Hydrolysis precipitation synthesis of monodisperse α-Fe2O3 nanorods/graphene oxide nanocomposites

A nanocomposite of graphene oxide supported by monodisperse rod-like α-Fe₂O₃ nanocrystals (GO/α-Fe₂O₃ nanocomposites) has been fabricated through a simple hydrolysis precipitation route in a water–ethanol system. The nanocomposites were characterized by X-ray diffraction, Raman spectra and transmission electron microscopy, respectively. The GO/α-Fe₂O₃ nanocomposites are GO nanosheets decorated randomly by α-Fe₂O₃ nanorods with diameters in the range of 3–5 nm and lengths of 20–30 nm, while only hollow α-Fe₂O₃ microspheres constructed by the radically oriented single-crystalline nanorods are observed in the absence of GO. Compared with pure α-Fe₂O₃ nanoparticles, α-Fe₂O₃/GO nanocomposites exhibited excellent photocatalytic activity as evident from the degradation of rhodamine B in water under UV irradiation. The superior photocatalytic activity performance of α-Fe₂O₃/GO nanocomposites could be attributed to the synergetic effect between the conducting GO nanosheets and monodisperse α-Fe₂O₃ nanorods.     

Ultrafine α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles grown in confinement of in situ self-formed “cage” and their superior adsorption performance on arsenic(III)

Without the addition of surfactants or templates, ultrafine α-Fe₂O₃ nanoparticles were successfully synthesized by a solvent thermal process at low temperature. During the synthesis, in situ self-formed “cage” of crystallized NaCl confined the growth of α-Fe₂O₃ nanoparticles in both the precipitation and solvent thermal processes, resulting in the creation of well-crystallized α-Fe₂O₃ nanoparticles with an average particle size about 4–5 nm and a high-specific surface area of ~162 m²/g. High resolution TEM investigations provided clear evidences of the in situ self-formation of NaCl “cage” during the synthesis and its confinement effect on the growth of α-Fe₂O₃ nanoparticles. The superior performance of these α-Fe₂O₃ nanoparticles on the adsorption of arsenite(III) (As) from aqueous environment was demonstrated with both lab-prepared and natural water samples at near neutral pH environment when compared with previously reported removal effects of As(III) by Fe₂O₃. This unique approach may also be utilized in the synthesis of other ultrafine metal oxide nanoparticles for a broad range of technical applications.     

Crystal structure of iron-oxide nanoparticles synthesized from ferritin

We have investigated the crystal structure of nanosized iron-oxide by X-ray diffraction (XRD), extended X-ray absorption fine structure measurements at the iron K-edge as well as by transmission electron microscopy (TEM). Iron-oxide nanoparticles were produced by thermal treatment of horse spleen ferritin molecules. The structure of these particles was compared to α-Fe₂O₃ and γ-Fe₂O₃ nanopowder references. The thermal treatment of a submonolayer film of ferritin molecules results in pure γ-Fe₂O₃ nanoparticles, while for films above a certain thickness α-Fe₂O₃ and γ-Fe₂O₃ coexist, exhibiting two different crystallite sizes. TEM shows a characteristic particle diameter of ~7 nm for γ-Fe₂O₃ resulting from thermal treatment of monolayers, consistent with the crystallite size of the γ-phase as obtained from XRD measurements on multi-layered samples. XRD shows the α-Fe₂O₃ phase to be characterized by a crystallite size of ~34 nm.     

Template-free synthesis of hollow <Emphasis Type="Italic">α</Emphasis>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> microspheres

Nearly monodisperse hollow α-Fe₂O₃ microspheres composed of nanoparticles have been successfully synthesized through a facile template-free hydrothermal method. The products were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. It is shown that the hollow α-Fe₂O₃ microspheres consist of well-aligned α-Fe₂O₃ nanoparticles with a mean diameter of about 15 nm. This facile reaction route presents an efficient method for mass production of monodisperse hollow magnetic nanomaterials. The final α-Fe₂O₃ microspheres exhibit special magnetic properties with a small remnant magnetization of 0.09 emu g⁻¹ and a high coercivity of 1121.67 Oe at room temperature.     

