-Cr/Al2O3 metal-ceramic composites prepared by hydrogen reduction at different temperatures and for different periods have been investigated by a combined use of Mossbauer spectroscopy, x-ray diffraction, transmission electron microscopy, and energy-dispersive x-ray spectroscopy in order to obtain information on the nature of the metallic species formed. Total reduction of Fe3+ does not occur by increasing the reduction time at 1320 K from 1 to 30 h, and the amount of superparamagnetic metallic species is essentially constant (about 10%). Temperatures higher than 1470 K are needed to achieve nearly total reduction of substitutional Fe3+. Interestingly, iron favors the reduction of chromium. The composition of the Fe-Cr particles is strongly dependent on their size, the Cr content being higher in particles smaller than 10 nm.

Iron, cobalt and nickel nanoparticles encapsulated in carbon obtained by the arc evaporation of graphite with the metals

Are evaporation of graphite with Fe, Co and Ni yields two distinct types of metal nanoparticles, wrapped in graphitic layers and highly resistant to oxidation. Electron microscopy shows that the metal particles (10-40 nm) in the stub region are encapsulated in carbon onions, the particles in the soot being considerably smaller (2-15 nm). The metal particles in the soot are either ferromagnetic with lowered Curie temperatures or superparamagnetic.

Investigations of the reduction behavior of Iron-impregnated alumina gels (Fe/AlOOH) and the formation of Fe0-Al2O3 metal-ceramic composites

Fe/AlOOH gels calcined and reduced at different temperatures have been investigated by a combined use of Mossbauer spectroscopy, x-ray diffraction, and electron microscopy in order to obtain information on the nature of the iron species formed as well as the various reduction processes. Calcination at or below 1070 K mainly gives reducible Fe3+ while calcination at higher temperatures gives substitutional Fe3+ in the form of Al2-xFexO3. The Fe3+ species in the calcined samples are, by and large, present in the form of small superparamagnetic particles. Crystallization of Al2O3 from the gels is catalyzed by Fe2O3 as well as FeAl2O4. Fe (20 wt. %)/AlOOH gels calcined at or below 870 K give FeAl2O4 when reduced in hydrogen at 1070 K or lower and a ferromagnetic Fe0-Al2O3 composite (with the metallic Fe particles >100 angstrom) when reduced at 1270 K. Samples calcined at 1220 K or higher give the Fe0-Al2O3 composite when reduced in the 870-12,70 K range, but a substantial proportion of Fe3+ remains unreduced in the form of Al2-xFexO3, showing thereby the extraordinary stability of substitutional Fe3+ to reduction even at high temperatures. Besides the ferromagnetic Fe0-Al2O3 composite, high-temperature reduction of Al2-xFexO3 yields a small proportion of superparamagnetic Fe0-Al2O3 wherein small metallic particles (<100 angstrom) are embedded in the ceramic matrix. In order to preferentially obtain the Fe0-Al2O3 composite on reduction, Fe/AlOOH gels should be calcined at low temperatures (less-than-or-equal-to 1100 K); high-temperature calcination results in Al2-xFexO3. Several modes of formation of FeAl2O4 are found possible during reduction of the gels, but a novel one is that involving the reaction, 2Fe3+ + Fe0 --> 3Fe2+.

Synthesis of acicular hydrogoethite (alpha-FeOOH center dot xH(2)O; 0.1 < x < 0.22) particles using morphology controlling cationic additives and magnetic properties of maghemite derived from hydrogoethite

A method for the preparation of acicular hydrogoethite (alpha -FeOOH.xH(2)O, 0.1 < x < 0.22) particles of 0.3-1 mm length has been optimized by air oxidation of Fe( II) hydroxide gel precipitated from aqueous (NH4)(2)Fe(SO4)(2) solutions containing 0.005-0.02 atom% of cationic Pt, Pd or Rh additives as morphology controlling agents. Hydrogoethite particles are evolved from the amorphous ferrous hydroxide gel by heterogeneous nucleation and growth. Preferential adsorption of additives on certain crystallographic planes thereby retarding the growth in the perpendicular direction, allows the particles to acquire acicular shapes with high aspect ratios of 8-15. Synthetic hydrogoethite showed a mass loss of about 14% at similar to 280 degreesC, revealing the presence of strongly coordinated water of hydration in the interior of the goethite crystallites. As evident from IR spectra, excess H2O molecules (0.1- 0.22 per formula unit) are located in the strands of channels formed in between the double ribbons of FeO6 octahedra running parallel to the c- axis. Hydrogoethite particles constituted of multicrystallites are formed with Pt as additive, whereas single crystallite particles are obtained with Pd (or Rh). For both dehydroxylation as well as H-2 reduction, a lower reaction temperature (similar to 220 degreesC) was observed for the former (Pt treated) compared to the latter (Pd or Rh) (similar to 260 degreesC). Acicular magnetite (Fe3O4) was prepared either by reducing hydrogoethite (magnetite route) or dehydroxylating hydrogoethite to hematite and then reducing it to magnetite (hematite- magnetite route). According to TEM studies, preferential dehydroxylation of hydrogoethite along < 010 > leads to microporous hematite. Maghemite (gamma -Fe2O3 (-) (delta), 0 < < 0.25) was obtained by reoxidation of magnetite. The micropores are retained during the topotactic transformation to magnetite and finally to maghemite, whereas cylindrical mesopores are formed due to rearrangement of the oxygen sublattice from hexagonal to cubic close packing during the conversion of hydrogoethite to magnetite and then to maghemite. Accordingly, three different types of maghemite particles are realized: strongly oriented multicrystalline particles, single crystalline acicular particles with micropores or crystallites having mesopores. Higher values of saturation magnetization ((s) = 74 emu g(-1)) and coercivity (H-c = 320 Oe) are obtained for single crystalline mesoporous particles. In the other cases, the smaller size of particles and larger distribution of micropores decreases sigma (s) considerably ( < 60 emu g(-1)) due to relaxation effects of spins on the surface atoms as revealed by Mossbauer spectroscopy.

