Phase transformations in CaCO3/iron oxide composite induced by thermal treatment and laser irradiation

Calcium carbonate (CaCO₃)/iron oxide composites were synthesized through a simple one‐step impregnation procedure by mixing iron oxide nanoparticles (γ‐Fe₂O₃ and Fe₃O₄) of about 6 nm in size and CaCO₃ microparticles (Φ = 2 µm–8 µm, vaterite phase). The morphology and structural properties of CaCO₃, iron oxide nanoparticles and CaCO₃/iron oxide composites were characterized as a function of low iron content (0 %w to 3.2 %w) by scanning electron microscopy and transmission electron microscopy, X‐ray diffraction and ⁵⁷Fe Mössbauer spectrometry. The phase transformations induced by thermal treatment and laser irradiation were investigated in situ by X‐ray thermodiffraction (XRTD) and Raman spectroscopy. We have shown that the phase transformations observed by XRTD are also observed under laser irradiation as a consequence of the absorption of the laser irradiation by iron oxide nanoparticles. Copyright © 2012 John Wiley & Sons, Ltd.     

Thermomagnetically Responsive γ‐Fe2O3@Wax@SiO2 Sub‐Micrometer Capsules

A three steps synthesis route is proposed to generate thermosensitive and magnetically responsive γ‐Fe₂O₃@Wax@SiO₂ sub‐micrometer capsules with a paraffinic core and a solid and brittle shell. The process integrates Pickering‐based emulsions, inorganic and sol–gel chemistries to promote monodisperse in size wax droplets, γ‐Fe₂O₃ nanoparticles and mineralization of the wax/water interfaces. Hybrid capsules are obtained with an average size around 800 nm, representing the first example of sub‐micrometer capsules generated employing Pickering emulsions as templates. Cetyltrimethylammonium bromide (CTAB) cationic surfactant added during mineralization at concentrations between 0.17 and 1.0 wt% impacts the shell density. The shell density seems to improve its mechanical strength while affording a low wax expansion volume without breaking for CTAB concentrations above 1.0 wt%. At lower CTAB concentration (0.17 wt%), the silica shell becomes less bulky and cannot resist the wax dilatation induced by the solid‐to‐liquid phase transition imposed by hyperthermia. The magnetically induced heating provided by the internal magnetic moments is sufficient to melt the wax core, expanding its volume, inducing thereby the surrounding silica shell rupture. Such γ‐Fe₂O₃@Stearic Acid@Wax@SiO₂ sub‐micrometer capsules allow a sustained wax release with time, whereby 20% of the wax is released after 50 min of alternating magnetic field treatment.     

Micro‐Raman investigation of transition‐metal‐doped ZnO nanoparticles

We measured the Raman spectra of ZnO nanoparticles (ZnO‐NPs), as well as transition‐metal‐doped (5% Mn(II), Fe(II) or Co(II)) ZnO nanoparticles, with an average size of 9 nm. A typical Raman peak at 436 cm⁻¹ is observed in the ZnO‐NPs, whereas Zn_1−xMn_xO, Zn_1−xFe_xO and Zn_1−xCo_xO presented characteristic peaks at 661, 665 and 675 cm⁻¹, respectively. These peaks can be related to the formation of Mn₃O₄, Fe₃O₄ and Co₃O₄ species in the doped ZnO‐NPs. Moreover, these samples were analyzed at various laser powers. Here, we observed new vibrational modes (512, 571 and 528 cm⁻¹), which are specific to Mn, Fe and Co dopants, respectively, and ZnO‐NPs did not reveal any additional modes. The new peaks were interpreted either as disorder activated phonon modes or as local vibrations of Mn‐, Fe‐ and Co‐related complexes in ZnO. Copyright © 2007 John Wiley & Sons, Ltd.     