Ultra-sharp α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoflakes: growth mechanism and field-emission

We report the synthesis of single-crystalline α-Fe₂O₃ nanoflakes from a simple Fe–air reaction within the temperatures range of 260–400 °C. The nanoflakes synthesized at the lowest temperature (260 °C) in this work show an ultra-sharp morphology: 5–10 nm in thickness, 1–2 μm in length, 20 nm in base-width and around 5 nm at the tips; successfully demonstrate the promising electron field emission properties of a large-scaled α-Fe₂O₃ nanostructure film and exhibit the potential applications as future field-emission (FE) electron sources and displays (FEDs). The formation and growth of α-Fe₂O₃ nanostructures were discussed based on the surface diffusion mechanism. PACS 79.60.Jv; 79.70.+q; 77.84.Bw     

Facile synthesis of monodispersed α-Fe2O3 microspheres through template-free hydrothermal route

Monodisperse α-Fe₂O₃ microspheres have been selectively synthesized through a facile hydrothermal method without the assistance of any surfactant, employing FeCl₃·6H₂O and NH₄NaHPO₄ as initial materials. The products were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. α-Fe₂O₃ microspheres with average size about 250 nm were constructed by single crystalline nanoparticles with average diameter about 15 nm. The investigation on the evolution formation revealed that growth temperature was critical to control the assembly of the fresh formed nanocrystallites, and the microsphere formation was proved to be the Ostwald ripening process by tracking the structures of the products at different growth temperature. α-Fe₂O₃ microspheres showed a weak ferromagnetic behavior with a remanent magnetization of 0.208 emu g⁻¹ and a coercivity of 1,034.27 Oe at room temperature.     

Acceleration and inhibition of amyloid-β fibril formation by peptide-conjugated fluorescent-maghemite nanoparticles

The formation of amyloid aggregates by association of peptides into ordered structures is hallmark of certain neurodegenerative disorders. Exploring the effect of specific nanoparticles on the formation of amyloid fibrils may contribute toward a mechanistic understanding of the aggregation processes, leading to design nanoparticles that modulate the formation of toxic amyloid plaques. Uniform maghemite (γ-Fe₂O₃) magnetic nanoparticles, containing fluorescein covalently encapsulated within (F-γ-Fe₂O₃)_, were prepared. These F-γ-Fe₂O₃ nanoparticles of 14.0 ± 4.0 nm were then coated with human serum albumin (HSA) via a precipitation process. Covalent conjugation of the spacer arm succinimidyl polyethylene glycol succinimidyl ester (NHS–PEG–NHS) to the F-γ-Fe₂O₃~HSA nanoparticles was then accomplished by interacting the primary amine groups of the HSA coating with excess NHS–PEG–NHS molecules. Covalent conjugation of the peptides amyloid-β 40 (Aβ₄₀) or Leu-Pro-Phe-Phe-Asp (LPFFD) onto the surface of the former fluorescent nanoparticles was then performed, by interacting the terminal activated NHS groups of the PEG derivatized F-γ-Fe₂O₃~HSA nanoparticles with primary amino groups of the peptides. Kinetics of the Aβ₄₀ fibrillation process in the absence and presence of varying concentrations of the Aβ₄₀ or LPFFD conjugated nanoparticles were also elucidated. The non-peptide conjugated fluorescent nanoparticles do not affect the Aβ₄₀ fibrillation process significantly. However, the Aβ₄₀-conjugated nanoparticles (F-γ-Fe₂O₃~HSA–PEG–Aβ₄₀) accelerate the fibrillation process while the LPFFD-conjugated nanoparticles (F-γ-Fe₂O₃~HSA–PEG–LPFFD) inhibit it. By applying MRI and fluorescence imaging techniques simultaneously these bioactive fluorescent magnetic iron oxide nanoparticles can be used as an efficient tool to study and control the Aβ₄₀ amyloid fibril formation process.     

