Ethylenediaminetetraacetic acid as capping ligands for highly water-dispersible iron oxide particles

Monodispersed magnetite (Fe₃O₄) particles were synthesized using a high-temperature hydrolysis reaction with the assistance of ethylenediaminetetraacetic acid (EDTA) as capping ligands. These particles were composed of small primary nanocrystals and their sizes could be tuned from about 400 to about 800 nm by simply changing the EDTA or precursor concentration. Surface-tethered EDTA made the particles highly water-dispersible. The as-prepared magnetite particles also showed superparamagnetic behavior at room temperature, and their magnetic properties were size dependent. In addition, the particles had a strong response to external magnetic field due to their high magnetization saturation values. These properties were very important for some potential biomedical applications, such as magnetic separation and magnetic-targeted substrate delivery.     

Fluorine doped zinc oxide nanowires: Enhanced photocatalysts degrade malachite green dye under visible light conditions

Enhanced visible-light absorption of 4 at% fluorine (F) doped zinc oxide (ZnO) nanowires (F:ZnO) produced via a hydrothermal method with 15 M sodium hydroxide (NaOH) is explored with various characterization techniques: XRD, TEM, UV–vis spectra, Pl spectra, XPS, and surface area analysis. Moreover, photocatalytic performance of as-prepared samples is studied via degradation of malachite green dye under visible light irradiation. Finally, the photocatalyst’s optimal amount to use is determined as well as its recyclability. Results show that band gaps of ZnO nanostructures depend on NaOH concentration, doping 15 M NaOH resultant ZnO nanowires with 4 at% F further narrows the band gap, F:ZnO nanowires perform 1.6 times better than the pure ZnO nanowires in malachite green dye (MG) degradation tests, overloading the solution with the photocatalyst actually hinders degradation performance, and the F:ZnO photocatalyst remains a robust performer even after five cycles.     

2. Sensitized degradation of chlorophenols on iron oxides induced by visible light: Comparison with titanium oxide

The sensitized photocatalytic degradation of mono-, di- and trichlorophenols on iron oxides aqueous suspensions of -Fe₂O₃ and -FeOOH is reported in detail. The degradation of these compounds followed pseudo-first-order kinetics when -Fe₂O₃ was used as photocatalyst. -FeOOH was found to be inactive for chlorophenols degradation with the exception of 2,4-dichlorophenol (2,4-DCP) where a modest effect was observed. The formation of a surface complex by the chlorophenols with the iron oxide and the solubility of the particular chlorophenol in aqueous solution were observed to be the controlling parameters during the photodegradation. The results obtained with the most active catalyst -Fe₂O₃ are compared with TiO₂. Total mineralization of chlorophenols was observed on TiO₂ while on -Fe₂O₃ only partial mineralization was observed. In either case, the intermediates produced in solution during the photodegradation were found to be significantly more biodegradable than the initial compound. For mono-, di- and trichlorophenols the overall photocatalytic degradation was observed to increase in the order: 2,4,6-trichlorophenol (2,4,6-TCP)<2,3-dichlorophenol (2,3-DCP)<2-chlorophenol (2-CP)<2,4-DCP. The former sequence shows that the recalcitrant 2,4-DCP degrades more rapidly than other chlorophenols tested during this study. The photodegradation of chlorophenols on -Fe₂O₃ and TiO₂ proceeds mechanistically through para-hydroxylation of the initial compound as suggested by the intermediates found by high-pressure liquid chromatography HPLC during the course of the degradation.     

Preparation of cerium and nitrogen co-doped titania hollow spheres with enhanced visible light photocatalytic performance

N,Ce-codoped titania hollow spheres were prepared using carbon spheres as template and using N,Ce-codoped titania nanoparticles as building blocks. The N,Ce-codoped titania nanoparticles were synthesized at low temperature. The prepared hollow spheres were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and UV-Vis diffuse reflectance spectrum (DRS). The effect of N and Ce content on the physical structure and photocatalytic properties of the as-prepared hollow sphere samples was investigated. The mechanism of photocatalytic degradation of dyes under visible light irradiation was also discussed.     