Facile Synthesis of Gd(OH)3‐Doped Fe3O4 Nanoparticles for Dual‐Mode T1‐ and T2‐Weighted Magnetic Resonance Imaging Applications

The facile hydrothermal synthesis of polyethyleneimine (PEI)‐coated iron oxide (Fe₃O₄) nanoparticles (NPs) doped with Gd(OH)₃ (Fe₃O₄‐Gd(OH)₃‐PEI NPs) for dual mode T₁‐ and T₂‐weighted magnetic resonance (MR) imaging applications is reported. In this approach, Fe₃O₄‐Gd(OH)₃‐PEI NPs are synthesized via a hydrothermal method in the presence of branched PEI and Gd(III) ions. The PEI coating onto the particle surfaces enables further modification of poly(ethylene glycol) (PEG) in order to render the particles with good water dispersibility and improved biocompatibility. The formed Fe₃O₄‐Gd(OH)₃‐PEI‐PEG NPs have a Gd/Fe molar ratio of 0.25:1 and a mean particle size of 14.4 nm and display a relatively high r₂ (151.37 × 10^?3m ^?1 s^?1) and r₁ (5.63 × 10^?3m ^?1 s^?1) relaxivity, affording their uses as a unique contrast agent for T₁‐ and T₂‐weighted MR imaging of rat livers after mesenteric vein injection of the particles and the mouse liver after intravenous injection of the particles, respectively. The developed Fe₃O₄‐Gd(OH)₃‐PEI‐PEG NPs may hold great promise to be used as a contrast agent for dual mode T₁‐ and T₂‐weighted self‐confirmation MR imaging of different biological systems.     

Multifunctional Plasmonic Co‐Doped Fe2O3@polydopamine‐Au for Adsorption,Photocatalysis, and SERS‐based Sensing

A new type of multifunctional plasmonic nanoparticles, cobalt‐doped Fe₂O₃@polydopamine‐Au (Co‐Fe₂O₃@PDA‐Au), is fabricated via coating PDA through self‐polymerization onto Co‐Fe₂O₃ and further loading gold nanoparticles by in situ reduction onto the surface of PDA shell. Benefiting from the universal adhesive ability of PDA and negative zeta potetntial of the composite, the Co‐Fe₂O₃@PDA‐Au shows strong adsorptivity for cationic dyes. The presence of gold nanoparticle with the diameter of 15 nm in the Co‐Fe₂O₃@PDA‐Au system promotes surface‐enhanced Raman scattering (SERS) activity with an impressive detection limit of 1 × 10^?6 m . Thanks to the synergistic effect of the light harvesting of PDA, the surface plasmon resonance of Au, and the electron conductibility of PDA and Au, the Co‐Fe₂O₃@PDA‐Au exhibits an enhanced photocatalytic activity comparing with unmodified Co‐Fe₂O₃. All the above‐mentioned functions enable Co‐Fe₂O₃@PDA‐Au to be a multifunctional material system for various applications toward environmental pollutants.     

Surface‐enhanced Raman scattering of 4‐mercaptopyridine on sub‐monolayers of α‐Fe2O3 nanocrystals (sphere,spindle, cube)

We report surface‐enhanced Raman scattering (SERS) spectra from 4‐mercaptopyridine (4‐Mpy) adsorbed on sub‐monolayers of α‐Fe₂O₃ nanocrystals (sphere, spindle, cube). The maximum enhancement factor has been estimated to be about 10⁴ compared to that of 4‐Mpy in solution. A possible mechanism has been proposed that the charge transfer between the α‐Fe₂O₃ nanocrystals and the 4‐Mpy molecules is most likely responsible for the observed enhancement of Raman intensity of adsorbed 4‐Mpy molecules as surface plasmon resonances have not occurred. Copyright © 2009 John Wiley & Sons, Ltd.     

Yolk–Shell‐Structured Cu/Fe@γ‐Fe2O3 Nanoparticles Loaded Graphitic Porous Carbon for the Oxygen Reduction Reaction

Core–shell Cu/γ‐Fe₂O₃@C and yolk–shell‐structured Cu/Fe@γ‐Fe₂O₃@C particles are prepared by a facile synthesis method using copper oxide as template particles, resorcinol‐formaldehyde as the carbon precursor, and iron nitrate solution as the iron source via pyrolysis. With increasing carbonization temperature and time, solid γ‐Fe₂O₃ cores are formed and then transformed into Fe@γ‐Fe₂O₃ yolk–shell‐structured particles via Ostwald ripening under nitrogen gas flow. The composition variations are studied, and the formation mechanism is proposed for the generation of the hollow and yolk–shell‐structured metal and metal oxides. Moreover, highly graphitic carbons can be obtained by etching the metal and metal oxide nanoparticles through an acid treatment. The electrocatalytic activity for oxygen reduction reaction is investigated on Cu/γ‐Fe₂O₃@C, Cu/Fe@γ‐Fe₂O₃@C, and graphitic carbons, indicating comparable or even superior performance to other Fe‐based nanocatalysts.     

