八面体尖晶石型铁氧体的水热法制备

尖晶石型铁氧体(MeFe2O4,M为金属离子Co2+,Mn2+,Ni2+,Zn2+等)作为一类重要的功能材料,广泛应用于电子、通讯和化工行业[1].铁氧体的制备方法很多,经典的方法是陶瓷方法,需要很高的温度和很长的反应时间,而且伴随研磨,这就导致了杂质的产生.     

Nanoscale spinel ferrites prepared by mechanochemical route

Among the many types of preparation and processing techniques, the nonconventional mechanochemical route has been recognized as a powerful method for the production of novel, high-performance, and low-cost nanomaterials. Because of their small constituent sizes and disordered structural state, nanoscale materials prepared by mechanochemical route are inherently unstable with respect to structural changes at elevated temperatures. Taking into account the considerable relevance of the thermal stability of nanoscale complex oxides to nanoscience and nanotechnology, in the present work, results on the response of mechanochemically prepared MgFe₂O₄ and NiFe₂O₄ to changes in temperature will be presented. Several interesting features are involved in the work, e.g., a relaxation of the mechanically induced cation distribution towards its equilibrium configuration, a disappearance of the superparamagnetism on heating, an increase of both the saturation magnetization and the Néel temperature with increasing particle size, and a core-shell structure of nanoparticles.     

Nonstoichiometric spinel ferrites obtained from alpha-NaFeO2 via molten media reactions

Different solid/liquid "exchange" reactions involving divalent cations, protons, or ammonium ions have been performed at low/moderate temperatures (between 80 and 500 degrees C) on alpha-NaFeO2 dipped in molten salts (or acid) media. Several ferrites have been obtained which are nonstoichiometric with partially inverse spinel structures. When sodium is replaced by divalent cations (Mg2+, Co2+, Ni2+, and Zn2+), the obtained ferrites are hyperstoichiometric (cation/oxygen ratio higher than 3/4) whereas proton or ammonium reactions result in hypostoichiometric materials (cation/oxygen lower than 3/4). All these ferrites present a platelet-like morphology and show ferrimagnetic, soft magnet behavior.     

Thermal stability and reactivity in oxygen of potassium ferrites with spinel structure

The potassium content really incorporated in the spinel lattice of the magnetite determined by thermogravimetric analysis in vacuum or in oxygen was about 2.45 wt%. In spite of this low content, the potassium strongly stabilises the defect spinel structure resulted by the potassium-substituted magnetite oxidation and increases the transformation temperature of the defect phases into -Fe₂O₃ or KFe₁₁O₁₇.

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Zusammenfassung Der tatsächlich in das Spinellgitter von Magnetit eingebaute Kaliumgehalt beträgt 2.45 Gewichtsprozente. Dies wurde durch TG-Analyse in Vakuum bzw. Sauerstoff ermittelt. Trotz dieses geringen Gehaltes wird das defekte Spinell des durch Oxydation erhaltenen kaliumsubstituierten Magnetits durch Kalium stark stabilisiert, was ein Ansteigen der Temperatur für die Umwandlung der defekten Phase in Fe₂O₃ oder KFe₁₁O₁₇ nach sich zieht.

     

Sol-gel synthesis,characterisation, and photocatalytic activity of porous spinel Co3O4 nanosheets

Mesoporous spinel Co₃O₄ nanosheets were synthesised via a simple sol-gel route using the Pluronic P123 triblock copolymer as the stabilising agent. Their structural, morphological, and textural properties were characterised. FTIR spectrum revealed the formation of cobalt oxide without any surface adsorbed impurities. Face centered cubic phase of spinel Co₃O₄ with the mean crystalline size of 26 nm was assigned by the X-ray diffraction analysis without the formation of other phases. Porous nanosheets and cave-like morphologies were identified from the scanning electron microscopy (SEM) images. Highly agglomerated more or less spherical particles with well separated lattice fringes, representing the oriented growth of nanocrystals, were noticed on the transmission electron microscopy photographs. Surface area analysis revealed that the spinel has high surface area of about 25 m² g^?1 with monomodal mesoporosity. The average pore size distribution was found to be about 15.8 nm. The as-prepared spinel photocatalyst showed a mild photocatalytic activity in the degradation of methylene blue (2.5 mg L^?1) under UV light irradiation with air as the oxidising agent. Photocatalytic activity of the as-prepared reusable Co₃O₄ was found to be higher than that of the commercial spinel powder.     

