Photoelectrochemical properties of Fe2O3-Nb2O5 films prepared by sol-gel method

Fe2O3-Nb2O5 coating films of various Nb/(Fe + Nb) mole ratios were prepared on nesa silica glass substrates from Fe(NO3)3.9H2O - NbCl5 - CH3(CH2)2CH2OH - CH3COOH solutions by the sol-gel method. The photoanodic properties were studied in a three-electrode cell with an aqueous buffer solution of pH = 7 as the supporting electrolyte. The crystalline phases identified were alpha-Fe2O3 (Nb/(Fe + Nb) = 0), alpha-Fe2O3 + FeNbO4 (Nb/(Fe + Nb) = 0.25), FeNbO4 (Nb/(Fe + Nb) = 0.5), FeNbO4 + Nb2O5 (Nb/(Fe + Nb) = 0.75), and Nb2O5 (Nb/(Fe + Nb) = 1). When the Nb/(Fe + Nb) mole ratio increased from 0 to 0.25, the crystalline phases changed from alpha-Fe2O3 to alpha-Fe2O3 + FeNbO4, the photoanodic current under white light illumination increased, and the photoanodic current under monochromatized light illumination increased in both visible and ultraviolet regions. When the Nb/(Fe + Nb) ratio increased over 0.25, the crystalline phases changed to FeNbO4, FeNbO4 + Nb2O5, or Nb2O5, and the photoanodic current decreased. The sample consisting of alpha-Fe2O3 and FeNbO4 (Nb/(Fe + Nb) = 0.25) exhibited photoresponse extending to 600 nm and an IPCE of 18% at a wavelength of 325 nm.     

Excited carrier dynamics of alpha-Cr2O3/alpha-Fe2O3 core-shell nanostructures

In this work alpha-Cr(2)O(3)/alpha-Fe(2)O(3) core-shell polycrystalline nanostructures were synthesized by using alpha-Cr(2)O(3) nanoparticles as seed crystals during aqueous nucleation. The formation of alpha-Fe(2)O(3) polycrystallites on alpha-Cr(2)O(3) surfaces was confirmed by X-ray diffraction, transmission electron microscopy, and energy-dispersive X-ray analysis. The excited-state relaxation dynamics of as-grown core-shell structures and "pure" alpha-Fe(2)O(3) particles of the same size were measured with femtosecond transient absorption spectroscopy. The results show the carrier lifetimes decay within a few picoseconds regardless of sample. This is likely due to fast recombination/trapping of carriers to defects and iron d-states.     

Synthesis and magnetic properties of the exchange-coupled SrFe10.7Al1.3O19/Co composite

The magnetic composite SrFe_10.7A_l1.3O₁₉/Co was synthesized by ethylene glycol reduction of cobalt ions on the surface of hexaferrite particles dispersed in the solvent. The resulting material contained magnetically hard submicron hexaferrite particles covered by soft magnetic cobalt nanoparticles. The composite demonstrated the exchange-coupling effect between hard and soft magnetic phases.     

Fe/Co alloys for the catalytic chemical vapor deposition synthesis of single- and double-walled carbon nanotubes (CNTs). 2. The CNT-Fe/Co-MgAl2O4 system

A detailed 57Fe M?ssbauer study of the Mg(0.8)Fe(0.2-y)Co(y)Al2O4 (y = 0, 0.05, 0.1, 0.15, 0.2) solid solutions and of the CNT-Fe/Co-MgAl2O4 nanocomposite powders prepared by reduction in H2-CH4 has allowed characterization of the different iron phases involved in the catalytic process of carbon nanotube (CNT) formation and to correlate these results with the carbon and CNT contents. The oxide precursors consist of defective spinels of general formulas (Mg(1-x-y)(2+)Fe(x-3alpha)(2+)Fe(2alpha)(3+)[symbol: see text](alpha)Co(y)(2+)Al2(3+))O4(2-) . The metallic phase in the CNT-Fe/Co-MgAl2O4 nanocomposite powders is mostly in the form of the ferromagnetic alpha-Fe/Co alloy with the desired composition. For high iron initial proportions, the additional formation of Fe3C and gamma-Fe-C is observed while for high cobalt initial proportions, the additional formation of a gamma-Fe/Co-C phase is favored. The higher yield of CNTs is observed for postreaction alpha-Fe(0.50)Co(0.50) catalytic particles, which form no carbide and have a narrow size distribution. Alloying is beneficial for this system with respect to the formation of CNTs.     