Effect of nanosizing on lattice and magnon modes of hematite

Broadening of Raman lines and a decrease of frequencies relative to the bulk material are observed for the lattice modes of nanoparticles of the hematite phase of Fe₂O₃. The magnon mode frequency is observed to shift up with reduced particle size in contrast to the lattice modes. The effects are suggested to be a result of phonon confinement and represent the first observation of phonon confinement effects on magnon modes. The Fe₂O₃ nanoparticles are produced by laser decomposition of Fe₃O₄ nanoparticles. X-ray diffraction and Raman frequency shifts indicate the Fe₂O₃ nanoparticles are smaller than the parent Fe₃O₄ nanoparticles.     

Effects of the agglomeration state on the Raman properties of Co3O4 nanoparticles

The features of the Raman spectra of Co₃O₄ 30‐nm nanoparticles depend strongly on their agglomeration state. When measured at low incident laser power, the spectrum of isolated nanoparticles corresponds to that found in bulk materials, whereas the agglomerated nanoparticles present a clear red‐shift and broadening of the Raman bands. On the other hand, when measured at even lower power, both agglomerated and isolated nanoparticles show the same spectrum of microscopic particles. These effects have been studied by variations of the 532‐nm laser power and the environmental temperature. The thermal dependence of Raman spectra of agglomerated nanoparticles is different to that of isolated nanoparticles but is comparable to the one of bulk material. The different behaviour of the nanoparticles at different agglomeration state is associated to the transmission of phonons among the particles. On the other hand, an increase of the laser power causes a larger number of acoustic phonons, producing a variation of the vibration anharmonicity of the nanoparticles. This increase is more pronounced in the agglomerated nanoparticles, due to the transmission of phonons, causing a much intense modification of the Raman spectrum produced by the laser power. These results clearly indicate that the agglomeration state of the nanoparticles affects their Raman properties. Copyright © 2012 John Wiley & Sons, Ltd.     

Magnetization of Fe‐oxide based nanocomposite tuned by surface charging

Aiming at a voltage‐control of magnetism, the magnetization of a porous γ‐Fe₂O₃–Pt nanocomposite is studied under the influence of charging the surfaces of the porous structure in an electrolyte. Reversible variations of the magnetization of up to 10.4% could be achieved upon charging in the regime where electrochemical adsorption and desorption occurs. The observed variation of the magnetization with electrochemical charging is assigned to the γ‐Fe₂O₃ nanoparticles whereas the conductive network of Pt nanoparticles is necessary for charging. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman study of ultrathin Fe3O4 films on GaAs(001) substrate: stoichiometry,epitaxial orientation and strain

The growth and characterization of high‐quality ultrathin Fe₃O₄ films on semiconductor substrates is a key step for spintronic devices. A stable, single‐crystalline ultrathin Fe₃O₄ film on GaAs(001) substrate is obtained by post‐growth annealing of epitaxial Fe film with thicknesses of 5 and 12 nm in air. Raman spectroscopy shows a high ability to convincingly characterize the stoichiometry, epitaxial orientation and strain of such ultrathin Fe₃O₄ films. Polarized Raman spectroscopy confirms the unit cell of Fe₃O₄ films is rotated by 45° to match that of the Fe (001) layer on GaAs, which results in a built‐in strain of − 3.5% in Fe₃O₄ films. The phonon strain‐shift coefficient(−126 cm⁻¹) of the A_1g mode is proposed to probe strain effect and strain relaxation of thin Fe₃O₄ films on substrates. It can be used to identify whether the Fe layer is fully oxidized to Fe₃O₄ or not. Copyright © 2011 John Wiley & Sons, Ltd.     

