Growth and magnetic properties of oriented alpha-Fe2O3 nanorods

alpha-Fe(2)O(3) nanorods have been deposited on Si substrates using the metal-organic chemical vapor deposition method. Structural analyses indicated that alpha-Fe(2)O(3) nanorods are preferentially oriented in the [104] direction on Si(100) substrates, and the nanorod possesses the single-crystalline structure. MFM image suggests that a spin domain is formed in the alpha-Fe(2)O(3) nanorod. Anisotropic magnetic property of the alpha-Fe(2)O(3) nanorods, i.e., the discrepancy of the saturation magnetization, is observed from SQUID measurements when the magnetic field are applied parallel and perpendicular to the substrate. A lower Morin temperature than that of the macroscopically crystalline hematite is observed when the magnetic field is applied parallel to the substrate.     

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.     

N-TiO_2/ZnO复合纳米管阵列的掺杂机理及其光催化活性

以ZnO纳米柱阵列为模板,采用溶胶-凝胶法制备出TiO2/ZnO和N掺杂TiO2/ZnO的复合纳米管阵列.扫描电镜(SEM)、X射线光电子能谱(XPS)和紫外-可见漫反射吸收光谱(UV-Vis)的结果表明:两种阵列的纳米管均为六角形结构,直径约为100nm,壁厚约为20nm;在N-TiO2/ZnO复合纳米管阵列中,掺入的N离子主要是以N-Ox、N-C和N-N的形式化学吸附在纳米管表面,仅有少量的N离子以取代式掺杂的方式占据TiO2晶格O的位置;表面N物种形成的表面态能级和取代式掺杂导致带隙的窄化,增强了纳米管阵列的光吸收效率,促进了光生载流子的分离.光催化实验结果表明,N离子的掺杂有利于N-TiO2/ZnO复合纳米管阵列光催化活性的提高.     

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.     

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.     

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.     

Iron oxide nanopropellers prepared by a low-temperature solution approach

The alpha-Fe(2)O(3) (hematite) nanopropellers were synthesized via a low-temperature solution-based method using FeCl(2) as a precursor in the presence of urea and glycine hydrochloride. The formation of alpha-Fe(2)O(3) nanopropellers is strongly depended on the addition of glycine hydrochloride, which serves as a pH modulator and affects the oxidation rate of Fe(2+). The structural evolution of the propeller-structured hematite was found to follow dissolution and recrystallization processes. For the structural conformation, each nanopropeller presents a hexagonal central column closed by six equivalent surfaces of {(-)1100} and the six arrays of the nanopropeller structure are a result of growth along +/- [(-)1100], +/- [(-)1010], and +/-[0(-)110]. Preliminary results show that the magnetic maghemite (gamma-Fe(2)O(3)) nanopropellers could also be prepared by a reduction and reoxidation process from the alpha-Fe(2)O(3) (hematite) nanopropeller precursors.     

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.     

P3HT/CdS/TiO2/ZnO一维有序核壳式纳米棒阵列的构制及其在杂化太阳电池中的应用研究

采用恒电位法在铟锡氧化物导电玻璃(ITO)上制备了高度有序一维ZnO纳米棒阵列,将ZnO纳米棒阵列在TiO2溶胶中采用提拉法制备出了一维TiO2/ZnO核壳式纳米棒阵列.在一维TiO2/ZnO核壳式纳米棒阵列上电沉积CdS纳米晶得到一维CdS/TiO2/ZnO核壳式纳米棒阵列,然后在一维CdS/TiO2/ZnO核壳式纳米棒阵列上电沉积聚3-己基噻吩(P3HT)薄膜得到P3HT/CdS/TiO2/ZnO核壳式纳米结构薄膜.以该纳米结构薄膜电极为光阳极制备出新型纳米结构杂化太阳电池,研究了该类电池的光电转换性能,初步探讨了该类电池的工作机理.     

Doping gamma-Fe(2)O(3) nanoparticles with Mn(III) suppresses the transition to the alpha-Fe(2)O(3) structure

Here we report on a mixed oxide system, gamma-Fe2O3 nanoparticles doped with Mn(III), where the transition from the cubic to the more stable hexagonal alpha-Fe2O3 structure is suppressed. When amorphous Fe2O3 is heated at 300 degrees C for 3 h, ferrimagnetic gamma-Fe2O3 is observed as the sole product. On the other hand, when the temperature is raised to 500 degrees C, one observes only antiferromagnetic alpha-Fe2O3 as the product. However, upon doping with 8.5 wt % Mn(III), the amorphous nanoparticles crystallized to mainly the gamma-Fe2O3 matrix after heating at 500 degrees C for 3 h, and need to be heated to >650 degrees C for the complete transition to the alpha-Fe2O3 structure to take place.     

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.     

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.     

Facile route to alpha-FeOOH and alpha-Fe2O3 nanorods and magnetic property of alpha-Fe2O3 nanorods

alpha-FeOOH nanorods with diameters of 15-25 nm and lengths up to 170-300 nm were synthesized in high yield via a facile and template-free hydrothermal method at low temperature. After calcining the as-synthesized alpha-FeOOH at 250 degrees C for 2 h, we could obtain alpha-Fe2O3 nanorods. Interestingly, the as-obtained alpha-Fe2O3 nanorods exhibited weakly ferromagnetic characteristics at low temperature and superparamagnetic property at room temperature, which is different from the behavior of the corresponding bulk material.     

