Fabrication of chloroform sensor based on hydrothermally prepared low-dimensional β-Fe2O3 nanoparticles

Hydrothermally prepared as-grown low-dimensional nano-particles (NPs) have been characterized using UV–vis spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Raman spectroscopy, and electron dispersion spectroscopy (EDS). The uniformity of the nano-material was executed by the scanning electron microscopy, where the single phase of the nano-crystalline β-Fe₂O₃ was characterized using XRD techniques. β-Fe₂O₃ nanoparticles fabricated glassy carbon electrode (GCE) have improved chloroform-sensing performances in terms of electrical response (I–V technique) for detecting analyte in liquid phase. The analytical performances were investigated, which showed that the better sensitivity, stability, and reproducibility of the sensor improved significantly by using Fe₂O₃ NPs thin-film on GCE. The calibration plot was linear (R = 0.9785) over the large range of 12.0 μM to 12.0 mM. The sensitivity was calculated as 2.1792 μA cm⁻² mM⁻¹ with a detection limit of 4.4 ± 0.10 μM in short response time (10.0 s).     

One-step solution synthesis of Fe2O3 nanoparticles at low temperature

A new synthesis method of α-Fe₂O₃ nanoparticles was developed, in which the ferrous and ferric salts as well as polyaniline acted as the precursor and dispersant, respectively. From the investigation of X-ray diffraction and FT-IR spectra, the α-Fe₂O₃ nanoparticles can be directly prepared by the co-precipitation method without high-temperature calcining. Transmission electron microscope (TEM) and scanning electron microscope (SEM) observation revealed that the α-Fe₂O₃ nanoparticles had average diameters ranging from 30.0 to 75.0 nm. Compared with previous methods, this present method shows an easy processing and can be applied on the large-scale produce of α-Fe₂O₃ nanoparticles in one step.     

Polyvinylpyrrolidone and arsenic-induced changes in biological responses of model aquatic organisms exposed to iron-based nanoparticles

The efficiency of zero-valent iron particles used in the remediation of contaminated groundwater has, with the emergence of nanotechnology, stimulated interest on the use of nano-size particles to take advantage of high-specific surface area and reactivity characteristics of nanoparticles (NPs). Accordingly, engineered iron-NPs are among the most widely used nanomaterials for in situ remediation. However, while several ecotoxicity studies have been conducted to investigate the adverse impacts of these NPs on aquatic organisms, research on the implications of spent iron-based NPs is lacking. In this study, a comparative approach is used, in which the biological effects of three iron-based NPs (Fe₃O₄ and γ-Fe₂O₃ NPs with particle sizes ranging from 20 to 50 nm, and Fe⁰-NPs with an average particle size of 40 nm) on Raphidocelis subcapitata (formely known as Pseudokirchneriella subcapitata) and Daphnia magna were investigated using both as-prepared and pollutant-doped Fe-based NPs. For the latter, arsenic (As) was used as example sorbed pollutant. The results show that improved degree of NP dispersion by use of polyvinylpyrrolidone overlapped with both increased arsenic adsorption capacity and toxicity to the tested organisms. For R. subcapitata, Fe-oxide NPs were more toxic than Fe⁰-NPs, due primarily to differences in the degree of NPs aggregation and ability to produce reactive oxygen species. For the invertebrate D. magna, a similar trend of biological responses was observed, except that sorption of As to Fe⁰-NPs significantly increased the toxic response when compared to R. subcapitata. Overall, these findings point to the need for research on downstream implications of NP-pollutant complexes generated during water treatment by injection of NPs into aquatic systems.     

Dependence of pH and surfactant effect in the synthesis of magnetite (Fe3O4) nanoparticles and its properties

Nanoparticles of Fe₃O₄ were synthesized by co-precipitation in an aqueous solution containing ferrous and ferric salts (1:2) at varying pH with ammonia as a base. It was found that the value of pH influences the reaction mechanism for the formation of Fe₃O₄. Furthermore, the addition of mercaptoethanol significantly reduced the crystalline size of Fe₃O₄ nanoparticles from 15.03 to 8.02 nm. X-ray diffraction (XRD) spectra revealed that the synthesized nanoparticles were ε-Fe₂O₃ or Fe₃O₄ phase. To further prove the composition of the product, as-prepared Fe₃O₄ were examined by X-ray photoelectron spectroscopy (XPS). Magnetic properties of the obtained particles were determined by vibrating sample magnetometer (VSM). Further analysis of the X-ray studies shows that while maintaining a pH value of 6 and 9 in a solution containing iron salts II and III ions produces ε-Fe₂O₃. Whereas a pH value of 11 produces magnetite (Fe₃O₄) phase. All of these results show that the pH has a major role in the observed phase formation of (Fe₃O₄) nanoparticles.     