Understanding of the finite size effects on lattice vibrations and electronic transitions of nano alpha-Fe2O3

Alpha-Fe(2)O(3) nanocrystals with controlled diameters ranging from 10 to 63 nm were successfully prepared. The finite size effects in alpha-Fe(2)O(3) nanocrystals were probed by X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, UV-visible spectrum, and magnetization measurements. With a size reduction, alpha-Fe(2)O(3) nanocrystals showed a lattice expansion and an enlarged axial ratio of c/a that is in apparent contradiction to the previous conjecture of high lattice symmetry for alpha-Fe(2)O(3) nanocrystals at small sizes. The surface terminations of alpha-Fe(2)O(3) nanocrystals were found to be highly hydrated with a size dependence that surprisingly follows the surface hydration chemistry of anatase TiO2 nanocrystals reported recently by us. The lattice vibrations, electronic transitions, and magnetic properties of alpha-Fe(2)O(3) nanocrystals were significantly modified by surface hydration and lattice expansion. The finite size effects that occurred in alpha-Fe(2)O(3) nanocrystals at small sizes were first found to give a red shift in frequencies of perpendicular mode at 540 cm(-1), a blue shift in the electronic transition of double exciton process in visible region, and a significant decrease in the coercive force.     

Translucent thin film Fe2O3 photoanodes for efficient water splitting by sunlight: nanostructure-directing effect of Si-doping

Thin, silicon-doped nanocrystalline alpha-Fe2O3 films have been deposited on F-doped SnO2 substrates by ultrasonic spray pyrolysis and chemical vapor deposition at atmospheric pressure. The photocatalytic activity of these films with regard to photoelectrochemical water oxidation was measured at pH 13.6 under simulated AM 1.5 global sunlight. The photoanodes prepared by USP and APCVD gave 1.17 and 1.45 mA/cm2, respectively, at 1.23 V vs RHE. The morphology of the alpha-Fe2O3 was strongly influenced by the silicon doping, decreasing the feature size of the mesoscopic film. The silicon-doped alpha-Fe2O3 nano-leaflets show a preferred orientation with the (001) basal plane normal to the substrate. The best performing photoanode would yield a solar-to-chemical conversion efficiency of 2.1% in a tandem device using two dye-sensitized solar cells in series.     

Photoinduced transformation of gamma-HCH in the presence of dissolved organic matter and enhanced photoreactive activity of humate-coated alpha-Fe2O3

This study examined phototransformation of gamma-hexachlorocyclohexane (gamma-HCH) in different solutions. The presence of dissolved organic matter (DOM) inhibited the phototransformation of gamma-HCH. This phenomenon could be correlated to the binding interaction between gamma-HCH and DOM. Alpha-Fe2O3 promoted the transformation of gamma-HCH. The humate-coated alpha-Fe2O3 revealed a slight, however significant, favorable effect compared to the bare one. Fourier transform infrared spectroscopy (FTIR) offered the direct evidence that humate-coated alpha-Fe2O3 could form surface Fe(III)-carboxylate complexes by ligand exchange. Additional experiments demonstrated that the photocorrosion of alpha-Fe2O3 coated by DOM was much more acute than that of the bare one. These combined results suggested that the transformation of gamma-HCH on humate-coated alpha-Fe2O3 is more related to a surface complex and not to a semiconductor-assisted photoreaction. In the humate-coated alpha-Fe2O3, absorption of a photon results in an excited ligand-to-metal charge-transfer state of the complexes, and a rich variety of free radical reactions ensue, which is concurrently accompanied by the dissolution of the iron oxide. Such reactions may generate reactive transients such as superoxide and hydroxyl radicals, which may be expected to transform gamma-HCH.     

