Architectures of YF<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> solid and hollow sub-microspheres: a facile arginine-assisted hydrothermal synthesis and luminescence properties

Solid and hollow YF₃:Eu³⁺ spheres assembled by nanorods have been successfully synthesized via a facile arginine-assisted hydrothermal method and followed by a subsequent heat-treatment process. The experimental results reveal that the as-prepared YF₃:Eu³⁺ spheres are composed of the nanorods with a diameter of 20–50 nm and a length of 200–500 nm, the morphologies of YF₃:Eu³⁺ have been changed from solid to hollow spheres assembled by nanorods. With increase of hydrothermal temperature and time, the diameter of YF₃:Eu³⁺ spheres can be controlled from 300 to 800 nm. The solid and hollow spheres show an intense orange red emission peak near 595 nm, corresponding to the ⁵D₀ → ⁷F₁ transition of Eu³⁺. The possible formation mechanism for the hollow spheres has been presented in detail. This amine acid-assisted method is very simple, economic and environmental friendly for organic-free solvent, which would be potentially used in synthesizing other hollow materials.     

Carbon nanotubes/magnetite hybrids prepared by a facile synthesis process and their magnetic properties

In this paper, a facile synthesis process is proposed to prepare multiwalled carbon nanotubes/magnetite (MWCNTs/Fe₃O₄) hybrids. The process involves two steps: (1) water-soluble CNTs are synthesized by one-pot modification using potassium persulfate (KPS) as oxidant. (2) Fe₃O₄ is assembled along the treated CNTs by employing a facile hydrothermal process with the presence of hydrazine hydrate as the mineralizer. The treated CNTs can be easily dispersed in aqueous solvent. Moreover, X-ray photoelectron spectroscopy (XPS) analysis reveals that several functional groups such as potassium carboxylate (-COOK), carbonyl (-CO) and hydroxyl (-C-OH) groups are formed on the nanotube surfaces. The MWCNTs/Fe₃O₄ hybrids are characterized with respect to crystal structure, morphology, element composition and magnetic property by X-ray diffraction (XRD), transmission electron microscopy (TEM), XPS and superconducting quantum interference device (SQUID) magnetometer. XRD and TEM results show that the Fe₃O₄ nanoparticles with diameter in the range of 20-60 nm were firmly assembled on the nanotube surface. The magnetic property investigation indicated that the CNTs/Fe₃O₄ hybrids exhibit a ferromagnetic behavior and possess a saturation magnetization of 32.2 emu/g. Further investigation indicates that the size of assembled Fe₃O₄ nanoparticles can be turned by varying experiment factors. Moreover, a probable growth mechanism for the preparation of CNTs/Fe₃O₄ hybrids was discussed.     

Preparation and optical properties of HgWO<Subscript>4</Subscript> nanorods by hydrothermal method coupled with ultrasonic technique

For the first time, a newly luminescent nanomaterial, monoclinic wolframite-type HgWO₄ nanorods (diameter: ∼200 nm; length: ~2000 nm) are prepared by hydrothermal method together with ultrasonic technique. Fluorescent (FL) and UV–Vis results both show that for HgWO₄, ultrasonic irradiation procedure will change its optical behaviors greatly. When the crystals become into nanorods, the fluorescent emitting peaks (365 and 495 nm) shift to central region, and finally form a wider one at 435 nm. Similar results of UV–visible absorption peaks are observed for these two products. FTIR spectra further characterize their structure. All above unique optical performances might result from both small sizes caused by ultrasonic irradiation procedure and involvement of incompact d¹⁰ electrons. Moreover, possible synthesis mechanisms of HgWO₄ nanorods are also investigated.     

Structure and ultrafast ethanol sensing properties of In2O3-capped Zn-doped Fe2O3 nanorods

This paper reports the facile synthesis of In₂O₃-capped Zn-doped Fe₂O₃ nanorods along with their ethanol gas sensing properties. A two-stage process involving thermal oxidation of Fe foils and Zn powders in air and the sputter-deposition of In₂O₃ was used to synthesize these nanostructures. The nanorods synthesized using this method were ∼5 μm in length and 50–120 nm in diameter with a shell layer thickness of 10–15 nm. The multiple-networked In₂O₃-capped Zn-doped Fe₂O₃ nanorod sensor showed a significantly enhanced and ultrafast response to ethanol gas. The enhanced sensing performance was explained by modulation of the potential barrier height and the strong catalytic activity of In₂O₃ for ethanol oxidation.     