Characterization and applications of as-grown β-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles prepared by hydrothermal method

The production of low-dimensional nanoparticles (NPs) with appropriate surface modification has attracted increasing attention in biological, biochemical, and environmental applications including chemical sensing, photocatalytic degradation, separation, and purification of toxic molecules from the matrices. In this study, iron oxide NPs have been prepared by hydrothermal method using ferric chloride and urea in aqueous medium under alkaline condition (pH 9 ~ 10). As-grown low-dimensional NPs have been characterized by UV–vis spectroscopy, FT-IR, X-ray diffraction, Field emission scanning electron microscopy, Raman spectroscopy, High-resolution Transmission electron microscopy, and Electron Diffraction System. The uniformity of the NPs size was measured by the scanning electron microscopy, while the single phase of the nanocrystalline β-Fe₂O₃ was characterized using powder X-ray diffraction technique. As-grown NPs were extensively applied for the photocatalytic degradation of acridine orange (AO) and electrochemical sensing of ammonia in liquid phase. Almost 50% photo-catalytic degradation with AO was observed in the presence of UV sources (250 W) with NPs. β-Fe₂O₃ NP-coated gold electrodes (GE, surface area 0.0216 cm²) have enhanced ammonia-sensing performances in their electrical response (I–V characterization) for detecting ammonia in liquid phase. The performances of chemical sensor were investigated, and the results exhibited that the sensitivity, stability, and reproducibility of the sensor improved significantly using β-Fe₂O₃ NPs on GE surface. The sensitivity was approximately 0.5305 ± 0.02 μAcm⁻²mM⁻¹, with a detection limit of 21.8 ± 0.1 μM, based on a signal/noise ratio of 3 with short response time.     

An optimal low-temperature tartrate precursor method for the synthesis of monophasic nanosized ZnFe2O4

In this study, the synthesis of monophasic nanocrystalline zinc ferrite (ZnFe₂O₄) was achieved by controlling the thermal decomposition conditions of a zinc–iron tartrate precursor method. Differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), Fe²⁺ content analysis, transmission electron microscopy (TEM), and Brunauer-Emmett-Teller (BET) techniques were used to investigate the effect of heat treatment conditions on the calcined powders. The thermal decomposition of the precursor led to an intermediate phase formation of ZnO, Fe₃O₄, and γ-Fe₂O₃. It was found that the Fe₃O₄ → γ-Fe₂O₃ oxidation reaction is the key step in producing monophasic nanosized ZnFe₂O₄. The monophasic nanoparticles of ZnFe₂O₄ can be obtained when the precursor is heat treated under a low temperature (300–400 °C) and long residence time (4 h) process that can prompt the Fe₃O₄ oxidation and prevent the formation of α-Fe₂O₃.     

Assembly of γ-Fe2O3/polyaniline nanofilms with tuned dipolar interaction

The internal morphology and magnetic properties of layer-by-layer assembled nanofilms of polyaniline (PANI) and maghemite (γ-Fe₂O₃—7.5-nm diameter) were probed with cross-sectional transmission electron microscopy (TEM) and magnetization measurements (magnetic hysteresis loops, magnetization using zero-field cooled/field-cooled protocols, and ac magnetic susceptibility). Additionally, simulations of the as-produced samples were performed to assess both the nanofilm’s morphology and the corresponding magnetic signatures using the cell dynamic system (CDS) approach and Monte Carlo (MC) through the standard Metropolis algorithm, respectively. Fine control of the film thickness and average maghemite particle–particle within this magnetic structure was accomplished by varying the number of bilayers (PANI/γ-Fe₂O₃) deposited onto silicon substrates or through changing the concentration of the maghemite particles suspended within the colloidal dispersion sample used for film fabrication. PANI/γ-Fe₂O₃ nanofilms comprising 5, 10, 25 and 50 deposited bilayers displayed, respectively, blocking temperatures (T _B) of 30, 35, 39 and 40 K and effective energy barriers (ΔE/k _B) of 1.0 × 10³, 2.3 × 10³, 2.8 × 10³ and 2.9 × 10³ K. Simulation of magnetic nanofilms using the CDS model provided the internal morphology to carry on MC simulation of the magnetic properties of the system taking into account the particle–particle dipolar interaction. The simulated (using CDS) surface–surface particle distance of 0.5, 2.5 and 4.5 nm was obtained for nanofilms with thicknesses of 36.0, 33.9 and 27.1 nm, respectively. The simulated (using MC) T _B values were 33.0, 30.2 and 29.5 K for nanofilms with thicknesses of 36.0, 33.9 and 27.1 nm, respectively. We found the experimental (TEM and magnetic measurements) and the simulated data (CDS and MC) in very good agreement, falling within the same range and displaying the same systematic trend. Our findings open up new perspectives for fabrication of magnetic nanofilms with pre-established (simulated) morphology and magnetic properties.     

