Structural and catalytic properties of ZnO and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanostructures loaded with metal nanoparticles

Nanostructured zinc oxide (ZnO) nanobelts and aluminum oxide (Al₂O₃) nanoribbons have been grown successfully from the vapor phase. XRD results confirmed the purity and the high quality of the formed crystalline materials. TEM images showed that ZnO nanostructures grew in the commonly known tetrapod structure with nanobelts separated from the tetrapods with an average width range of 10–30 nm and a length of about 500 nm. Al₂O₃ nanostructures grew in the form of nanoribbons with an average width range of 20–30 nm and a length of up to 1 μm. The catalytic oxidation of CO gas into CO₂ gas over the synthesized nanostructures is also reported. Higher catalytic activity was observed for Pd nanoparticles loaded on the ZnO nanobelts (100% conversion at 270 °C) and Al₂O₃ nanoribbons (100% conversion at 250 °C). The catalytic activity increased in the order Cu < Co < Au < Pd for the metal-loaded nanostructures. The preparation methods could be applied for the synthesis of novel nanostructures of various materials with novel properties resulting from the different shapes and morphologies.     

Catalytic growth and characterization of Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

β-Ga₂O₃ nanowires have been synthesized using Ga metal and H₂O vapor at 800 °C in the presence of Ni catalyst on the substrate. Remarkable reduction of the diameter and increase of the length of the Ga₂O₃ nanowires are achieved by separation of Ga metal and H₂O vapor before they reach the substrate. Transmission electron microscopy analyses indicate that the β-Ga₂O₃ nanowires possess a single-crystalline structure. Photoluminescence measurements show two broad emission bands centered at 290 nm and 390 nm at room temperature. Received: 27 June 2002 / Accepted: 7 October 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +886-6/234-4496, E-mail: wujj@mail.ncku.edu.tw     

Preparation of Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> nanowires by calcining the precursor powders synthesized in a novel inverse microemulsion

Manganese oxide (hausmannite) nanowires were prepared by annealing precursor powders at a temperature of 800 °C for 3 h, which were produced in a novel inverse microemulsion (IμE) system. The microstructures of the as-prepared Mn₃O₄ nanowires were investigated by means of X-ray diffraction, transmission electron microscopy, and Raman spectra. It has been found that the Mn₃O₄ nanowires were relatively straight and their surfaces were smooth with a typical diameter of 75–150 nm. The formation mechanism of the Mn₃O₄ nanowires is discussed. Received: 30 May 2002 / Accepted: 7 October 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +86-25/359-5535, E-mail: wangqun@nju.edu.cn     

Magnetic properties of ordered nanowires of the quasi-two-dimensional antiferromagnet SpFeMn(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript>

Ordered arrays of nanowires of the photochromic antiferromagnet SpFeMn(C₂O₄)₃ (where Sp is 1-{(1′,3′,3′-trimethyl-6-nitro-5′-chlorospiro[2H-1-benzopyran-2,2′-indolin]-8-yl)methyl}pyridinium) have been fabricated in anodized aluminum oxide pores with diameters of 20 and 200 nm. It has been revealed that the growth of the spin-glass phase with noncollinear ordering of spins in nanowires is suppressed in favor of the uniaxial antiferromagnetic phase. A decrease in the nanowire diameter leads to an increase in the anisotropy of the magnetic resonance spectra. This is associated with the magnetocrystalline anisotropy that considerably exceeds the anisotropy of the nanowire shape.     

Surface modification of polycrystalline oxides (V<Subscript>2</Subscript>O<Subscript>5</Subscript>, MoO<Subscript>3</Subscript>, and WO<Subscript>3</Subscript>) irradiated with high-power ion beams

The influence of a high-power ion beam on polycrystalline oxides (V₂O₅, MoO₃, and WO₃) is investigated. Oxide irradiation with ion beams with current densities of greater than ～30 A/cm² is established to initiate changes in the color of irradiated layers and lead to surface-layer particle melting. It is demonstrated that a distinctive feature of the interaction between a high-power ion beam and V₂O₅ is the formation of surface nanosheets and nanowires whose characteristic cross-sectional size and thickness are ～1 μm and up to ～40 nm, respectively. The nanosheets are generated near emerging surface cracks if the beam current density is ～100 A/cm². Possible mechanisms of surface nanostructures formation under the action of pulsed ion beams are discussed.     