Superhydrophobic iron material surface with flower-like structures obtained by a facile self-assembled monolayer

A simple and economical route based on a K₂CO₃ mediated process was developed to synthesize three-dimensional (3D) flower-like Fe₃O₄ micro/nanoflakes on the surface of iron plates by a direct in-situ hydrothermal synthesis method. The prepared micro/nanoflakes were characterized by X-ray diffraction and scanning electron microscopy. It was found that the width of the nanoflakes ranges from 50 to 100 nm, and the length of the flakes is about 3 μm. The morphology of Fe₃O₄ nanostructures can be tuned from simple isolated nanoflakes to the ordered 3D flower-like shape by increasing the reaction temperature. The wettability of the surface with 3D flower-like micro/nanoflakes was changed from hydrophilicity to superhydrophobicity by chemical modification with vinyl tirethoxy-silane. The static contact angles for water on both of the modified surfaces were larger than 150°, which was closely related to the chemical modification and hierarchical structure. Furthermore, the surfaces retained good superhydrophobic stability in long-term storage as well, which should be critical to the application of iron materials in engineering.     

Synthesis of VO2 (B) nanorods for Li battery application

Vanadium dioxide nanorods were synthesized through a hydrothermal reaction from V₂O₅ xerogel, poly(vinyl pyrrolidone) (PVP) and lithium perchlorate (LiClO₄). The prepared samples were characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical discharge–charge cycling in lithium battery. SEM images reveal the nanorods to have dimensions on the order of 1–3 μm in length and 10–50 nm in diameter. The measured initial discharge capacity of the lithium battery with a cathode made of VO₂ (B) nanorods was 152 mA h/g.     

Fabrication of magnetic gold nanorod particles for immunomagnetic separation and SERS application

The preparation and application of rod-shaped core–shell structured Fe₃O₄–Au nanoparticles for immunomagnetic separation and sensing were described for the first time with this study. To synthesize magnetic gold nanorod particles, the seed-mediated synthetic method was carried out and the resulting nanoparticles were characterized with transmission electron microscopy (TEM), ultraviolet visible spectroscopy (UV–Vis), energy-dispersive X-ray (EDX), and X-ray diffraction (XRD). Magnetic properties of the nanoparticles were also examined. Characterization of the magnetic gold nanorod particles has proven that the resulting nanoparticles were composed of Fe₃O₄ core and the gold shell. The rod-shaped gold-coated iron nanoparticles have an average diameter of 16 ± 2 nm and an average length of about 50 ± 5 nm (corresponding aspect ratio of 3). The saturation magnetization value for the magnetic gold nanorod particles was found to be 37 emu/g at 300 K. Rapid and room temperature reaction synthesis of magnetic gold nanorod particles and subsequent surface modification with E. coli antibodies provide immunomagnetic separation and SERS application. The analytical performance of the SERS-based homogenous sandwich immunoassay system with respect to linear range, detection limit, and response time is also presented.     

Controlled synthesis and magnetic properties of nickel phosphide and bimetallic iron–nickel phosphide nanorods

Nickel phosphide (Ni₂P) and bimetallic iron–nickel phosphides [(Fe _x Ni _y )₂P] nanorods were fabricated by a seeded growth strategy. This strategy utilized pre-synthesized Fe₃O₄ nanoparticles as seeds and the thermal decomposition of metal precursors by multiple injections in a solution containing trioctylphosphine and didodecyldimethylammonium bromide (DDAB). The nanorods were characterized by transmission electron microscopy, X-ray diffraction, and magnetic measurements were carried out using superconducting quantum interference device (SQUID). The rod length was tunable, ranging from 10 to 110 nm depending on the number of injections, whereas the diameter of the rods was nearly 6 nm. It was found that the rod size increased with the number of injections under the constant total injection concentration and reaction time. In addition, the effect of the DDAB quantity used as a co-surfactant was studied, which showed that an optimum quantity was required to achieve uniform nanorods. Magnetic characterizations were performed over the two kinds of nanorods to identify their respective magnetic phases. The results demonstrated that the Ni₂P nanorods were defined as a Curie–Weiss paramagnet, whereas the (Fe _x Ni _y )₂P nanorods exhibited superparamagnetic characteristics.     