Facile synthesis of ultrathin magnetic iron oxide nanoplates by Schikorr reaction

In this work, a very facile one-pot hydrothermal synthesis approach has been developed for the preparation of ultrathin magnetite nanoplates. The hydrothermal procedure was performed by aging ferrous hydroxide under anaerobic conditions, which is known as Schikorr reaction. Ethylene glycol (EG), which was introduced to the reaction as another solvent, played a critical role in the formation process of these nanoplates. Typically, hexagonal Fe₃O₄ nanoplates with a thickness of 10 to 15 nm and a side length of 150 to 200 nm have been synthesized with EG/H₂O = 1:1 in experiments. Our data suggest that the thickness of Fe₃O₄ nanoplates decreases, and the shape of the nanoplate becomes more irregular when the concentration of EG increases. The as-prepared Fe₃O₄ nanoplates were highly crystallized single crystals and exhibited large coercivity and specific absorption rate coefficient.     

Electrodeposition of copper–magnetite magnetic composite films

Electrodeposition was demonstrated to be useful for the preparation of copper–magnetite magnetic composites. An acidic bath was tested for the incorporation of nanometric magnetite (Fe₃O₄) particles into an electrodeposited copper matrix. Cationic surfactant (dodecyltrimethylammonium chloride—DTAC) was used to keep particles suspended in the electrolyte as well as to assist magnetite incorporation. The influence of several parameters (bath temperature, deposition technique, stirring regimes and deposition conditions) on composites composition was analysed. Low stirring rate, moderate temperature (15 °C) and an applied magnetic field provided a greater incorporation of magnetite. Field emission scanning electron microscopy revealed magnetite distribution through the deposit thickness. Electrodeposited composites showed ferromagnetic behaviour. Magnetic force microscopy showed a magnetic response for the composites.     

Reduced graphene oxide as co-catalyst for enhanced visible light photocatalytic activity of BiOBr

BiOBr-reduced graphene oxide (RGO) composites were successfully synthesized via a simple hydrothermal method. Their morphology, structure and photocatalytic activity in the degradation of nitrobenzene were characterized by scanning electron microscopy, X-ray diffraction, nitrogen adsorption-desorption, UV–vis absorption spectroscopy, photoluminescence spectra, electrochemical impedance spectra and total organic carbon, respectively. The results showed that the introduction of RGO could enhance the visible light photocatalytic activity of BiOBr. The BiOBr-RGO composite with 0.6 wt% RGO exhibited an optimal photocatalytic activity, and the maximum degradation rate of nitrobenzene was about 2.16 times that of pure BiOBr due to the increased light absorption and the reduced electron-hole pair recombination in BiOBr with the introduction of RGO.     

Transparent zinc silicate/ zinc oxide crystallized glass-ceramics for water remediation application under visible light

The present study focuses on taking advantage of both Zinc Silicate (Zn₂SiO₄) and Zinc Oxide (ZnO) crystals in the glass matrix for enhancing photocatalytic activity. The fabricated samples were used as a photocatalyst for degrading ～ 5 mg/L concentrated “Methylene Blue” (MB) and “Rhodamine B” (RB) dye separately under visible light. For this, 44 SiO₂:11 Al₂O₃:35 ZnO:10 K₂O compositions were prepared via the traditional melt quench process followed by heat treating at a temperature of 750 °C at 2, 4, and 6 h. Scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) was employed to characterize the fabricated samples. The bandgap measured from Differential reflectance spectroscopy (DRS) was found to decrease with an increase in the heat treatment duration. 44 SiO₂:11 Al₂O₃:35 ZnO:10 K₂O composition heat-treated at 750 °C for 2 h degraded ～59% and ～71% of Rhodamine B (RB) dye and Methylene Blue (MB) dye under visible light in 4 h.     

Crystallization and magnetic property of iron oxide nanoparticles precipitated in silica glass matrix

Crystallization and magnetic property of Fe₂O₃ nanoparticle precipitated in SiO₂ matrix was investigated. Fe₂O₃/SiO₂ nanocomposite thin film was obtained by annealing of the amorphous Fe-Si-O thin film deposited by RF-magnetron sputtering of (α-Fe₂O₃)_1−x/(SiO₂)_x composite targets. The Fe₂O₃ crystallite size increased with decreasing SiO₂ area ratio, x of the target and increasing annealing temperature. ?-Fe₂O₃ with the crystallite size of 20-30 nm was obtained after annealing the film deposited in SiO₂ area ratio, x = 0.33-0.42 at 900 °C. Lower SiO₂ area ratio (x) than 0.25 and higher annealing temperature resulted in precipitation of α-Fe₂O₃ with the larger crystallite size than 40 nm. In the case of SiO₂ area ratio, x ≥ 0.50, the annealed film was amorphous and showed higher magnetization and smaller coercivity due to the precipitation of very small crystalline γ-Fe₂O₃. The ?-Fe₂O₃/SiO₂ composite thin film showed ferromagnetic hysteresis with coercive force of 0.14 T.     