Structure analysis and photocatalytic properties of spinel zinc gallium oxonitrides

This report describes a detailed structural, electronic, and catalytic characterization of zinc gallium oxonitride photocatalysts with a spinel crystal structure. The bandgap decreases to less than 3 eV with increasing nitrogen content (<3 wt%) and these photocatalysts are active in visible light (λ>420 nm) for the degradation of cresol and rhodamine B. Density functional theory calculations show that this bandgap reduction is in part associated with hybridization between the dopant N 2p states and Zn 3d orbitals at the top of the valence band. X-ray photoelectron measurements indicate that nitrogen is indeed interacting with the oxide precursor through the formation of both nitride- and oxonitride-type species. The incorporation of nitrogen reduces the uniformity of the local structure of the spinel Zn-Ga-O-N (ZGON) species, as reflected in X-ray absorption spectra and Raman measurements relative to zinc gallate, which suggests the presence of defects. The oxonitrides exhibit faster photocatalytic rates of reaction than the oxide precursor. The degradation mechanisms were determined to be via the attack by hydroxyl radicals and holes for rhodamine B and cresol, respectively. Addition of Pt as a co-catalyst increased the rate of photodegradation, a result attributed to better charge separation.     

Visible light photocatalytic activity of BiVO4 particles with different morphologies

Bismuth vanadate (BiVO₄) particles with different morphologies were synthesized by a one-step hydrothermal process and their optical and photocatalytic properties were investigated. Their crystal structure and microstructures were characterized using X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). XRD patterns demonstrate that the as-prepared samples are monoclinic cell. FESEM shows that BiVO₄ crystals can be fabricated in different morphologies by simply manipulating the reaction parameters of hydrothermal process. The UV–visible diffuse reflectance spectra (UV–vis DRS) reveal that the band gaps of BiVO₄ photocatalysts are about 2.07–2.21 eV. The as-prepared BiVO₄ photocatalysts exhibit higher photocatalytic activities in the degradation of rhodamine B (Rh B) under visible light irradiation (λ > 420 nm) compared with traditional N-doped TiO₂ (N-TiO₂). Furthermore, wheat like BiVO₄ sample reveals the highest photocatalytic activity. Up to 100% Rh B is decolorized after visible light irradiation for 180 min. The reason for the difference in the photocatalytic activities for BiVO₄ samples obtained at different conditions were systematically studied based on their shape, size and the variation of local structure.     

Enhanced photocatalytic performance of CuAl2O4 nanoparticles spinel for dye degradation under visible light

Research on Chemical Intermediates - Environmental problems on a global scale have become more prominent with the population growth. For the removal of organic contaminants, the solar energy and...     

Synthesis of Mg-Doped TiO2 nanoparticles under different conditions and its photocatalytic activity

In this study, TiO(2)- and Mg-doped TiO(2) nanoparticles with different dopant contents were prepared by sol-gel method. The prepared photocatalysts were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) and diffuse reflectance spectroscopy (DRS) techniques. The results of BET analysis indicated a pore diameter of 8 nm and surface area of 48.5 m(2) g(-1). XRD patterns of pure and doped TiO(2) nanoparticles at 450 °C revealed that all phases are anatase. The particle size obtained from TEM was less than 20 nm. The band gap energy of Mg-doped TiO(2) nanoparticles was lower than that of TiO(2) . The photocatalytic activity of the pure and doped nanoparticles has been compared in the removal of C.I. Acid Red 27 (AR27). The photocatalytic activity of Mg-doped (0.2 mol%) TiO(2) for the degradation of AR27 was higher than that of bare TiO(2) nanoparticles. Results of total organic carbon analysis and changes in the AR27 UV-Vis peaks indicated 99% mineralization and extinguishing of all peaks in UV and visible regions is possible with Mg-doped TiO(2) nanoparticles. Removal efficiency of AR27 was sensitive to the parameters such as catalyst dose, pollutant concentration and light intensity.     

Improved activity of SnO for the photocatalytic oxygen evolution

SnO prepared by soft chemistry exhibits a black color and semiconducting properties. The X-ray diffraction indicates a tetragonal symmetry (SG: P4/nmm) with nano crystallites of an average size of 85 nm. The forbidden band, determined from the diffuse reflectance is found to be 1.46 eV. The electrical conductivity occurs by polaron hopping and follows an Arrhenius type law with activation energy of 0.21 eV, the change in the slope at 526 K is attributed to the oxidation to SnO₂. The photo-electrochemical study shows n type conduction with a flat band potential of ?0.45 V, close to the photocurrent onset potential (?0.40 V). The electrochemical impedance spectroscopy shows the bulk contribution of SnO (R_b = 1.7 kΩ cm²) and decreases down to 1.89 kΩ cm² under illumination. The photocatalytic properties have been evaluated for the first time for to the oxygen evolution. The valence band, deriving from Sn²⁺: 5p orbital with a potential (?0.80 V_SCE/5.55 eV), is suitably positioned with respect to O₂/H₂O level (～0.6 V_SCE), leading to water oxidation under visible light. The best performance occurs at pH ～ 7 with an oxygen liberation rate of 23 µmol mL h^?1 (mg catalyst)^?1 and a quantum efficiency of 1.2%. An improvement of ～13% is observed on the system SnO/clay.     