Visible light photocatalytic decomposition of 2-naphthol by anodic-biased alpha-Fe2O3 film

Transparent alpha-Fe2O3 films with varying film thickness were formed on a SnO2 transparent conducting film-coated glass substrate by metal organic deposition. Under anodic-biased conditions, the alpha-Fe2O3 film showed a high photocatalytic activity for the decomposition of 2-NAP with visible light irradiation. The alpha-Fe2O3 is transformed to inactive hydroxide as the reaction proceeds, while the activity of alpha-Fe2O3 is almost maintained in acetonitrile.     

丁苯、丁腈基聚氨酯的形态与性能

用示差扫描量热法 (DSC)、红外分光光度计 (FTIR)和原子力显微镜 (AFM)研究了端羟基聚丁二烯 苯乙烯共聚物 (HTBS)、端羟基聚丁二烯 丙烯腈共聚物 (HTBN)和端羟基聚丁二烯 (HTPB)与甲苯二异氰酸酯、1 ,4 丁二醇构成的溶液法聚二烯烃基聚氨酯 (PU)的形态结构 .结果表明HTPB和HTBS基PU的相分离程度很大 ,而HTBN基PU的相分离程度小 .这可能归因于HTBS软段的极性低 ,不能与硬段形成氢键 ,而HTBN软段中的腈基具有很强的极性 ,且可以与硬段形成氢键作用 ,增加了软硬段间的相容性 ,相分离程度明显降低 .AFM表明HTBN PU随着硬段含量提高 ,表面粗糙度增大 ,由软段为连续相逐渐过渡到双连续结构 .在硬段含量 6 3%时 ,HTBN和HTPB基PU均呈双连续结构 ,而HTBS PU中硬段为连续相 .HTBN PU软段的相区尺寸在1 2nm左右 ,表面粗糙度较大 ,HPBS PU软段的相区尺寸在 1 1nm左右 ,表面粗糙度最小 ,HTPB PU存在 1 4nm和 5 0nm大小不等的软段相区尺寸 .力学性能表明 ,在软段中引入苯乙烯和丙烯腈结构 ,可使聚氨酯抗张强度分别提高 1 5和 2倍 ,模量和断裂伸长率也明显提高     

Quantitative SAXS analysis of the P123/water/ethanol ternary phase diagram

The ternary phase diagram of the amphiphilic triblock copolymer PEO-PPO-PEO ((EO)(20)(PO)(70)(EO)(20) commercialized under the generic name P123), water, and ethanol has been investigated at constant temperature (T = 23 degrees C) by small-angle X-ray scattering (SAXS). The microstructure resulting from the self-assembly of the PEO-PPO-PEO block copolymer varies from micelles in solution to various types of liquid crystalline phases such as cubic, 3D hexagonal close packed spheres (HCPS), 2D hexagonal, and lamellar when the concentration of the polymer is increased. In the isotropic liquid phase, the micellar structural parameters are obtained as a function of the water-ethanol ratio and block copolymer concentration by fitting the scattering data to a model involving core-shell form factor and a hard sphere structure factor of interaction. The micellar core, the aggregation number, and the hard sphere interaction radius decrease when increasing the ethanol/water ratio in the mixed solvent. We show that the fraction of ethanol present in the core is responsible for the swelling of the PPO blocks. In the different liquid crystalline phases, structural parameters such as lattice spacing, interfacial area of PEO block, and aggregation number are also evaluated. In addition to classical phases such as lamellar, 2D hexagonal, and liquid isotropic phases, we have observed a two-phase region in which cubic Fm3m and P6(3)mmc (hexagonally close packing of spheres (HCPS)) phases coexist. This appears at 30% (w/w) of P123 in pure water and with 5% (w/w) of ethanol. At 10% (w/w) ethanol, only the HCPS phase remains present.     