Synthesis and magnetic properties of CdS/α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> hierarchical nanostructures

CdS/α-Fe₂O₃ hierarchical nanostructures, where the CdS nanorods grow irregularly on the side surface of α-Fe₂O₃ nanorods, were synthesized via a three-step process. The diameters and lengths of CdS nanorods can be tuned by changing the ethylenediamine (EDA) and Cd ion concentrations. The magnetic investigations by superconducting quantum interference device indicate that the hierarchical nanostructures have an Morin transition at lower temperature (230 K) than that of the single bulk α-Fe₂O₃ materials (263 K). Importantly, the hierarchical nanostructures exhibit weakly ferromagnetic characteristics at 300 K. A sharp peak assigned to the surface trap induced emission are observed in room temperature PL spectra. Combining with the optoelectronic properties of CdS, the CdS/α-Fe₂O₃ hierarchical nanostructures may be used as multi-functional materials for optoelectronic and magnetic devices. Supported by the National Natural Science Foundation of China (Grant Nos. 50772025 and 50872159), the Ministry of Science and Technology of China (Grant No. 2008DFR20420), the China Postdoctoral Science Foundation (Grant Nos. 20060400042 and 200801044), the Natural Science Foundation of Heilongjiang Province, China (Grant No. F200828), the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20070217002), and the Innovation Foundation of Harbin City (Grant No. RC2006QN017016)     

Synthesis and growth of hematite nanodiscs through a facile hydrothermal approach

This study reports a facile hydrothermal method for the synthesis of monodispersed hematite (α-Fe₂O₃) nanodiscs under mild conditions. The method has features such as no use of surfactants, no toxic precursors, and no requirements of high-temperature decomposition of iron precursors in non-polar solvents. By this method, α-Fe₂O₃ nanodiscs were achieved with diameter of 50 ± 10 nm and thickness of ~6.5 nm by the hydrolysis of ferric chloride. The particle characteristics (e.g., shape, size, and distribution) and functional properties (e.g., magnetic and catalytic properties) were investigated by various advanced techniques, including TEM, AFM, XRD, BET, and SQUID. Such nanodiscs were proved to show unique magnetic properties, i.e., superparamagnetic property at a low temperature (e.g., 20 K) but ferromagnetic property at a room temperature (~300 K). They also exhibit low-temperature (<623 K) catalytic activity in CO oxidation because of extremely clean surfaces due to non-involvement of surfactants, compared with those spheres and ellipsoids capped by PVP molecules.     

Synthesis and photocatalytic activity of polyaniline–TiO<Subscript>2</Subscript> composites with bionic nanopapilla structure

Polyaniline (PANI)–TiO₂ nanocomposites possessing both nano and microscale structures were prepared through a facile hydrothermal route in the presence of PANI. The nanopapilla particles were characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray analysis, X-ray photoelectron spectra, X-ray diffraction, FTIR spectra, UV–Vis spectroscopy, and N₂ adsorption analysis, etc. The results show that the composites possess both nano and microscale structures. The TiO₂ nanorods are dispersed on PANI with one end fixed to the surface. The photocatalytic properties of the powders were verified by the photodegradation of gaseous acetone under UV (λ = 254 nm) and visible-light irradiation (λ > 400 nm). In fact, the photocatalytic effects exhibited by the composite particles were superior to that of pure TiO₂ and P25 samples. This excellent behavior is attributed to the structural features of PANI–TiO₂ microspheres and the synergistic effect between PANI and TiO₂ which facilitates a larger amount of surface active sites. This in turn causes a faster charge separation and slower charge recombination which results in a more efficient decomposition of gaseous pollutants.     