Dye-sensitized solar cells with 3D flower-like α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-decorated reduced graphenes oxide as photoanodes

For the first time, we report a one-step fabrication of an environment-friendly approach to synthesize flower-like α-Fe₂O₃ hierarchical nanoparticles (NPs)/reduced graphene oxide (RGO) hybrids by combining the graphene oxide (GO) with the growth of α-Fe₂O₃ NPs. The GO sheet which possesses the functional group, such as hydroxyl (–OH) and carbonyl groups (–OOH), can be easily incorporated with the petal of the flower-like α-Fe₂O₃ in ethanol and water solution through a solvothermal process, during which GO is reduced to RGO without the addition of any strong reducing agent or requiring any post-high-temperature annealing process. The as-prepared samples are loose and porous with flower-like structure, and the RGO hybrids were wrapped up uniformly on the sheet of α-Fe₂O₃ NPs. To demonstrate the potential applications, we have fabricated dye-sensitized solar cells (DSSCs) from the as-synthesized hierarchical flower-like α-Fe₂O₃/RGO and investigated it for the photoanode of DSSCs. Results show that the hierarchical α-Fe₂O₃/RGO solar cell exhibits improved performances in comparison with the free α-Fe₂O₃ NPs. The enhancement of photovoltaic properties is attributed to the unique porous nature and good conductivity which allow more efficient diffusion of I^? ions and facilitate the transfer of electron in the network.     

Mechanisms of effective gold shell on Fe3O4 core nanoparticles formation using sonochemistry method

Sonochemical synthesis (sonochemistry) is one of the most effective techniques of breaking down large clusters of nanoparticles (NPs) into smaller clusters or even individual NPs, which ensures their dispersibility (stability) in a solution over a long duration. This paper demonstrates the potential of sonochemistry becoming a valuable tool for the deposition of gold (Au) shell on iron oxide nanoparticles (Fe₃O₄ NPs) by explaining the underlying complex processes that control the deposition mechanism. This review summarizes the principles of the sonochemistry method and highlights the resulting phenomenon of acoustic cavitation and its associated physical, chemical and thermal effects. The effect of sonochemistry on the deposition of Au NPs on the Fe₃O₄ surface of various sizes is presented and discussed. A Vibra-Cell ultrasonic solid horn with tip size, frequency, power output of ½ inch, 20 kHz and 750 W respectively was used in core@shell synthesis. The sonochemical process was shown to affect the surface and structure of Fe₃O₄ NPs via acoustic cavitation, which prevents the agglomeration of clusters in a solution, resulting in a more stable dispersion. Deciphering the mechanism that governs the formation of Au shell on Fe₃O₄ core NPs has emphasized the potential of sonication in enhancing the chemical activity in solutions.     

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.     

The study of novel Fe3O4@γ-Fe2O3 core/shell nanomaterials with improved properties

The surface structure of the iron oxide nanoparticles obtained by the co-precipitation method has been investigated, and a thin layer of α-FeOOH absorbed on surface of the nanoparticle is confirmed by analyses of Fourier transform infrared (FTIR), X-ray photoelectron spectra (XPS) and surface photovoltage spectroscopy (SPS). After annealed at 400 °C, the α-FeOOH can be converted to γ-Fe₂O₃. The simple-annealed procedure resulted in the formation of Fe₃O₄@γ-Fe₂O₃ core/shell structure with improved stability and a higher magnetic saturation value, and also the simple method can be used to obtain core/shell structure in other similar system.     

Local structure of polymeric ferrogels

We synthesize hybrid gels incorporating γ‐Fe₂O₃ nanoparticles (NPs), citrate coated, in a polyacrylamide (PAM) network. The local organisation and the rotational degrees of magnetic nanoparticles are probed in the conditions of gel synthesis and also at swelling equilibrium, to correlate the homogeneous/inhomogeneous structure of the ferrogels to the synthesis parameters and to their macroscopic elasticity. NP adsorption on the PAM network at low citrate concentration is responsible for the reinforcing of the polymer structure. At higher citrate concentration, due to a competition between citrate and NPs, the nanoparticles desorb from the polymer structure weakening the system.     