Monodisperse Polypyrrole Nanoparticles Prepared via γ‐Ray Radiolysis of Water: An Efficient Near‐Infrared Photothermal Agent for Cancer Therapy

Biosafe nanoparticles with strong near‐infrared (NIR) light photothermal conversion effect can bring effective hyperthermia as one of the promising approaches in cancer therapy. In this work, a new facile and green preparation method of polypyrrole (PPy) nanoparticles based on ⁶⁰Co γ‐ray radiation on a simple air‐saturated strong acidic aqueous solution of pyrrole (pH ≤ 1) is studied. According to the MCAP‐FACSIMILE simulation on the concentrations of the radiolysis products of water at the presence of H⁺ and O₂, the main strong oxidative radiolysis products · OH and H₂O₂ rapidly induce the polymerization of pyrrole. The size of the prepared PPy nanoparticles is about several tens of nanometers and can be controlled by the pH, the concentration of the stabilizer poly(vinyl alcohol), and the absorbed dose rate (the amount of energy absorbed per unit mass of the irradiated material within per unit of time). The PPy nanoparticles show rapid and remarkable NIR (808 nm) photothermal conversion efficiency up to 40.1% in water. Furthermore, the in vitro and in vivo experiments confirm that the prepared PPy nanoparticles exhibit enough strong NIR photothermal effect in tumor cells (4T1 and HeLa) and show a promising prospect as the NIR photothermal agent for the future cancer therapy.     

Microwave synthesis of magnetic Fe3O4 nanoparticles used as a precursor of nanocomposites and ferrofluids

Methods to synthesize magnetic Fe₃O₄ nanoparticles and to modify the surface of particles are presented in the present investigation. Fe₃O₄ magnetic nanoparticles were prepared by the co-precipitation of Fe³⁺ and Fe²⁺, NH₃·H₂O was used as the precipitating agent to adjust the pH value, and the aging of Fe₃O₄ magnetic nanoparticles was accelerated by microwave (MW) irradiation. The obtained Fe₃O₄ magnetic nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and vibrating sample magnetometer (VSM). The average size of Fe₃O₄ crystallites was found to be around 8–9 nm. Thereafter, the surface of Fe₃O₄ magnetic nanoparticles was modified by stearic acid. The resultant sample was characterized by FT-IR, scanning electron microscopy (SEM), XRD, lipophilic degree (LD) and sedimentation test. The FT-IR results indicated that a covalent bond was formed by chemical reaction between the hydroxyl groups on the surface of Fe₃O₄ nanoparticles and carboxyl groups of stearic acid, which changed the polarity of Fe₃O₄ nanoparticles. The dispersion of Fe₃O₄ in organic solvent was greatly improved. Effects of reaction time, reaction temperature and concentration of stearic acid on particle surface modification were investigated. In addition, Fe₃O₄/polystyrene (PS) nanocomposite was synthesized by adding surface modified Fe₃O₄ magnetic nanoparticles into styrene monomer, followed by the radical polymerization. The obtained nanocomposite was tested by thermogravimetry (TG), differential scanning calorimetry (DSC) and XRD. Results revealed that the thermal stability of PS was not significantly changed after adding Fe₃O₄ nanoparticles. The Fe₃O₄ magnetic fluid was characterized using UV–vis spectrophotometer, Gouy magnetic balance and laser particle-size analyzer. The testing results showed that the magnetic fluid had excellent stability, and had susceptibility of 4.46×10⁻⁸ and saturated magnetization of 6.56 emu/g. In addition, the mean size d (0.99) of magnetic Fe₃O₄ nanoparticles in the fluid was 36.19 nm.     

Synthesis and Characterization of La‐Doped Fe3O4‐Polyaniline Magnetic Response Nanocomposites

Lanathum (La)‐doped Fe₃O₄ magnetic nanoparticles were prepared in aqueous solution at room temperature, then La‐doped Fe₃O₄‐polyaniline (PANI) nanocomposites containing a dispersion of La‐doped Fe₃O₄ nanoparticles were synthesized via in‐situ polymerization of aniline monomer. The structure and properties of the synthesized samples were characterized with X‐ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectrometry (FTIR), thermogravimetric analysis (TGA), inductively coupled plasma atomic emission spectrometry (ICPAES), and a vibrating sample magnetometer (VSM). The resulting particles of La‐doped Fe₃O₄ and La‐doped Fe₃O₄‐PANI were almost spherical with diameters ranging from 15 to 25 nm and 25 to 85 nm, respectively. The La‐doped Fe₃O₄‐PANI composite presented core‐shell structures; polyaniline covered the La‐doped Fe₃O₄ completely. The specific saturation magnetization of La‐doped Fe₃O₄‐PANI depended on the starting material of La‐doped Fe₃O_4. It increased with increasing amounts of La and Fe₃O₄ content.     