A study of nanostructures formed in the hydrogen reduction of Fe(OH)<Subscript>3</Subscript>

A complex study of the hydrogen reduction of nanosized iron hydroxide Fe(OH)₃ at 400°C was performed. It was shown that, during the reduction of Fe(OH)₃ to iron metal α-Fe, intermediate compounds such as Fe(OH)₂, α-FeOOH, β-FeOOH, γ-FeOOH, δ-FeOOH, and FeO are formed along with stable iron oxides α-Fe₂O₃, γ-Fe₂O₃, and Fe₃O₄. A scheme of chemical and structural transformations that occur in the reduction of nanosized Fe(OH)₃ is presented. The scheme takes into account the possibility of the bifurcation mechanism of reaction development.     

Synthesis and characterization of “mulberry”-like Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/multiwalled carbon nanotube nanocomposites

Nanocomposites composed of multi-wall carbon nanotubes (MWNTs) and Fe₃O₄ nanoparticles were fabricated using solvothermal method. Transmission and scanning electron microscopy, energy dispersive spectroscopy, and X-ray powder diffraction measurements confirmed that these mulberry-like Fe₃O₄ microparticles which were combined with the MWNTs in a random pattern are constructed with tiny nanocrystallites (12 nm in average diameter). The magnetic properties of the Fe₃O₄/MWNTs nanocomposites were measured using a vibrating sample magnetometer. Results showed that the Fe₃O₄/MWNTs nanocomposites exhibited superparamagnetism at room temperature and possessed a lower saturation magnetization (around 27.6 emu/g) than that of the pure Fe₃O₄ nanoparticles (around 33.7 emu/g). The Fe₃O₄/MWNTs nanocomposites have potential applications in engineering and medicine.     

Novel carbon nanotube iron oxide magnetic nanocomposites

A novel magnetic nanocomposite of γ-Fe₂O₃ nanoparticles decorated multiwalls carbon nanotubes (MWNTs) was synthesized for the first time by a simple chemistry precipitation method. The structure and morphology of the composite was characterized by X-ray powder diffractometer (XRD), TEM and EDS. The results of XRD and TEM show that γ-Fe₂O₃ nanoparticles is immobilized on the side wall of the MWNTs, the size of most of the particle is <5 nm.The EDS analysis shows that the atomic ratio of Fe to O is 2:3. The magnetization curves of the MWNTs and γ-Fe₂O₃ decorated MWNTs were measured by VSM at room temperature, which indicate that the saturated magnetization (Ms), remanence (Mr) and coercivity (Hc) of the decorated MWNTs are much larger than those of MWNTs, and the decorated MWNTs exhibit well magnetic properties.     

Microstructure and gas sensitive properties of α(M: Sn and Ti) materials prepared by ball milling

Metastable α-Fe₂O₃-MO₂(M: Sn and Ti) solid solutions can be synthesized by mechanical alloying. The alloy formation, microstructure, and gas sensitive properties of mechanically milled α-Fe₂O₃-SnO₂ materials are discussed. Tin ions in α-Fe₂O₃ are found to occupy the empty octahedral holes in the α-Fe₂O₃ lattice. This interstitial model can also describe the structure of α-Fe₂O₃-TiO₂solid solutions. Finally, a correlation of gas sensitive properties with microstructure of α-Fe₂O₃-SnO₂ materials is presented. This revised version was published online in August 2006 with corrections to the Cover Date.     