CVD synthesis of coal-gas-derived carbon nanotubes and nanocapsules containing magnetic iron carbide and oxide

Iron carbide-oxide filled carbon nanotubes and nanocapsules (CNCs) are separately synthesized by catalytic chemical vapor deposition of coal gas at 950 °C with ferrocene as catalyst. The products are examined using transmission electron microscopy and XRD techniques, showing that nanosized iron carbide-oxide particles are encapsulated by well ordered carbon layers. Magnetic moment measurement reveals that these carbon encapsulated iron carbide-oxides exhibit large magnetic coercivity at room temperature. It has been found that the filled CNCs are corrosion-proof and stable in hydrochloric acid. The effect and interaction between different gaseous components in the coal-gas during the formation of magnetic iron carbide-oxide filled carbon nanostructures are discussed.     

Fabrication of CdS and CuWO4 modified TiO2 nanoparticles and its photocatalytic activity under visible light irradiation

CdS and CuWO₄ modified TiO₂ nanoparticles (CdS–CuWO₄-TiO₂) were prepared by the chemical impregnation method. The as-prepared nanoparticles were characterized using UV–visible-diffuse reflectance spectroscopy (UV–vis-DRS), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and B.E.T. surface area analysis techniques. The photocatalytic activity was evaluated based on the degradation of a dye (eosin-Y) and inactivation of a bacterium (Pseudomonas aeruginosa). The results revealed that CdS–CuWO₄-TiO₂ showed high photocatalytic activity over CdS-TiO₂, CuWO₄-TiO₂ and TiO₂. Moreover the reusability and stability of the photocatalyst for the degradation of eosin-Y was also studied.     

Characterization of TiO2 photocatalysts used in trichloroethene oxidation

Kinetic studies show deactivation of TiO₂ catalysts during aqueous-phase and gas-phase photooxidation of trichloroethene (TCE). Temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) were used to examine adsorbed species on TiO₂ photocatalyst surfaces after reaction, and TPD was used to determine how reactants and products adsorb on the TiO₂ surface. Used and deactivated catalysts were analyzed after participating in either aqueous-phase or gas-phase photooxidation of TCE. The XPS spectra showed little difference between the surface composition of fresh TiO₂ and that of a deactivated catalyst from the aqueous-phase photoreactor. Chlorine was observed only on catalysts used in the gas-phase photocatalytic decomposition of TCE. Differences due to photoreaction were observed in TPD spectra of water, carbon monoxide, and carbon dioxide. Both the total amount desorbed and the temperature of desorption of carbon monoxide and carbon dioxide were quite different for used and deactivated catalysts from the two photoreactions. Apparently strongly bound species, such as carbonates, accumulated on the surface and formed carbon monoxide upon high-temperature decomposition. Small amounts of chlorinated compounds desorbed from the used and deactivated catalysts following gas-phase photoreaction. Dichloroacetyl chloride (DCAC), a reaction intermediate, can adsorb strongly on TiO₂ and readily displaces TCE. Thermally decomposed DCAC reduces the number of available adsorption sites for DCAC and TCE. An interesting low-temperature oxygen desorption peak was observed from catalysts treated with H₂O₂, which improves catalytic activity. This feature indicates that H₂O₂ is stable on TiO₂ at room temperature and decomposes at 420 K.     

Synthesis of ‘ready-to-adsorb’ polymeric nanoshells for magnetic iron oxide nanoparticles via atom transfer radical polymerization

Polymer-magnetite nanoparticle complexes that respond to both magnetic fields and to temperature have been demonstrated. Novel alkyl halide-functional bis(diethylphosphonate) esters were prepared and utilized as initiators for polymerizing N-isopropylacrylamide by controlled atom transfer radical polymerization. The phosphonate esters were removed after polymerization to afford poly(N-isopropylacrylamide) with a bis(phosphonic acid) moiety precisely placed at one terminus. The bis(phosphonic acid) endgroups were adsorbed onto magnetite nanoparticles to yield nanoscale complexes that were stable against any polymer desorption and that were colloidally-stable in physiological media. Thus, the bis(phosphonate) endgroup provides a robust anchoring moiety onto the magnetite. Hydrodynamic sizes of the complexes were predicted with a density distribution model and using the measured sizes of the magnetite cores. Good agreement between the measured and predicted hydrodynamic sizes suggested that the complexes were primarily discrete, non-agglomerated nanoparticles. The complexes exhibited thermosensitive aggregation behavior near the lower critical solution temperature of the poly(N-isopropylacrylamide) component.     