电沉积种子层化学控制生长氧化锌纳米棒和纳米管

采用水溶液法在电沉积的ZnO种子层上制备了高度取向的ZnO纳米棒阵列,并通过碱溶液化学腐蚀法获得了ZnO纳米管。对ZnO纳米棒和纳米管的溶液生长和腐蚀过程进行了分析。结果表明,种子层的结构和性能对ZnO纳米棒有着重要的影响,在-700 mV电位下沉积的种子层薄膜均匀性好,生长的纳米棒密度大、与基底垂直性好;碱溶液对纳米棒的腐蚀具有选择性,通过控制腐蚀液的浓度和时间,可获得中空的ZnO纳米管。     

Conversion of anisotropically phase-segregated Pd/gamma-Fe2O3 nanoparticles into exchange-coupled fct-FePd/alpha-Fe nanocomposite magnets

Exchange-coupled fct-FePd/alpha-Fe nanocomposite magnets were fabricated by converting anisotropically phase-segregated Pd/gamma-Fe2O3 nanoparticles via the interfacial atom diffusion. The magnetically hard fct-FePd phases formed by the interdiffusion between alpha-Fe and fcc-Pd phases nearly preserve their sizes at the nanometer scale because they are surrounded by the alpha-Fe matrix. The VSM measurements reveal that the exchange coupling between the soft and hard phases has been realized.     

Ni-V2O5.nH2O core-shell nanocable arrays for enhanced electrochemical intercalation

We have prepared Ni-V(2)O(5).nH(2)O core-shell nanocable arrays for Li(+) intercalation applications. Ni-V(2)O(5).nH(2)O nanocables were prepared via formation of Ni nanorod arrays through the template based electrochemical deposition, followed by coating of V(2)O(5).nH(2)O on Ni nanorods through electrophoretic deposition. Transmission electron microscopy (TEM) micrograph clearly shows the Ni core was covered completely by a V(2)O(5).nH(2)O shell. Electrochemical analysis demonstrates that in a current density of 1.6 A/g, the Li(+) intercalation capacity of Ni-V(2)O(5).nH(2)O nanocable array is approximately 10 times higher than that of single-crystal V(2)O(5) nanorod array and 20 times higher than that of sol-gel-derived V(2)O(5) film. Both energy density and power density of such nanocable-array electrodes are higher than the V(2)O(5) film electrode by at least 1 order of magnitude. Such significant improvement in electrochemical performance is due to the large surface area and short diffusion path offered by the nanostructured V(2)O(5).nH(2)O.     

Distinct visible-light response of composite films with CdS electrodeposited on TiO2 nanorod and nanotube arrays

Thorough infiltration of CdS nanoparticles into spaces of titania nanorod and nanotube arrays was achieved by an ac electrodeposition technique to construct composite films of CdS over titania. The substrate affected not only the electrodeposition rate but also the oriented growth of CdS. A photocurrent much larger than the simple summation of those arising from the two component layers of CdS and titania was detected for both composite films under visible-light illumination. Such an enhancement in the photocurrent was even more prominent for the composite film based on the titania nanorod arrays, which was contributed to the higher charge separation rate arising from the nearly single-crystalline nanorods when compared with the polycrystalline nanotubes.     

Facile electrochemical synthesis of hexagonal Cu2O nanotube arrays and their application

Large-scale and highly oriented single-crystalline hexagonal Cu(2)O nanotube arrays have been successfully synthesized using a two-step solution approach, which involves the electrodeposition of oriented Cu(2)O nanorods and a subsequent dissolution technique along the c axis to form a tubular structure. Herein, NH(4)Cl was found to be an effectual additive, and it can successfully realize the dissolution process of Cu(2)O from nanorods to nanotubes. The dissolution mechanism of Cu(2)O from nanorods to nanotubes was illustrated in detail. These prepared Cu(2)O nanotube arrays were characterized by SEM, EDS, XRD, XPS, and TEM. The photoluminescence (PL) spectrum of Cu(2)O nanotube arrays was also measured, and it shows there is a greater fraction of copper or oxygen vacancies in these prepared Cu(2)O nanotubes. Finally, the applications of Cu(2)O nanotube arrays for gas sensors were investigated in this paper.     

Flutelike porous hematite nanorods and branched nanostructures: synthesis, characterisation and application for gas-sensing

Flute-like porous alpha-Fe2O3 nanorods and branched nanostructures such as pentapods and hexapods were prepared through dehydration and recrystallisation of hydrothermally synthesised beta-FeOOH precursor. Transmission electron microscopy (TEM), high-resolution TEM and selected area electron diffraction analyses reveal that the nanorods, which grow along the [110] direction, have nearly hollow cavities and porous walls with a pore size of 20-50 nm. The hexapods have six symmetric arms with a diameter of 60-80 nm and length of 400-900 nm. The growth direction of the arms in the hexapod-like nanostructure is also along the [110] direction, and there is a dihedral angle of 69.5 degrees between adjacent arms. These unique iron oxide nanostructures offer the first opportunity to investigate their magnetic and gas sensing properties. The nanostructures exhibited unusual magnetic behaviour, with two different Morin temperatures under field-cooled and zero-field-cooled conditions, owing to their shape anisotropy and magnetocrystalline anisotropy. Furthermore, the alpha-Fe2O3 nanostructures show much better sensing performance towards ethanol than that of the previously reported polycrystalline nanotubes. In addition, the alpha-Fe2O3 nanostructure based sensor can selectively detect formaldehyde and acetic acid among other toxic, corrosive and irritant vapours at a low working temperature with rapid response, high sensitivity and good stability.     

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.