Non-catalytic and substrate-free method to titania-doped W18O49 nanorods: growth, characterizations, and electro-optical properties

In the present study, titania-doped (Ti-doped) W₁₈O₄₉ nanorods have been prepared using a modified plasma arc gas condensation technique. Characterizations by field-emission gun scanning electron microscopy, X-ray powder diffraction, high-resolution transmission electron microscopy and high-resolution X-ray photoelectron spectroscopy indicate that the as-prepared nanorods with a single-crystalline monoclinic W₁₈O₄₉ phase are of 20–100 nm in diameter and several micrometers in length. The Raman peaks of the Ti-doped W₁₈O₄₉ nanorods show a red-shift Raman peaks, and an additional green-emission peak at 497 nm is observed in the photoluminescence (PL) spectrum compared to pure W₁₈O₄₉ nanorods. Field-emission (FE) measurements reveal that the turn-on (E _to) and threshold (E _thr) voltages of the Ti-doped W₁₈O₄₉ nanorods are 2.2 and 3.4 V/μm, respectively. A vapor–solid process that does not involve the use of catalyst is proposed for the nanorod growth mechanism. Experimental results show that the additional defects resulting from titania doping are responsible for the enhancement of the optical and FE properties of the pure W₁₈O₄₉ nanorods.     

Synthesis and characterization of hybrid nanocomposites of polypyrrole filled with iron oxide nanoparticles

Hybrid polypyrrole (PPy)/α-Fe₂O₃ nanocomposite films were fabricated by spin coating on a glass substrate. X-Ray diffraction analysis revealed the crystalline structure of α-Fe₂O₃ nanostructures and the nanocomposites. The broad PPy peak weakened in intensity as the α-Fe₂O₃ content increased in PPy/α-Fe₂O₃ nanocomposites. Characteristic Fourier-transform IR peaks for pure PPy shifted to higher wavenumbers on addition of α-Fe₂O₃ to PPy/α-Fe₂O₃ nanocomposites. This can be attributed to better conjugation and interactions between PPy and α-Fe₂O₃ nanoparticles. Field-emission scanning electron microscopy, transmission electron microscopy, and atomic force microscopy images of the nanocomposites reveal a uniform distribution of α-Fe₂O₃ nanoparticles in the PPy matrix. UV-vis absorption spectroscopy revealed a blue shift from λ_max= 441 nm for PPy to λ_max= 392 nm for PPy/α-Fe₂O₃, reflecting strong interactions between PPy and α-Fe₂O₃ nanoparticles. The room-temperature dc electrical conductivity increased from 4.33×10⁻⁹ to 1.81×10⁻⁸ S/cm as the α-Fe₂O₃ nanoparticle content increased from 10 to 50 wt.% in PPy/α-Fe₂O₃ nanocomposites.     

Thickness dependent activity of nanostructured TiO2/α-Fe2O3 photocatalyst thin films

The effect of thickness of TiO₂ coating on synergistic photocatalytic activity of TiO₂ (anatase)/α-Fe₂O₃/glass thin films as photocatalysts for degradation of Escherichia coli bacteria in a low-concentration H₂O₂ solution and under visible light irradiation was investigated. Nanograined α-Fe₂O₃ films with optical band-gap of 2.06 eV were fabricated by post-annealing of thermal evaporated iron oxide thin films at 400 °C in air. Increase in thickness of the Fe₂O₃ thin film (here, up to 200 nm) resulted in a slight reduction of the optical band-gap energy and an increase in the photoinactivation of the bacteria. Sol-gel TiO₂ coatings were deposited on the α-Fe₂O₃ (200 nm)/glass films, and then, they were annealed at 400 °C in air for crystallization of the TiO₂ and formation of TiO₂/Fe₂O₃ heterojunction. For the TiO₂ coatings with thicknesses ≤50 nm, the antibacterial activity of the TiO₂/α-Fe₂O₃ (200 nm) was found to be better than the activity of the bare α-Fe₂O₃ film. The optimum thickness of the TiO₂ coating was found to be 10 nm, resulting in about 70 and 250% improvement in visible light photo-induced antibacterial activity of the TiO₂/α-Fe₂O₃ thin film as compared to the corresponding activity of the bare α-Fe₂O₃ and TiO₂ thin films, respectively. The improvement in the photoinactivation of bacteria on surface of TiO₂/α-Fe₂O₃ was assigned to formation of Ti-O-Fe bond at the interface.