Synthesis and characterization of superparamagnetic iron oxide nanoparticles for biomedical applications

Monodisperse iron oxide nanoparticles (NPs) of 4 nm were obtained through high-temperature solution phase reaction of iron (III) acetylacetonate with 1, 2-hexadecanediol in the presence of oleic acid and oleylamine. The as-synthesized iron oxide nanoparticles have been characterized by X-ray diffraction, transmission electron microscopy, Mössbauer spectroscopy and magnetic measurements. The species obtained were Fe₃O₄ and/or $\upgamma$ -Fe₂O₃. These NPs are superparamagnetic at room temperature and even though the reduced particle size they show a high saturation magnetization (MS ≈ 90 emu/g).     

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.     

Optimization of ultrasonic-assisted approach for synthesizing a highly stable biocompatible bismuth-coated iron oxide nanoparticles using a face-centered central composite design

The incorporation of additional functional groups such as bismuth nanoparticles (Bi NPs) into magnetite nanoparticles (Fe₃O₄ NPs) is critical for their properties modification, stabilization, and multi-functionalization in biomedical applications. In this work, ultrasound has rapidly modified iron oxide (Fe₃O₄) NPs via incorporating their surface through coating with Bi NPs, creating unique Fe₃O₄@Bi composite NPs. The Fe₃O₄@Bi nanocomposites were synthesized and statistically optimized using an ultrasonic probe and response surface methodology (RSM). A face-centered central composite design (FCCD) investigated the effect of preparation settings on the stability, size, and size distribution of the nanocomposite. Based on the numerical desirability function, the optimized preparation parameters that influenced the responses were determined to be 40 ml, 5 ml, and 12 min for Bi concentration, sodium borohydride (SBH) concentration, and sonication time, respectively. It was found that the sonication time was the most influential factor in determining the responses. The predicted values for the zeta potential, hydrodynamic size, and polydispersity index (PDI) at the highest desirability solution (100%) were −45 mV, 122 nm, and 0.257, while their experimental values at the optimal preparation conditions were −47.1 mV, 125 nm, and 0.281, respectively. Dynamic light scattering (DLS) result shows that the ultrasound efficiently stabilized and functionalized Fe₃O₄NPs following modification to Fe₃O₄@Bi NPs, improved the zeta potential value from –33.5 to −47.1 mV, but increased the hydrodynamic size from 98 to 125 nm. Energy dispersive spectroscopy (EDX) validated the elemental compositions and Fourier transform infrared spectroscopy (FTIR) confirmed the presence of Sumac (Rhus coriaria) compounds in the composition of the nanocomposites. The stability and biocompatibility of Fe₃O₄@Bi NPs were improved by using the extract solution of the Sumac edible plant. Other physicochemical results revealed that Fe₃O₄NPs and Fe₃O₄@Bi NPs were crystalline, semi-spherical, and monodisperse with average particle sizes of 11.7 nm and 19.5 nm, while their saturation magnetization (Ms) values were found to be 132.33 emu/g and 92.192 emu/g, respectively. In vitro cytotoxicity of Fe₃O₄@Bi NPs on the HEK-293 cells was dose- and time-dependent. Based on our findings, the sonochemical approach efficiently produced (and RSM accurately optimized) an extremely stable, homogeneous, and biocompatible Fe₃O₄@Bi NPs with multifunctional potential for various biomedical applications.     

Controlled synthesis and phase characterization of Fe-based nanoparticles obtained by thermal decomposition

Iron oxide nanoparticles were synthesized by the thermal decomposition of Fe(acac)₃ and Fe(CO)₅. Three different homogeneous procedures were used for the controlled synthesis of Fe₃O₄, γ-Fe₂O₃ and Fe₃O₄/γ-Fe₂O₃ mixture nanocrystals. A combination of characterization techniques was used in order to distinguish these oxides. The controllable size, the narrow distribution and the rhombic self-assembly of the nanoparticles were revealed by the high-resolution transmission electron microscopy images and the X-ray powder diffraction results. For the quantitative analysis of the samples manganometry was used. Preliminary magnetic measurements indicated the size and composition dependence of saturation magnetization, a superparamagnetic behavior of the samples and some ferromagnetic features.     