Genesis of nanostructured, magnetically tunable ceramics from the pyrolysis of cross-linked polyferrocenylsilane networks and formation of shaped macroscopic objects and micron scale patterns by micromolding inside silicon wafers

The ability to form molded or patterned metal-containing ceramics with tunable properties is desirable for many applications. In this paper we describe the evolution of a ceramic from a metal-containing polymer in which the variation of pyrolysis conditions facilitates control of ceramic structure and composition, influencing magnetic and mechanical properties. We have found that pyrolysis under nitrogen of a well-characterized cross-linked polyferrocenylsilane network derived from the ring-opening polymerization (ROP) of a spirocyclic [1]ferrocenophane precursor gives shaped macroscopic magnetic ceramics consisting of alpha-Fe nanoparticles embedded in a SiC/C/Si(3)N(4) matrix in greater than 90% yield up to 1000 degrees C. Variation of the pyrolysis temperature and time permitted control over the nucleation and growth of alpha-Fe particles, which ranged in size from around 15 to 700 A, and the crystallization of the surrounding matrix. The ceramics contained smaller alpha-Fe particles when prepared at temperatures lower than 900 degrees C and displayed superparamagnetic behavior, whereas the materials prepared at 1000 degrees C contained larger alpha-Fe particles and were ferromagnetic. This flexibility may be useful for particular materials applications. In addition, the composition of the ceramic was altered by changing the pyrolysis atmosphere to argon, which yielded ceramics that contain Fe(3)Si(5). The ceramics have been characterized by a combination of physical techniques, including powder X-ray diffraction, TEM, reflectance UV-vis/near-IR spectroscopy, elemental analysis, XPS, SQUID magnetometry, M?ssbauer spectroscopy, nanoindentation, and SEM. Micromolding of the spirocyclic [1]ferrocenophane precursor within soft lithographically patterned channels housed inside silicon wafers followed by thermal ROP and pyrolysis enabled the formation of predetermined micron scale designs of the magnetic ceramic.     

New type of thermoplastic multiblock elastomers––poly(ester-block-amide)s––based on oligoamide 12 and oligoester prepared from dimerized fatty acid

Multiblock poly(ester-block-amide)s (PEA) elastomers comprising hard blocks of oligoamide and oligoester soft segments were prepared and their structure-property relations were analysed. The polycondensation reaction of oligoesters (prepared from 1,4-butanediol and dimerized fatty acid) with oligolaurolactam (PA12) gave copolymer series with variable blocks content (the soft segments content was varied from 24 to 60 wt.%). PEAs are the phase system composed of crystallised sequences of oligoamide (hard segment phase) as well as oligoesters (soft segment phase). Mixing between the hard and soft phases was studied by thermal and mechanical measurements (DSC, DMTA). These results have indicated on a multiphase structure of investigated materials. The relationship between the observed thermal and tensile properties and the soft/hard segments content indicated on an increase of the phase separation with soft segments content.     

Ordered mesoporous Fe2O3 with crystalline walls

Alpha-Fe(2)O(3) has been synthesized with an ordered mesoporous structure and crystalline walls that exhibit a near-single crystal-like order. The unique magnetic behavior of the material, distinct from bulk nanoparticles of alpha-Fe(2)O(3) or mesoporous Fe(2)O(3) with disordered walls, has been established. Magnetic susceptibility, M?ssbauer, and neutron diffraction data show that the material possesses the same long-range magnetic order as bulk alpha-Fe(2)O(3), despite the wall thickness being less than the 8 nm limit below which magnetic ordering breaks down in nanoparticulate alpha-Fe(2)O(3), yet the Morin transition of bulk alpha-Fe(2)O(3) is absent. It is also shown by TEM, PXRD, and EXAFS that alpha-Fe(2)O(3) with the same ordered mesoporous structure but disordered walls contains small crystalline domains. M?ssbauer and magnetic susceptibility data demonstrate that this material exhibits no long-range magnetic order but superparamagnetic behavior.     