Visible light response of silver 4‐aminobenzenethiolate and silver 4‐dimethylaminobenzenethiolate probed by Raman scattering spectroscopy

Silver thiolate is a layered compound with a Raman spectrum that is known to change with time, becoming the same as the surface‐enhanced Raman scattering (SERS) spectrum of the parent thiol molecule adsorbed on Ag nanoparticles. On this basis, the Raman scattering characteristics of silver 4‐aminobenzenethiolate (Ag‐4ABT) compounds were investigated to determine whether certain peaks that are identifiable in the SERS spectrum of 4‐aminobenzenethiol (4‐ABT) but absent in its normal Raman spectrum were also apparent in the Ag salt spectrum. For comparative purposes, the Raman scattering characteristics of silver 4‐dimethylaminobenzenethiolate (Ag‐4MABT) were also examined. Raman spectra acquired while spinning the sample were typified by only a₁‐type vibrational bands of Ag‐4ABT and Ag‐4MABT, whereas in the static condition, several non‐a₁‐type bands were identified. The spectral patterns acquired in the static condition were similar to the intrinsic SERS spectra of 4‐ABT or 4‐dimethylaminobenzenethiol (4‐MABT) adsorbed on pure Ag nanoparticles. Notably, the CH₃ group vibrational bands were observable for Ag‐4MABT irrespective of the sample rotation. In addition, no decrease in intensity during irradiation with a visible laser was observed for any of the bands, suggesting that no chemical conversion actually took place in either 4‐ABT or 4‐MABT. The preponderance of evidence led to the conclusion that the non‐a₁‐type bands observable in the SERS spectra must be associated with the chemical enhancement mechanism acting on the Ag nanoparticles. The chemical enhancement effect was more profound at 514.5 nm than at 632.8 nm, and was more favorable for 4‐ABT than 4‐MABT at both wavelengths. Copyright © 2012 John Wiley & Sons, Ltd.     

The growth of the passive film on iron in 0.05 M NaOH studied in situ by Raman micro‐spectroscopy and electrochemical polarisation. Part I: near‐resonance enhancement of the Raman spectra of iron oxide and oxyhydroxide compounds

Raman spectroscopy, in principle, is an excellent technique for the study of molecular species developed on metal surfaces during electrochemical investigations. However, the use of the more common laser wavelengths such as the 514.5‐nm line results in spectra of less than optimal intensity, particularly for iron oxide compounds. In the present work, near‐resonance enhancement of the Raman spectra was investigated for the iron oxide and iron oxyhydroxide compounds previously reported to be present in the passive film on iron, using a tuneable dye laser producing excitation wavelengths between 560 and 637 nm. These compounds were hematite (α‐Fe₂O₃), maghemite (γ‐Fe₂O₃), magnetite (Fe₃O₄), goethite (α‐FeOOH), akaganeite (β‐FeOOH), lepidocrocite (γ‐FeOOH) and feroxyhyte (δ‐FeOOH). Optimum enhancement, when compared to that with the 514.5‐nm line, was obtained for all the iron oxide and oxyhydroxide standard samples in the low wavenumber region (<1000 cm⁻¹) using an excitation wavelength of 636.4 nm. Particularly significant enhancement was obtained for lepidocrocite, hematite and goethite. Copyright © 2010 John Wiley & Sons, Ltd.     