Sol-gel low-temperature synthesis of stable anatase-type TiO2 nanoparticles under different conditions and its photocatalytic activity

In this work, TiO(2) nanoparticles in anatase phase was prepared by sol-gel low temperature method from titanium tetra-isopropoxide (TTIP) as titanium precursor in the presence of acetic acid (AcOH). The effects of synthesis parameters such as AcOH and water ratios, sol formation time, synthesis and calcination temperature on the photocatalytic activity of TiO(2) nanoparticles were evaluated. The resulting nanoparticles were characterized by X-ray diffraction, UV-Vis reflectance spectroscopy, transmission electron microscopy and Brunauer-Emmett-Teller techniques. Photocatalytic activity of anatase TiO(2) nanoparticles determined in the removal of C. I. Acid Red 27 (AR27) under UV light irradiation. Results indicate that with increasing AcOH/TTIP molar ratio from 1 to 10, sol formation time from 1 to 3 h and synthesis temperature from 0 to 25°C, increases crystallite size of synthesized nanoparticles. It was found that optimal conditions for low temperature preparation of anatase-type TiO(2) nanoparticles with high photocatalytic activity were as follows: TTIP:AcOH:water molar ratio 1:1:200, sol formation time 1 h, synthesis temperature 0°C and calcination temperature 450°C.     

Comparison of photocatalytic degradation kinetic characteristics of different organic compounds at anatase TiO2 nanoporous film electrodes

Photoelectrochemical method was adopted to investigate the photocatalytic oxidation of different organic compounds. It was found that at the anatase TiO₂ nanoporous electrode, the potential bias changes the rate-determining step from electron migration in the film at low potentials to photohole capture at relatively high potentials. When the applied potential bias is sufficient, the steady state photocurrent obtained reflects exclusively the rate of photohole capture at TiO₂ surface. Under such conditions, the photocatalytic degradation of various organic compounds with different chemical structures was studied.At very low concentrations, the linear increase of steady state photocurrent with the concentration was observed for all compounds investigated, due to the mass transfer limitation, although the number of electron needed for complete mineralization of these compounds differs markedly. It was demonstrated that the substrate molecules that reaches the electrode surface have been exhaustively mineralized under mass transfer-controlled conditions regardless of their chemical nature.At high concentration, substrate molecules (or intermediates) are accumulated on the surface (or in the reaction zone). As a result, the steady state photocurrent deviated from the linear relationship. Under such conditions, the interaction of substrate molecules and/or partially degraded intermediates with TiO₂ determines the overall photohole capture rate. The differences in photohole capture rate among different organic compounds were observed. The kinetic characteristics of different organic compounds at high concentrations were also explained based on the structural differences.     

Water-insoluble Ag-U-organic assemblies with photocatalytic activity

Two metal-organic coordination polymers [Ag(bipy)(UO(2))(bdc)(1.5)] (bipy=2,2'-bipyridyl, bdc=1,4-benzenedicarboxylate) and [Ag(2)(phen)(2)UO(2)(btec)] (phen=1,10-phenanthroline, btec=1,2,4,5-benzenetetracarboxylate) were obtained by hydrothermal assembly of the d(10) metal silver and the 5f metal uranium with mixed ligands. Both compounds form two-dimensional networks with pi-pi overlap interactions between the aromatic fragments in the neighboring layers. In aqueous suspension the two water-insoluble materials show photocatalytic degradation performance superior to that of commercial TiO(2) (Degussa P-25) when tested on nonbiodegradable rhodamine B (RhB) as model pollutant. The relationship between the structure of the photocatalysts and the photocatalytic activity was also elucidated. On the basis of the monitored intermediate species and the final mineralized products, it is proposed that the possible reaction mechanism for the photodegradation (oxidation) of RhB in aqueous solution catalyzed by the two assembly compounds involves photoexcitation of uranyl centers and molecular oxygen.     