Tuning electronic properties of In<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires by doping control

We present two effective routes to tune the electronic properties of single-crystalline In₂O₃ nanowires by controlling the doping. The first method involves using different O₂ concentrations during the synthesis. Lightly (heavily) doped nanowires were produced by using high (low) O₂ concentrations, respectively, as revealed by the conductances and threshold voltages of nanowire-based field-effect transistors. Our second method exploits post-synthesis baking, as baking heavily doped nanowires in ambient air led to suppressed conduction and a positive shift of the threshold voltage, whereas baking lightly doped nanowires in vacuum displayed the opposite behavior. Our approaches offer viable ways to tune the electronic properties of many nonstoichiometric metal oxide systems such as In₂O₃, SnO₂, and ZnO nanowires for various applications. PACS 85.35.-p     

Synthesis and characteristics of Fe<Subscript>96-x</Subscript>Zr<Subscript>x</Subscript>B<Subscript>4</Subscript> nanowire arrays

Fe-rich Fe_96-xZr_xB₄ (0≤x≤7) nanowires were first prepared by electrodepositing into anodic aluminum oxide templates. Transmission electron microscope analysis shows that the nanowires are uniform and are about 100 nm in diameter with an aspect ratio of around 75. The broad peaks of X-ray diffraction and the Mössbauer spectrum indicate that the Fe_96-xZr_xB₄ nanowires are composed of α-Fe-like and Zr-rich FeZrB phases. Selected area electro diffraction results also indicate that the structure of Fe₈₉Zr₇B₄ nanowires is amorphous. A vibrating sample magnetometer is employed to study the magnetic properties of nanowire arrays at room temperature. The coercivity of nanowire arrays in parallel to the wire axis decreases with increasing Zr content.     

Temperature-controlled synthesis of Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> nanobelts and nanosheets

We have investigated the effect of growth temperature on structural morphology and photoluminescence (PL) properties of as-synthesized gallium oxide (Ga₂O₃) nanostructures. The products consisted of Ga₂O₃ nanobelts and nanosheets (i.e. wider nanobelts), which had monoclinic crystalline structures. The average width of structures grown at 1000 °C was relatively greater than those at 800 °C, revealing that higher temperature favored the formation of nanosheets. PL measurements of 800 °C- and 1000 °C-grown samples indicated that both samples exhibited a broad emission band peaked around the blue-light region, while only the 800 °C-grown sample showed a red peak. PACS 81.07.-b; 81.05.Je; 61.10.Nz; 68.37.Hk; 68.37.Lp     

Magnetic Core/Shell Nanocomposites MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> for Biomedical Application: Synthesis and Properties

Magnetic core/shell (CS) nanocomposites (MNCs) are synthesized using a simple method, in which a magnesium ferrite nanoparticle (MgFe₂O₄) is a core, and an amorphous silicon dioxide (silica SiO₂) layer is a shell. The composition, morphology, and structure of synthesized particles are studied using X-ray diffraction, field emission electron microscopy, transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), scattering electrophoretic photometer, thermogravimetric analysis (TGA), and Mössbauer spectroscopy. It is found that the MgFe₂O₄/SiO₂ MNC has the core/shell structure formed by the Fe?O–Si chemical bond. After coating with silica, the MgFe₂O₄/SiO₂ MNC saturation magnetization significantly decreases in comparison with MgFe₂O₄ particles without a SiO₂ shell. Spherical particles agglomerated from MgFe₂O₄ nanocrystallites ～9.6 and ～11.5 nm in size function as cores coated with SiO₂ shells ～30 and ～50 nm thick, respectively. The total size of obtained CS MNCs is ～200 and 300 nm, respectively. Synthesized CS MgFe₂O₄/SiO₂ MNCs are very promising for biomedical applications, due to the biological compatibility of silicon dioxide, its sizes, and the fact that the Curie temperature is in the region required for hyperthermal therapy, 320 K.     

The enhanced catalytic degradation of SiO<Subscript>2</Subscript>/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/C@TiO<Subscript>2</Subscript> photo-Fenton system on p-nitrophenol

Heterogeneous photo-Fenton SiO₂/Fe₃O₄/C@TiO₂ (SFCT) catalyst with a core-multishell structure and a diameter of about 550 nm was successfully prepared and was characterized by scanning electron microscopy (SEM), TEM, XRD, Raman, and Fourier transform infrared (FT-IR). The results illustrated that anatase TiO₂ coexisted with rutile TiO₂, in which the anatase phase was the main crystal phase. In addition, the catalytic activity of SFCT catalyst had been evaluated in the catalytic degradation on p-nitrophenol (PNP). The influence factors on the PNP degradation, including SFCT component ratio (m _SFC/ m _TiO2), H₂O₂ dosage, solution pH, and PNP concentration, had been investigated. And the contrast experiments about the photo-Fenton catalytic mechanism revealed that the SFCT-2 catalyst possessed a superior activity in the neutral environment due to the optimal activity matching between Fe₃O₄ and TiO₂, and it exhibited the stable catalytic performance after five successive recycles. Therefore, the SFCT-2 catalyst had a promising application for the photo-Fenton degradation of organic contaminant.     