Synthesis of carbon-coated Fe3O4 nanorods as electrode material for supercapacitor

Carbon-coated Fe₃O₄ and pure Fe₃O₄ nanorods are synthesized via hydrothermal reaction and subsequent sintering procedure. The as-prepared products characterized by X-ray diffraction and scanning electron microscopy analysis indicate that carbon coating does not affect the structure and morphology of Fe₃O₄. Transmission electron microscope shows that Fe₃O₄ nanorods are homogeneously coated by carbon layer with a thickness of approximately 2 nm. The electrochemical properties measured by cyclic voltammetry, galvanostatic charge–discharge cycling and electrochemical impedance spectroscopy tests show that carbon-coated Fe₃O₄ (Fe₃O₄/C) nanorods present improved electrochemical performance due to the carbon layer. A specific capacitance of 275.9 F?g^?1 is achieved at a current density of 0.5 A g^?1 in 1 M Na₂SO₃ aqueous solution for the Fe₃O₄/C nanorods in comparison to that of 208.6 F?g^?1 for pure Fe₃O₄.     

Biodegradable thermoresponsive polymeric magnetic nanoparticles: a new drug delivery platform for doxorubicin

The use of nanoparticles as drug delivery systems for anticancer therapeutics has great potential to revolutionize the future of cancer therapy. The aim of this study is to construct a novel drug delivery platform comprising a magnetic core and biodegradable thermoresponsive shell of tri-block-copolymer. Oleic acid-coated Fe₃O₄ nanoparticles and hydrophilic anticancer drug “doxorubicin” are encapsulated with PEO–PLGA–PEO (polyethylene oxide–poly d, l lactide-co-glycolide–polyethylene oxide) tri-block-copolymer. Structural, magnetic, and physical properties of Fe₃O₄ core are determined by X-ray diffraction, vibrating sample magnetometer, and transmission electron microscopy techniques, respectively. The hydrodynamic size of composite nanoparticles is determined by dynamic light scattering and is found to be ~36.4 nm at 25 °C. The functionalization of magnetic core with various polymeric chain molecules and their weight proportions are determined by Fourier transform infrared spectroscopy and thermogravimetric analysis, respectively. Encapsulation of doxorubicin into the polymeric magnetic nanoparticles, its loading efficiency, and kinetics of drug release are investigated by UV–vis spectroscopy. The loading efficiency of drug is 89% with a rapid release for the initial 7 h followed by the sustained release over a period of 36 h. The release of drug is envisaged to occur in response to the physiological temperature by deswelling of thermoresponsive PEO–PLGA–PEO block-copolymer. This study demonstrates that temperature can be exploited successfully as an external parameter to control the release of drug.     

Uniform Fe3O4–PANi/PS composite spheres with conductive and magnetic properties and their hollow spheres

Core–shell multifunctional composite spheres consisting of Fe₃O₄–polyaniline (PANi) shell and polystyrene (PS) core were fabricated using core–shell-structured sulfonated PS spheres (with uniform diameter of 250 nm) as templates. PANi was doped in situ by sulfonic acid resulting the composite spheres are well conductive. Dissolved with solvent, PS cores were removed from the core–shell composite spheres and hollow Fe₃O₄–PANi spheres were obtained. Removing the PANi and PS components by calcinations produced hollow Fe₃O₄ spheres. The cavity size of the hollow spheres was uniformly approximate to 190 nm and the shell thickness was 30 nm. The cavity size and the shell thickness can be synchronously controlled by varying the sulfonation time of the PS templates. The shell thickness in size range was of 20–86 nm when the sulfonation time was changed from 1 to 4 h. These resulting spheres could be arranged in order by self-assembly of the templates. Both the Fe₃O₄–PANi/PS composite spheres and the hollow Fe₃O₄ spheres exhibit a super-paramagnetic behavior. Scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray powder scattering were used to characterize these as-prepared spheres. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

One-step synthesis of Fe3O4 nanorods/graphene nanocomposites

A composite of graphene (GE) supported by rod-like Fe₃O₄ nanocrystals has been fabricated by a simple one-step chemical route. X-ray diffraction and transmission electron microscopy results show that the Fe₃O₄ nanorods with diameters in the range of 15?C20 nm and lengths of 150?C200 nm were firmly assembled on the GE nanosheet surface. Magnetic property investigation indicated that the Fe₃O₄/GE composites exhibit a ferromagnetic behavior and possess a saturation magnetization of 50.11?emu?g^?1. Moreover, Fe₃O₄/GE composites showed a very high adsorption capacity of Congo red.     

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.     