Effect of atmosphere control on magnetic properties of CaO-Al2O3-SiO2-Fe3O4 glass ceramics

The influences of atmosphere during processes of melting and heat treatment, heat treatment temperature, Fe₃O₄ content and basicity on the magnetic properties of magnetite-based glass ceramics were investigated. For sample containing 20 % Fe₃O₄ melted in different atmospheres, the highest saturation magnetisation was realized in 20vol% air + 80 vol% Ar, due to the fact that ratio of Fe³⁺ to Fe²⁺ in melt obtained in this atmosphere was close to 2. However, it was found that the coercivity of glass ceramics was not affected by the melting atmosphere. A high sintering temperature led to the decrease of saturation magnetisation and the increase of coercivity. As increasing Fe₃O₄ content, the main crystal phase transformed from CaSiO₃ to CaFe_0.6Al_1.3Si_1.08O₆ and finally to magnetite phase, accompanied by the increase of saturation magnetisation and coercivity. In addition, the increase of basicity caused the decrease of saturation magnetisation and the increase of coercivity.     

Effects of pH value on the microstructure and magnetic properties of solution combusted Fe3O4 powders

Magnetite (Fe₃O₄) powders were prepared by solution combustion synthesis method using conventional and microwave ignition at various pH values of starting solution, adjusted by NH₄OH. The chelated species in dried gels were predicted by theoretical calculations and Fourier transform infrared spectroscopy. The combustion reaction rate strongly depended on pH values as investigated by thermal analysis. Phase evolution and structure characterized by X-ray diffraction method showed single phase and well-crystalline Fe₃O₄ powders which were achieved using conventional ignition at pH ≥ 7. However, the microwave ignition led to the formation of impure FeO phase together with Fe₃O₄. The microwave combusted powders exhibited the disintegrated structure in comparison with the bulky microstructure for conventionally combusted powders, as observed by scanning electron microscopy. Magnetic properties of the as-combusted powders studied by vibration sample magnetometry showed the highest saturation magnetization of 81.3 emu/g for conventional ignition at pH of 7, due to the high purity and large crystallite size.     

A novel rapid microwave crystallization of photocatalysts for practical utility in the removal of phenol derivatives

A new concept of the microwave-assisted process was used for the crystallization of titania nanoparticles. The presented microwave crystallization can be indicated as truly environmentally friendly due to its energy efficiency and very short process time. In addition, it allows one to obtain pure materials without surface defects, which was confirmed by the EPR analysis. The physicochemical properties (such as crystallinity, morphology, and textural properties) of the synthesized TiO₂ nanomaterials are strongly dependent on the microwave crystallization temperature. In this work, for the first time, the novel and convenient LED photoreactor was compared directly with the classic high-pressure mercury lamp. Photocatalytic studies showed higher activity in the oxidation of phenol and 4-chlorophenol under UV-LED light, compare to high-pressure Hg-lamp. The reason for improving photo-oxidation performance under LED light is indicated that each of the LEDs has the same parameters, so they can be considered as many single sources of UV radiation occurring throughout the entire cross-section of the reactor. This confirms that microwave-assisted crystallization of TiO₂-photocatalysts and application of LEDs as light sources can be elements of a novel photocatalytic approach toward environmental protection. The presented results show that the simultaneous approach to the development of photocatalysts and novel light is the right route to further develop photocatalysis to enter this process into truly environmental protection.     