Synthesis and luminescent properties of Eu<Superscript>3+</Superscript>- and Eu<Superscript>2+</Superscript>-activated sodium pyrophosphate Na<Subscript>4</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

The luminescent properties of Eu³⁺ and Eu²⁺ ions in sodium pyrophosphate, Na₄P₂O₇, have been studied. The excitation spectrum of the Eu³⁺ emission in Na₄P₂O₇ consists of several sets of bands in the range 280–535 nm due to 4f–4f transitions of Eu³⁺ ions and a broad band with a maximum at about 240 nm interpreted to be due to a charge transfer (CT) transition from oxygen 2p states to empty states of the Eu³⁺ 4f⁶-configuration. Although the CT band energy is large enough, the quantum efficiency (η) of the Eu³⁺ emission in Na₄P₂O₇ under CT excitation was estimated to be very low (η ≤ 0.01). In terms of a configurational coordinate model, this fact is interpreted as a result of the high efficiency of a radiationless relaxation from the CT state to the ⁷F₀ ground state of Eu³⁺ ions occupying sodium sites in Na₄P₂O₇. A strong reducing agent is required in order to stabilize Eu²⁺ ions in Na₄P₂O₇ during the synthesis. Several nonequivalent Eu²⁺ luminescence centers in Na₄P₂O₇ were found.     

Spectroscopic Properties and Energy Transfer Analysis of Tm<Superscript>3+</Superscript>-Doped BaF<Subscript>2</Subscript>-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript> Glass

This paper reports on the spectroscopic properties and energy transfer analysis of Tm³⁺-doped BaF₂-Ga₂O₃-GeO₂-La₂O₃ glasses with different Tm₂O₃ doping concentrations (0.2, 0.5, 2.0, 2.5, 3.0, 3.5, 3.5, 4.0 wt%). Mid-IR fluorescence intensities in the range of 1,300 nm−2,200 nm have been measured when excited under an 808 nm LD for all the samples with the same pump power. Energy level structure and Judd-Ofelt parameters have been calculated based on the absorption spectra of Tm³⁺, cross-relaxation rates and multi-phonon relaxation rates have been estimated with different Tm₂O₃ doping concentrations. The maximum fluorescence intensity at around 1.8 μm has been obtained in Tm₂O₃-3 wt% sample and the maximum value of calculated stimulated emission cross-section of Tm³⁺ in this sample is about 0.48 × 10⁻²⁰ cm² at 1,793 nm, and there is not any crystallization peak in the DSC curve of this sample, which indicate the potential utility of Tm³⁺-doped BaF₂-Ga₂O₃-GeO₂- La₂O₃ glass for 2.0-μm optical fiber laser.     

EPR and optical absorption studies of Cu<Superscript>2+</Superscript> ions in [ZnPd(CN)<Subscript>4</Subscript>(C<Subscript>4</Subscript>H<Subscript>12</Subscript>N<Subscript>2</Subscript>O<Subscript>2</Subscript>)] single crystals

A Cu²⁺-doped single crystal of catena-trans-bis(N-(2-hydroxyethyl)-ethylenediamine) zinc(II)-tetra-m-cyanopaladate(II) [ZnPd(CN)₄(C₄H₁₂N₂O₂)] complex has been investigated by electron paramagnetic resonance (EPR) technique at room temperature. EPR spectra indicate that Cu²⁺ ions substitute for magnetically equivalent Zn²⁺ ions and form octahedral complexes in [ZnPd(CN)₄(C₄H₁₂N₂O₂)] hosts. The crystal field affecting the Cu²⁺ ion is nearly axial. The optical absorption studies show two bands at 322 nm (30864 cm⁻¹) and 634 nm (15337 cm⁻¹) which confirm the axial symmetry. The spin Hamiltonian parameters and the relevant wave function are determined.     

Methane sensor based on SnO<Subscript>2</Subscript>/In<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanostructure

Two sets of samples of SnO₂/In₂O₃/TiO₂ system have been fabricated with different concentrations of component materials. In the first set TiO₂ with rutile structure was used, while in the second set it has the structure of anatase. Thin films (up to 50 nm) of obtained mixtures were deposited. Their sensitivity and selectivity with respect to methane (CH4) were studied. Nanostructure on the basis of 70%SnO₂ — 10%In₂O₃ — 20%TiO₂(anatase) exhibits sufficient sensitivity to methane.     