Synthesis and physical properties of mixed Co3O4/CoO nanorods by microwave hydrothermal technique

A mixture of crystalline Co₃O₄/CoO nanorods with non-uniform dense distribution has been successfully synthesized by microwave hydrothermal technique. The synthesized nanorods have been characterized by several techniques such as X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier transforms infrared spectroscopy (FT-IR). The results showed that the as synthesized specimens contained mixed crystalline Co₃O₄/CoO nanorods with an average length of around 80 nm and an average diameter of 42 nm. UV–Vis spectrum of the nanorods exhibited a strong UV emission. The band energy gap of the product was 1.79 eV which lies between the energy gap of CoO and that for Co₃O₄. The obtained carrier concentration is of the order 4.32 × 10²⁷ m⁻³ and the dielectric constant is found to be 4.89. The electrical conductivity increases with increasing temperature and behaves as a semiconducting material with an activation energy of a bout 0.26 eV. This makes the as synthesized mixed Co₃O₄/CoO nanorods very useful for supercapacitor devices application. Magnetic hysteresis loops at room temperature of the as synthesized mixed oxides (Co₃O₄/CoO) nanorods exhibit typical soft magnetic behavior.     

Surfactant-free synthesis of novel copper oxide (CuO) nanowire–cobalt oxide (Co<Subscript>3</Subscript>O<Subscript>4</Subscript>) nanoparticle heterostructures and their morphological control

A simple and surfactant-free synthesis of novel heterostructures comprising of copper oxide (CuO) nanowires uniformly decorated with cobalt oxide (Co₃O₄) nanoparticles was demonstrated by combining thermal growth and wet-coating method. The heterostructures were synthesized by thermally decomposing cobalt salt (cobalt nitrate) into Co₃O₄ nanoparticles onto vapor–solid (VS)-grown CuO nanowires. X-ray diffraction (XRD) and high resolution transmission electron microscopy (TEM) confirmed the presence of CuO and Co₃O₄ phases as well as a narrow size distribution of Co₃O₄ nanoparticles (average diameter ~7.0 ± 1.5 nm) on CuO nanowires (average diameter of nanowire tips ~67.9 ± 18.6 nm). Unique interfacial lattice relationship was observed for (111) Co₃O₄ nanoparticles on (200) CuO nanowire surface resulting in hemispherical shape of the former. For the first time, further systematic studies were performed to understand the influence of various parameters (cobalt salt concentration and annealing temperature, atmosphere, and time) on the morphological evolution of Co₃O₄ nanoparticles on CuO nanowires. Interestingly, by varying these parameters, it was possible to grow Co₃O₄ in different shapes (spherical, triangular, rectangular, cubical, and hexagonal nanoparticles) and forms (shells and nanorods). It was observed that all these parameters play a critical role in influencing the surface migration, nucleation, and growth of Co₃O₄ nanoparticles on CuO nanowires and this assisted in understanding the involved growth mechanisms. Finally, UV–vis–NIR spectroscopy and band gap energies for these heterostructures were evaluated that showed higher photocatalytic degradation efficiency for Rhodamine B under low-power visible-light illumination.     

Hydrothermal synthesis and magnetic properties of CuSb<Subscript>2</Subscript>O<Subscript>6</Subscript> nanoparticles and nanorods

Nanoparticles and nanorods of CuSb₂O₆ are prepared by hydrothermal method and its high temperature α-phase is stabilized at room temperature. The average size of the nanoparticles is ca. 13.7 nm. The nanorods, with a width of ca. 20 nm and an aspect ratio of ca. 5, are the agglomerates composing of smaller nanoparticles with an average size of ca. 8.3 nm. Compared with the high temperature α-phase of bulk sample at 400 K, the lattice of nanophases elongated in ab plane and compressed along c direction. The CuSb₂O₆ nanoparticles exhibit predominant paramagnetic phenomenon. The difference in magnetic properties of the nanoparticles and nanorods indicates the interfacial interaction of agglomerated nanoparticles.     

A new one-step synthesis method for coating multi-walled carbon nanotubes with iron oxide nanorods

A facile solution-chemical method has been developed to be capable of covering a multiwalled carbon nanotube (MWNTs) with iron oxide nanorods without using any bridging species. MWNTs in this composite were decorated randomly by α-Fe₂O₃ nanorods with diameters in the range of 3–5 nm and lengths of 15–30 nm. The formation route to anchor α-Fe₂O₃ nanorods onto MWNTs was proposed as the intercalation and adsorption of iron ions onto the wall of MWNTs, followed by the nucleation and growth of α-Fe₂O₃ nanorods. α-Fe₂O₃/MWNTs nanocomposites show specific high Brunauer–Emmett–Teller surface areas. The photocatalytic activity experiment indicated that the prepared α-Fe₂O₃/MWNTs nanocomposites exhibited a higher photocatalytic activity for the photocatalytic decolorization of rhodamine B aqueous solution under the visible-light illumination than the single phase α-Fe₂O₃ samples. This methodology made the synthesis of MWNTs-nanorods composites possible and may be further extended to prepare more complicated nanocomposites based on MWNTs for technological applications.     