Adsorption-driven photocatalytic activity of mesoporous titanium dioxide

Titanium dioxide with a mesoporous structure, when photoactivated in water, demonstrates an unprecedented photocatalytic activity, driven strongly by an adsorption degree of molecules onto the catalyst surface, which promotes a preferential conversion of a well-adsorbed molecule. This catalyzes a selective transformation of a well-adsorbed molecule into a less-adsorbed molecule, so-labeled "stick-and-leave" transformation, which promotes a direct hydroxylation of benzene to phenol, one of the most difficult synthetic reactions, with very high selectivity (>80%) and using water as a source of oxidant.     

Preparation and photocatalytic activity of cuprous oxides

Cuprous oxide (Cu₂O) nanoparticles and microcubes have been successfully fabricated by reduce of CuSO₄ using ascorbic acid at room temperature. The as-synthesized products were easily separation and purification, because there were no template or surfactant has been introduced. All of the samples were characterized by X-ray powder diffractometer (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectrometer (FTIR) and ultraviolet and visible light spectrometer (UV–vis). The microscale Cu₂O samples exhibited a high catalytic activity on photodegradation of methyl orange by visible light. It was found that Cu₂O microcubes have higher photocatalytic activity and the photocatalytic degradation ratio of methyl orange reached to 98.1%.     

A novel magnetic silica supported spinel ferrites NiFe2O4 catalyst for heterogeneous Fenton-like oxidation of rhodamine B

As the heterogeneous Fenton-like catalyst, a series of spinel ferrites magnetic nanoparticles NiFe₂O₄ and NiFe₂O₄@SiO₂ catalysts were synthesized and were applied into the oxidation of rhodamine B, which exhibited the good catalytic performance and strong magnetic separation after reaction.     

Aggregation-induced photocatalytic activity and efficient photocatalytic hydrogen evolution of amphiphilic rhodamines in water

The development of photocatalysts is an essential task for clean energy generation and establishing a sustainable society. This paper describes the aggregation-induced photocatalytic activity (AI-PCA) of amphiphilic rhodamines and photocatalytic functions of the supramolecular assemblies. The supramolecular assemblies consisting of amphiphilic rhodamines with octadecyl alkyl chains exhibited significant photocatalytic activity under visible light irradiation in water, while the corresponding monomeric rhodamines did not exhibit photocatalytic activity. The studies on the photocatalytic mechanism by spectroscopic and microscopic analyses clearly demonstrated the AI-PCA of the rhodamines. Moreover, the supramolecular assemblies of the rhodamines exhibited excellent photocatalytic hydrogen evolution rates (up to 5.9 mmol g⁻¹ h⁻¹).

Simple amphiphilic rhodamines formed supramolecular assemblies and exhibited aggregation-induced photocatalytic activity and hydrogen evolution in water.     

Mesoporous bismuth titanate with visible-light photocatalytic activity

Visible-light-driven mesoporous bismuth titanate photocatalyst, which possesses wormlike channels, mixed phase mesostructured frameworks, large pore diameter (approximately 6.1 nm), and low band gap energy (2.5 eV), has been successfully prepared via a modified evaporation-induced self-assembly technique (EISA).     

Facile synthesis of solar light active spinel nickel manganite (NiMn2O4) by co-precipitation route for photocatalytic application

Research on Chemical Intermediates - The spinel nickel manganite (NiMn2O4) nanoparticles (NPs) were successfully synthesized through simple co-precipitation method, and their structural, optical,...     

Relationship between cation arrangement and photocatalytic activity for Sr-Al-Nb-O double perovskite

The relationship between the photocatalytic activity and the arrangement of metal cations was investigated with Sr-Al-Nb-O double perovskite (SAN) synthesized at 1400 °C for various calcination times using a solid state reaction. Transmission electron microscopic observation revealed that SAN particles had a domain structure of completely B-site ordered (Sr(2)AlNbO(6)) and disordered (SrAl(0.5)Nb(0.5)O(3)) phases. The ordered phase fraction was determined using a newly proposed mixed-phase model for the Rietveld refinement and a method using the relative intensity of the superlattice line of powder X-ray diffraction. It turned out that the mass fraction of the ordered phase in SAN calcined at 1400 °C could be controlled by the calcination time as 33% (10 h), 37% (20 h), 44% (30 h), and 48% (50 h). Photocatalytic activities of SAN for the evolution of H(2) and O(2) respectively from aqueous solutions of methanol and AgF decreased with increasing the calcination time, that is, with increasing the fraction of the ordered phase. These results suggested that the photocatalytic activity of ordered Sr(2)AlNbO(6) should be lower than that of disordered SrAl(0.5)Nb(0.5)O(3). This is practically the first report to reveal the photocatalytic activity of SAN as well as the effect of cation ordering in oxides on the photocatalytic activity.