Quantum size effect on surface photovoltage spectra: alpha-Fe(2)O(3) nanocrystals on the surface of monodispersed silica microsphere

A new method for the preparation of Fe(2)O(3) nanoparticle/SiO(2) microsphere composites is described, in which fine alpha-Fe(2)O(3) nanocrystals were prepared by forced hydrolysis of FeCl(3) aqueous solution. The structure and optical spectra of these alpha-Fe(2)O(3) nanocrystals have been studied. Their visible optical absorption can be enhanced by their adsorptions on the surface of SiO(2) microspheres and thereafter simple packing of these microspheres to the aggregated structures. The size-dependent photogenerated surface photovoltage spectra (SPS) of these composites were studied, and quantum confinement effects of the SPS properties were observed. The transport of photoinduced charges between nanocrystals with intrinsic electronic nature of confined states accounts for this phenomenon. These results are helpful in understanding the relationship among d-d transition and charge-transfer transition in transition metal oxides and find applications in photovoltaic devices.     

Study on the NaNp/Al2O3-SiO2 system

Sodium naphthenide (NaNp) deposited on aluminosilicate gels yields systems that exhibit signals in EPR spectra, the multiplicity, g values, and intensities of which depend on the gel composition. The symmetrical singlets (I) of a g(1) value of 2.00 were assigned to the complexed naphthalene anion radicals on the centers occurring on the surfaces of the alumina and silica phases of the gels studied. Those radicals complexed on surface Lewis acid sites are of hard acid/hard base type according to Pearson theory, and are bonded to the sites by ionic forces. The asymmetrical singlets (II) described by the value g(2)=1.95 were assigned to naphthalene anion radicals, which are complexed by the centers of the aluminosilicate phase of the gels studied. Those radicals, complexed on surface Lewis acid sites of this phase, are of soft acid/soft base type and are bonded to the sites by covalent bonds. The highest intensity of the singlet (I) was recorded for the system containing alumina gel. The highest intensity of the singlet (II) was recorded for the system containing Al(2)O(3) in 30 wt%. The structures of Lewis acid sites on aluminosilicate phases are postulated to be different from those on alumina or silica phases.     

Facile fabrication of long alpha-Fe(2)O(3), alpha-Fe and gamma-Fe(2)O(3) hollow fibers using sol-gel combined co-electrospinning technology

Long alpha-Fe(2)O(3) hollow fibers have been prepared through a facile sol-gel combined co-electrospinning technique using ferric citrate as precursor, and alpha-Fe and gamma-Fe(2)O(3) hollow fibers have been obtained by reduction and reoxidation at different conditions. The outer diameter of the as-prepared hollow fibers is 0.5-5 microm with wall thickness of 200-800 nm. The obtained tubular fibers were characterized by thermal gravimetric (TG), FT-IR spectra, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Raman techniques. In addition, magnetic properties of alpha-Fe and gamma-Fe(2)O(3) hollow fibers have also been investigated.     

Synthesis of ordered mesoporous Fe3O4 and gamma-Fe2O3 with crystalline walls using post-template reduction/oxidation

Ordered mesoporous Fe(3)O(4) with crystalline walls (inverse spinel structure) has been synthesized for the first time, representing to the best of our knowledge, the first synthesis of a reduced mesoporous iron oxide. Synthesis was achieved by reducing ordered mesoporous alpha-Fe(2)O(3) (corundum structure) to Fe(3)O(4) spinel then to gamma-Fe(2)O(3) by oxidation, while preserving the ordered mesostructure and crystalline walls throughout. Such solid/solid transformations demonstrate the stability of the mesostructure to structural phase transitions from the hexagonal close packed oxide subarray of alpha-Fe(2)O(3) (corundum structure) to the cubic close packed subarray of Fe(3)O(4) spinel and gamma-Fe(2)O(3). Preliminary magnetic measurements reveal that the spins in both Fe(3)O(4) and gamma-Fe(2)O(3) are frozen at 295 K, despite the wall thickness (7 nm) being less than the lower limit for such freezing in corresponding nanoparticles (>8 nm).     