Synthesis of magnetic core–shell Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>–Au nanoparticle for biomolecule immobilization and detection

The production of monodispersed magnetic nanoparticles with appropriate surface modification has attracted increasing attention in biomedical applications including drug delivery, separation, and purification of biomolecules from the matrices. In the present study, we report rapid and room temperature reaction synthesis of gold-coated iron nanoparticles in aqueous solution using the borohydride reduction of HAuCl₄ under sonication for the first time. The resulting nanoparticles were characterized with transmission electron microscopy (TEM), electron spectroscopy for chemical analysis (ESCA), ultraviolet visible spectroscopy (UV–Vis), and X-ray diffraction (XRD). Surface charges and magnetic properties of the nanoparticles were also examined. The pattern of Fe₃O₄ nanoparticles is face centered cubic with an average diameter of 9.5 nm and the initial reduction of gold on the surface of Fe₃O₄ particles exhibits uniform Fe₃O₄–Au nanoparticles with an average diameter of 12.5 nm. The saturation magnetization values for the uncoated and gold-coated Fe₃O₄ nanoparticles were found to be 30 and 4.5 emu/g, respectively, at 300 K. The progression of binding events between boronic acid terminated ligand shell and fructose based on the covalent bonding interaction was measured by absorbance spectral changes. Immunomagnetic separation was also performed at different E. coli concentration to evaluate capturing efficiency of resulting nanoparticles. Immunomagnetic separation percentages were varied in a range of 52.1 and 21.9% depend on the initial bacteria counts.     

A novel synthesis of FeNbO<Subscript>4</Subscript> nanorod by hydrothermal process

This study reports a facile, gram-scale synthesis of FeNbO₄ nanorods via hydrothermal route, using iron nitrate [Fe(NO₃)₃] and niobium tartarate (Nb tartarate) in presence of potassium peroxosulfate. The formation of single phase, polycrystalline orthorhombic structure of FeNbO₄ was confirmed by the careful analysis of the X-ray diffraction (XRD) pattern. The average crystallite size, calculated using a few XRD peaks, was found to be 12.8 nm. As indicated by transmission electron microscopy (TEM) and field emission scanning electron microscopy, the average length and diameter of the rods were found to be only 25 × 7 nm and 47 × 14 nm, respectively. The selected area electron diffraction and high-resolution transmission electron microscopy (HRTEM) data of the single rod implied that FeNbO₄ nanorods were polycrystalline in nature and grew up along the c-axis. HRTEM also revealed that the fringes are equidistant with a lattice separation of 0.91 Ǻ, which corresponded to the (111) plane of the FeNbO₄ crystal. Elemental composition of the nanorods was confirmed using electron dispersive X-ray spectroscopy analysis while binding state of the surface was intervened through X-ray photoelectron spectroscopy. Mechanistic investigations suggested that potassium peroxosulfate played a crucial role in the unidirectional growth of particles. The synthetic method is simple, amenable to scale up and contributes a new tool box for the development of FeNbO₄-based one-dimensional (1D) structures that appears to be more promising for a myriad of applications, compared to their 3D counterparts.     

Preparation and characterization of Fe3O4 magnetic composite microspheres covered by a P(MAH-co-MAA) copolymer

A magnetic core–shell-layered polymer microsphere (MPS) was successfully synthesized by a dispersion polymerization route, where the modified Fe₃O₄ nanoparticles (MFN) were used as a core, while poly(maleic anhydride-co-methacrylic acid) P(MAH-co-MAA) as a shell was covered on the surface of the Fe₃O₄ nanoparticles. Environmental scanning electron microscope (ESME) and transmission electron microscope (TEM) measurements indicate that the magnetic P(MAH-co-MAA)/Fe₃O₄ composite microspheres assume sphericity and have a novel core–shell-layered structure. The crystal particle sizes of the unimproved Fe₃O₄ and the MFN samples vary from 8 to 16 nm in diameter, and the average size is about 10.6 nm in diameter. The core–shell magnetic composite microspheres can be adjusted by changing the stirring speed. Since multiple Fe₃O₄ cores were coated with a proper percentage of P(MAH-co-MAA) copolymers, and therefore lower density was acquired for the MPS, which improved sedimentation and dispersion behavior. The saturated magnetization of pure Fe₃O₄ nanoparticles reaches 48.1 emu g⁻¹ and the value for composite nanoparticles was as high as 173.5 emu g⁻¹. The nanoparticles show strong superparamagnetic characteristics and can be expected to be used as a candidate for magnetism-controlled drug release.