Clean and reproducible SERS substrates for high sensitive detection by solid phase synthesis and fabrication of Ag‐coated Fe3O4 microspheres

The solid‐phase synthesis of Ag‐coated Fe₃O₄ microsphere was elaborated under argon atmosphere. This straightforward process utilized neither reducing agents nor electric current and involved the dry mixing of a precursor of CH₃COOAg with Fe₃O₄ microspheres followed by heating in an inert atmosphere. Ag nanoparticles with diameters of 30–50 nm were well‐decorated on the surfaces of Fe₃O₄ microspheres. The as‐synthesized Ag‐coated Fe₃O₄ microspheres were assembled into a surface‐enhanced Raman scattering (SERS) substrate holding clean and reproducible properties under an externally exerted magnetic force. Using these nanoprobes, analyte molecules can be easily captured, magnetically concentrated, and analyzed by SERS. This clean SERS substrate was used to detect 4‐aminothiophenol, even at a concentration as low as1.0 × 10^–12 M. In particular, the Ag‐coated Fe₃O₄ microspheres, acting as reproducible SERS substrates, were applied to detect methyl‐parathion and 4‐mercaptopyridine. Strong SERS signals were obtained with the analytes at a concentration of 1.0 × 10^–6 M. The unique, clean, and reproducible properties indicate a new route in eliminating the single‐use problem of traditional SERS substrates and show promising applications for detecting other organic pollutants. Similarly, this work may provide a new model system to a series of metal–Fe₃O₄ decorating reactions for a reproducible utilization. Copyright © 2012 John Wiley & Sons, Ltd.     

Spectroscopic and thermal studies on the inclusion of trans‐cinnamic acid and a number of its hydroxyl‐derivatives with α, β and γ‐cyclodextrins molecules

The inclusion compounds of α‐, β‐ and γ‐cyclodextrins (α‐CD, β‐CD and γ‐CD) with trans‐cinnamic acid (t‐CIA), 3‐hydroxy‐trans‐cinnamic acid (t‐3OHCIA), 4‐hydroxy‐trans‐cinnamic acid (t‐4OHCIA) and 3,4‐dihydroxy‐trans‐cinnamic acid (t‐3,4OHCIA) were prepared and characterized, in the solid state, by means of thermogravimetry and Raman spectroscopy. The effects of the inclusion process on the guest molecules and on the hydrogen bond interactions of the guest were studied by monitoring sensitive vibrational modes, such as CO, CC and ring C H stretching modes. By combining Raman and TG data with ab initio calculations and information from CSD database on similar compounds, inclusion geometries for the different compounds are proposed. The size of the host cavity and the maximization of host/guest hydrogen‐bonding contacts appear to be the main factors determining the inclusion geometries. Copyright © 2009 John Wiley & Sons, Ltd.     

Electro-precipitation of Fe3O4 nanoparticles in ethanol

The preparation of superparamagnetic magnetite (Fe₃O₄) nanoparticles by electro-precipitation in ethanol is proposed. Particle average size can be set from 4.4 to 9 nm with a standard deviation around 20%. Combination of wide-angle X-ray scattering (WAXS), Electron energy loss spectroscopy (EELS) and Mössbauer spectroscopy characterizations clearly identifies the particles as magnetite single-crystals (Fe₃O₄).     

Preparation and application of core–shell Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/polythiophene nanoparticles

The Fe₃O₄/polythiophene nanoparticles, possessing core–shell structure, were prepared by two-step method. In the first step, the Fe₃O₄ particles were synthesized via co-precipitation of FeCl₃ and FeSO₄, using the NH₃·H₂O and N₂H₄·H₂O as precipitant system. In the second step, the thiophene adsorbed and polymerized on the surface of the Fe₃O₄ in the solvent of chloroform. Raman, FTIR, EDS, XRD, TEM, Zeta potential measurement and TG-SDTA were employed to characterize the composition and structure of the products. The results showed that the Fe₃O₄/polythiophene nanoparticles were successfully synthesized with good dispersion and stable core–shell structure, provided with average particle size of approximately 20 nm, in which the diameter of Fe₃O₄ core was approximately 14 nm and the thickness of polythiophene shell was approximately 3–4 nm. Then, the nanoparticles were added into alkyd varnish to prepare a composite coating. The neutral salt spray test, paraffin control test and mechanical test were carried out to identify the properties of the composite coating. It was found that the composite coating had good performances of anticorrosion and paraffin controlling when the mass fraction of the nanoparticles was 0.8–1 wt% in alkyd varnish. As a multifunctional material, the Fe₃O₄/polythiophene nanoparticles can be used in the internal coating of pipeline and have great potential application in crude oil pipeline transportation.