Exchange‐Coupled fct‐FePd/α‐Fe Nanocomposite Magnets Converted from Pd/Fe3O4 Core/Shell Nanoparticles

We report the controlled synthesis of exchange‐coupled face‐centered tetragonal (fct) FePd/α‐Fe nanocomposite magnets with variable Fe concentration. The composite was converted from Pd/Fe₃O₄ core/shell nanoparticles through a high‐temperature annealing process in a reducing atmosphere. The shell thickness of core/shell Pd/Fe₃O₄ nanoparticles could be readily tuned, and subsequently the concentration of Fe in nanocomposite magnets was controlled. Upon annealing reduction, the hard magnetic fct‐FePd phase was formed by the interdiffusion between reduced α‐Fe and face‐centered cubic (fcc) Pd, whereas the excessive α‐Fe remained around the fct‐FePd grains, realizing exchange coupling between the soft magnetic α‐Fe and hard magnetic fct‐FePd phases. Magnetic measurements showed variation in the magnetic properties of the nanocomposite magnets with different compositions, indicating distinct exchange coupling at the interfaces. The coercivity of the exchange‐coupled nanocomposites could be tuned from 0.7 to 2.8 kOe and the saturation magnetization could be controlled from 93 to 160 emu g^?1. This work provides a bottom‐up approach using exchange‐coupled nanocomposites for engineering advanced permanent magnets with controllable magnetic properties.     

Hierarchical assembly of SnO2 nanorod arrays on alpha-Fe2O3 nanotubes: a case of interfacial lattice compatibility

SnO2 nanorod arrays were hierarchically assembled onto the surface of alpha-Fe2O3 nanotubes via a facile solution method. Determined by the hexagonal geometrical nature of the alpha-Fe2O3 nanotubes, the heterostructures were of 6-fold symmetry. HRTEM characterizations demonstrated that the lattice mismatch at the interface was an important factor in determining the growth direction of the secondary nanorod arrays.     

Adsorption of sulfur dioxide on hematite and goethite particle surfaces

The adsorption of sulfur dioxide (SO(2)) on iron oxide particle surfaces at 296 K has been investigated using X-ray photoelectron spectroscopy (XPS). A custom-designed XPS ultra-high vacuum chamber was coupled to an environmental reaction chamber so that the effects of adsorbed water and molecular oxygen on the reaction of SO(2) with iron oxide surfaces could be followed at atmospherically relevant pressures. In the absence of H(2)O and O(2), exposure of hematite (alpha-Fe(2)O(3)) and goethite (alpha-FeOOH) to SO(2) resulted predominantly in the formation of adsorbed sulfite (SO(3)(2-)), although evidence for adsorbed sulfate (SO(4)(2-)) was also found. At saturation, the coverage of adsorbed sulfur species was the same on both alpha-Fe(2)O(3) and alpha-FeOOH as determined from the S2p : Fe2p ratio. Equivalent saturation coverages and product ratios of sulfite to sulfate were observed on these oxide surfaces in the presence of water vapor at pressures between 6 and 18 Torr, corresponding to 28 to 85% relative humidity (RH), suggesting that water had no effect on the adsorption of SO(2). In contrast, molecular oxygen substantially influenced the interactions of SO(2) with iron oxide surfaces, albeit to a much larger extent on alpha-Fe(2)O(3) relative to alpha-FeOOH. For alpha-Fe(2)O(3), adsorption of SO(2) in the presence of molecular oxygen resulted in the quantitative formation of SO(4)(2-) with no detectable SO(3)(2-). Furthermore, molecular oxygen significantly enhanced the extent of SO(2) uptake on alpha-Fe(2)O(3), as indicated by the greater than two-fold increase in the S2p : Fe2p ratio. Although SO(2) uptake is still enhanced on alpha-Fe(2)O(3) in the presence of molecular oxygen and water, the enhancement factor decreases with increasing RH. In the case of alpha-FeOOH, there is an increase in the amount of SO(4)(2-) in the presence of molecular oxygen, however, the predominant surface species remained SO(3)(2-) and there is no enhancement in SO(2) uptake as measured by the S2p : Fe2p ratio. A mechanism involving molecular oxygen activation on oxygen vacancy sites is proposed as a possible explanation for the non-photochemical oxidation of sulfur dioxide on iron oxide surfaces. The concentration of these sites depends on the exact environmental conditions of RH.