Elevated electrochemical property of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> originated from nano-sized Mn<Subscript>3</Subscript>O<Subscript>4</Subscript>

By employment of nano-sized pre-prepared Mn₃O₄ as precursor, LiMn₂O₄ particles have been successfully prepared by facile solid state method and sol-gel route, respectively. And the reaction mechanism of the used precursors of Mn₃O₄ is studied. The structure, morphology, and element distribution of the as-synthesized LiMn₂O₄ samples are characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Compared with LiMn₂O₄ synthesized by facile solid state method (SS-LMO), LiMn₂O₄ synthesized by modified sol-gel route (SG-LMO) possesses higher crystallinity, smaller average particle size (~175 nm), higher lithium chemical diffusion coefficient (1.17 × 10^?11 cm² s^?1), as well as superior electrochemical performance. For example, the cell based on SG-LMO can deliver a capacity of 85.5 mAh g^?1 at a high rate of 5 °C, and manifests 88.3% capacity retention after 100 cycles at 0.5 °C when cycling at 45 °C. The good electrochemical performance of the cell based on SG-LMO is ascribed mainly to its small particle size, high degree of dispersion, and uniform element distribution in bulk material. In addition, the lower polarization potential accelerates Li⁺ ion migration, and the lower atom location confused degree maintains integrity of crystal structure, both of which can effectively improve the rate capability and cyclability of SG-LMO.     

Nanosecond photoelectric effects in all-oxide p-n junction of La<Subscript>0.9</Subscript>Sr<Subscript>0.1</Subscript>MnO<Subscript>3</Subscript>/SrNb<Subscript>0.01</Subscript>Ti<Subscript>0.99</Subscript>O<Subscript>3</Subscript>

Nanosecond (ns) photoelectric effects have been observed in all-oxide p-n junctions of La_0.9Sr_0.1MnO₃/SrNb_0.01Ti_0.99O₃ for the first time. The rise time was about 23 ns and the full width at half maximum was about 125 ns for the open-circuit photovoltaic pulse when the La_0.9Sr_0.1MnO₃ thin film in the p-n junction was irradiated by a laser of ≈20 ns pulse duration and 308 nm wavelength. The photovoltaic sensitivity was 80 mV/MJ for a 308 nm laser pulse.     

Synthesis and electrocatalytic activities of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocubes

In this article, a hydrothermal method was developed to synthesize Co₃O₄ nanocubes using hydrogen peroxide (H₂O₂) as oxidant, Co(NO₃)₂·6H₂O as a cobalt source. The products are characterized in detail by multiform techniques including X-ray diffraction (XRD), energy dispersive X-ray analysis (EDS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results show that the obtained products are Co₃O₄ nanocubes with size ranging between 20 and 40 nm. The effects of the hydrogen peroxide concentration on the size of the products have been studied. The electrocatalytic activities of H₂O₂ reduction on Co₃O₄ nanocubes in phosphate buffer were also evaluated.     

Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> nanosquaresheets grown on Si substrate

A novel morphology of Bi₂O₃ nanomaterial (nanosquaresheets) has been successfully synthesized in large area by thermal evaporation of commercial Bi₂O₃ powder at high temperatures. The Bi₂O₃ nanosquaresheets (NSSs) are perfect regular squares and have sharp, uniform edges. The typical length of the sides is in the range of 200–600 nm. The thickness varies from 30 to 100 nm. Electron microscopy observations show that the Bi₂O₃ NSSs are single crystalline. The growth of Bi₂O₃ NSSs is probably controlled by a vapor–solid mechanism. The dominate growth directions are [2̄10] and [1̄2̄2] within the (245) planes. PACS 81.05.Hd; 81.10.Bk; 81.16.Be     

Spin-wave resonances in Eu<Subscript>0.8</Subscript>Ce<Subscript>0.2</Subscript>Mn<Subscript>2</Subscript>O<Subscript>5</Subscript> and EuMn<Subscript>2</Subscript>O<Subscript>5</Subscript> multiferroics

Spin-wave resonances have been observed in superlattices arising due to the phase separation and self-organization of charge carriers in Eu_0.8Ce_0.2Mn₂O₅ single crystals. The resonances are found within the 5–80 K temperature range at frequencies close to 30 GHz. Similar resonances with intensities about an order of magnitude lower are also observed in EuMn₂O₅. The latter suggests the existence of charge transfer processes between the manganese ions of different valences in EuMn₂O₅.     

Controlled-synthesis,characterization, and magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanostructures

Fe₃O₄ nanostructures with different morphologies, including uniform nanoparticles, nanorods and nanowire bundles, have been successfully synthesized via a facile hydrothermal route. Based on the observation of TEM images, the growth mechanism of one-dimensional Fe₃O₄ nanostructures is in accordance with Ostwald ripening process. From the hysteresis loops of as-prepared Fe₃O₄ products, we found that the morphology has great influence on the magnetic properties. The uniform Fe₃O₄ nanoparticles have higher saturation magnetization and lower coercivity than that of Fe₃O₄ nanorods and nanowires bundles. These phenomena attribute to the high shape anisotropy of nanorods and nanowire bundles, which prevent them from magnetizing in directions other than along their easy magnetic axes. PACS 81.07.-b; 75.50.Bb; 75.30.Gw; 81.10.Dn; 81.16.Be