Microwave-assisted synthesis and magnetic property of magnetite and hematite nanoparticles

Nanoparticles of magnetite (Fe₃O₄) and hematite (α-Fe₂O₃) have been prepared by a simple microwave heating method using FeCl₃, polyethylene glycol and N₂H₄·H₂O. The amount of N₂H₄·H₂O has an effect on the final phase of Fe₃O₄. The morphology of α-Fe₂O₃ was affected by the heating method. Crystalline α-Fe₂O₃ agglomerates were formed immediately at room temperature and most of these nanoparticles within agglomerates show the same orientation along [110] direction. After microwave heating, ellipsoidal α-Fe₂O₃ nanoparticles were formed following an oriented attachment mechanism. Both Fe₃O₄ and α-Fe₂O₃ nanoparticles exhibit a small hysteresis loop at room temperature.     

Horizontal low gradient magnetophoresis behaviour of iron oxide nanoclusters at the different steps of the synthesis route

In this study, the use of horizontal low gradient magnetic field (HLGMF) (<100 T/m) for filtration, control and separation of synthesized magnetic nanoparticles (NPs) is investigated. The characteristics of the suspension, size and type of the NPs are considered and discussed. For these purposes, Fe₂O₃ silica-coated nanoclusters of about 150 nm are synthesized by co-precipitation, monodispersion and silica coating. Superconducting quantum interference device, TEM, XRD and ζ potential techniques were used to characterize the synthesized nanoclusters. An extensive magnetophoresis study was performed at different magnetophoretical conditions. Different reversible aggregation times were observed at different HLGMF, at each step of the synthesis route. In particular, differences of several orders of magnitude were observed when comparing citric acid-modified NPs with silica-coated nanoclusters. Reversible aggregation times are correlated to the properties of the NPs at different steps of synthesis route.     

Field-induced microwave absorption in Fe3O4 nanoparticles and Fe3O4/polyaniline composites synthesized by different methods

Three kinds of nanoscale powders containing Fe₃O₄ nanoparticles (NPs) have been studied by ferromagnetic resonance (FMR): (i) Fe₃O₄ NPs grown and then covered with polyaniline (PANI), (ii) unclad Fe₃O₄ NPs, and (iii) Fe₃O₄ NPs grown “in situ” with the PANI. In every case, there is no low field microwave absorption, rather a single FMR line is observed. However, the half-power widths are of order of 1 kOe presumably due to a distribution of internal fields. For type I particles with a low concentration (below 40%) of Fe₃O₄, the observed resonance fields (H_r) are close to those expected for spheres with negligible magnetocrystalline anisotropy. For all other cases, H_r values are significantly lower. Such shortfalls can be roughly understood by invoking dipolar interactions between the grains, stresses frozen in grains during manufacture (method III), as well as anisotropy fields when the specimens are prepared in an aligning field.     

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.     

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.     

Novel ionic liquid supported on Fe3O4 nanoparticles and its application as a catalyst in Mannich reaction under ultrasonic irradiation

A family of novel ionic liquid with l-alanine and choline chloride as environmentally benign materials have been synthesized and grafted on Fe₃O₄ nanoparticles using easy preparation techniques. The structure of ionic liquid supported on Fe₃O₄ nanoparticles (IL-Fe₃O₄ NPs) characterized by various analyses such as FE-SEM, EDX, XRD, NMR, FTIR and VSM. The catalytic activities of this catalyst are examined in the Mannich reaction for synthesis of β-aminocarbonyl compounds under ultrasonic irradiation. The recyclability of catalyst is investigated, and the results have indicated that the catalyst can be recycled six times without obvious activity decreasing.     

Thermal decomposition of almandine garnet: Mössbauer study

The thermal decomposition of almandine garnet from Zoltye Vody, Ukraine, has been studied using⁵⁷Fe Mössbauer spectroscopy. Room temperature Mössbauer spectrum of the initial powdered sample is characterised by one doublet corresponding to Fe²⁺ in dodecahedral position 24c. In the room temperature spectra of all heated almandine samples, a doublet corresponding to γ-Fe₂O₃ nanoparticles appeared. Depending on experimental conditions (heating temperature and time), the additional spectral lines of α-Fe₂O₃ and ε-Fe₂O₃ were observed in Mössbauer spectra. It is obvious that the thermal transformation of almandine garnet in air is related to the primary formation of γ-Fe₂O₃ superparamagnetic nanoparticles. γ-Fe₂O₃ nanoparticles are transformed into ε-Fe₂O₃ and consequently into α-Fe₂O₃ at higher temperatures. The mechanism and kinetics of the individual structural transformations depend on experimental conditions — mainly on the heating temperature and size of the particles.