Fe–Cr/Al2O3 metal-ceramic composites: Nature and size of the metal particles formed during hydrogen reduction

Fe-Cr/Al2O3 metal-ceramic composites prepared by hydrogen reduction at different temperatures and for different periods have been investigated by a combined use of Mössbauer spectroscopy, x-ray diffraction, transmission electron microscopy, and energy-dispersive x-ray spectroscopy in order to obtain information on the nature of the metallic species formed. Total reduction of Fe3+ does not occur by increasing the reduction time at 1320 K from 1 to 30 h, and the amount of superparamagnetic metallic species is essentially constant (about 10%). Temperatures higher than 1470 K are needed to achieve nearly total reduction of substitutional Fe3+. Interestingly, iron favors the reduction of chromium. The composition of the Fe-Cr particles is strongly dependent on their size, the Cr content being higher in particles smaller than 10 nm.

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.

Structure and Mechanistic Insights into Novel Iron-mediated Moonlighting Functions of Human J-protein Cochaperone, Dph4

J-proteins are obligate cochaperones of Hsp70s and stimulate their ATPase activity via the J-domain. Although the functions of J-proteins have been well understood in the context of Hsp70s, their additional co-evolved ``physiological functions'' are still elusive. We report here the solution structure and mechanism of novel iron-mediated functional roles of human Dph4, a type III J-protein playing a vital role in diphthamide biosynthesis and normal development. The NMR structure of Dph4 reveals two domains: a conserved J-domain and a CSL-domain connected via a flexible linker-helix. The linker-helix modulates the conformational flexibility between the two domains, regulating thereby the protein function. Dph4 exhibits a unique ability to bind iron in tetrahedral coordination geometry through cysteines of its CSL-domain. The oxidized Fe-Dph4 shows characteristic UV-visible and electron paramagnetic resonance spectral properties similar to rubredoxins. Iron-bound Dph4 (Fe-Dph4) also undergoes oligomerization, thus potentially functioning as a transient ``iron storage protein,'' thereby regulating the intracellular iron homeostasis. Remarkably, Fe-Dph4 exhibits vital redox and electron carrier activity, which is critical for important metabolic reactions, including diphthamide biosynthesis. Further, we observed that Fe-Dph4 is conformationally better poised to perform Hsp70-dependent functions, thus underlining the significance of iron binding in Dph4. Yeast Jjj3, a functional ortholog of human Dph4 also shows a similar iron-binding property, indicating the conserved nature of iron sequestration across species. Taken together, our findings provide invaluable evidence in favor of additional co-evolved specialized functions of J-proteins, previously not well appreciated.

Low temperature charge transport and microwave absorption of carbon coated iron nanoparticles-polymer composite films

In this paper, the low temperature electrical conductivity and microwave absorption properties of carbon coated iron nanoparticles-polyvinyl chloride composite films are investigated for different filler fractions. The filler particles are prepared by the pyrolysis of ferrocene at 980 degrees C and embedded in polyvinyl chloride matrix. The high resolution transmission electron micrographs of the filler material have shown a 5 nm thin layer graphitic carbon covering over iron particles. The room temperature electrical conductivity of the composite film changes by 10 orders of magnitude with the increase of filler concentration. A percolation threshold of 2.2 and an electromagnetic interference shielding efficiency (EMI SE) of similar to 18.6 dB in 26.5-40 GHz range are observed for 50 wt% loading. The charge transport follows three dimensional variable range hopping conduction. (C) 2012 Elsevier Ltd. All rights reserved.