Nanoscale zinc oxide based heterojunctions as visible light active photocatalysts for hydrogen energy and environmental remediation

ABSTRACT

In the recent years, zinc oxide has emerged as one of the promising alternate materials to titania for photocatalytic applications due to its several advantages properties. This review recapitulates the ongoing advancement in the field of ZnO-based heterojunctions as visible light responsive photocatalysts for energy conversion (hydrogen evolution) and environmental remediation (pollutants degradation) applications. After a short introduction about zinc oxide materials, the various approaches utilized in the design and development of efficient ZnO-based nanoheterostructures has been discussed in detail. Specifically, strategies such as coupling ZnO with other semiconductors, supporting on carbonaceous materials, decorating with noble metal nanoparticles, doping with heteroatoms and engineering defects in the semiconductor material have been elaborated with a particular emphasis on hydrogen energy and organic pollutants removal. Finally, the future perspective of this material has been highlighted. This comprehensive review not only summarizes the recent literature in this topic, but also provides a detailed insight on the scope of this material for hydrogen energy and environmental remediation applications.     

Magnetically recyclable Ni1-xCdxCeyFe2-yO4-rGO nanocomposite photocatalyst for visible light driven photocatalysis

In this study, a magnetically recyclable Ni_1-xCd_xCe_yFe_2-yO₄-rGO (x, y = 0.05) (NCCF-rGO) nanocomposite photocatalyst has been prepared by following a facile in-situ co-precipitation method combined with ultra-sonication means. The as-synthesized magnetically separable NCCF-rGO nanocomposite photocatalyst efficiently degrades methylene blue (MB) dye in comparison to bare Ni_1-xCd_xCe_yFe_2-yO₄ (x, y = 0.05) (NCCF) nanoparticles (NPs) under visible light irradiation. The photo-degradation rate of MB with NCCF-rGO was ~9 times higher than NCCF nanoparticles (NPs). This enhanced photocatalytic performance of NCCF-rGO photocatalyst was due to the presence of reduced graphene oxide, which greatly help in production of photoactive species by reducing the rate of electro-hole pair recombination. The role of photoactive species that were responsible for the photocatalytic degradation of methylene blue has also been investigated. The as-synthesized NCCF-rGO photocatalyst expressed superb chemical stability and photocatalytic activity even after seven cycle runs. Moreover, the NCCF-rGO nanocomposite worked at all pH values and showed good acid resistance. In particular, the as-synthesized NCCF-rGO photocatalyst could be collected for the next cycle run by simply applying an external magnetic field. Hence, the NCCF-rGO nanocomposite could have potential use in organic dyes contained wastewater treatment.     

Platinum/zinc oxide nanoparticles: Enhanced photocatalysts degrade malachite green dye under visible light conditions

Zinc oxide nanoparticles (ZnO) were prepared via a sol–gel method, and a photo-assisted deposition method was used to prepare platinum on zinc oxide nanoparticles (Pt/ZnO). Several techniques were used to characterize these enhanced photocatalysts: XRD, TEM, UV–vis spectra, PL spectra, XPS, and BET surface area analysis. As-prepared samples’ photocatalytic performances were studied via degradation of malachite green dye under various visible-light-only irradiation scenarios. Results demonstrated the following: platinum (Pt) was well dispersed on and in ZnO's surfaces and pores; as such, Pt/ZnO had less surface area than pure ZnO due to pore blockage; however, advantages gained from enhanced electron-hole separation and decreased band gap width more than made up for this negative effect; moreover, Pt/ZnO prepared with 0.3 wt% Pt exhibited the lowest band gap and the highest photocatalytic activity of the various samples with a solids loading of 0.8 g/l; finally, such samples were recyclable, i.e., photocatalytic performance remained stable even after five uses.     

Preparation and magnetic properties of iron titanium oxide nanotube arrays

FeTi alloy was prepared by a vacuum smelting method, iron titanium oxide nanotube arrays have been made directly by anodization of the FeTi alloy. Morphologies and microstructures of the samples were characterized by scanning electron microscope, transmission electron microscope, and X-ray diffractometer. Influences of temperature and H₂O concentration on the morphologies of the nanotube arrays have been discussed in detail. Magnetic properties of the samples have also been investigated. The as-prepared samples were amorphous. When annealed at 500 °C and 550 °C, pesudobrookite Fe₂TiO₅ was obtained. At 600 °C, there were mixed Fe₂TiO₅, rutile TiO₂, and α-Fe₂O₃. Magnetic performance of the nanotube arrays exhibited high sensitivity to temperature and changed interestingly upon annealing. The values of the coercivity and remanence were 340 Oe and 0.061 emu/g respectively for the sample annealed at 550 °C.