Synthesis of mesoporous γ-AlOOH@Fe3O4 magnetic nanomicrospheres

Mesoporous γ-AlOOH@Fe₃O₄ magnetic nanomicrospheres were synthesized using superparamagnetic Fe₃O₄ nanoparticles as the core and aluminum isopropoxide (AIP) as the aluminum source. The obtained magnetic nanomicrospheres were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N₂ adsorption–desorption and vibrating sample magnetometry (VSM). The effects of preparation parameters such as hydrolysis time of AIP, concentration of AIP and coating layer number on microspheres were investigated. The results indicated that the mesoporous γ-AlOOH@Fe₃O₄ magnetic nanomicrospheres consisted of a mesoporous γ-AlOOH shell and a Fe₃O₄ magnetic core. The diameter of γ-AlOOH@Fe₃O₄ nanomicrospheres was about 200 nm, the thickness of mesoporous γ-AlOOH shell was about 5 nm and the average pore size was 3.8 nm. The thickness of the mesoporous γ-AlOOH shell could be controlled via layer-by-layer coating times. The formation mechanism of the mesoporous γ-AlOOH shell involved a “chemisorption–hydrolysis” process.     

Fabrication of magnetic nanosized γ-FeNi-coated ceramic core–shell microspheres by heterogeneous precipitation and thermal reduction

Precursors with NiCO₃·2Ni(OH)₂·2H₂O- and Fe₂O₃·nH₂O-coated alumina, graphite and cenosphere were synthesized by precipitation using ferrous sulfate, nickel sulfate, ammonium bicarbonate, alumina, graphite and cenosphere as the main starting materials. Magnetic γ-FeNi-coated alumina, graphite and cenosphere core–shell structural microspheres were subsequently prepared by thermal reduction of the as-prepared precursors at 600 °C for 2 h. Precipitation parameters, e.g. concentration of ceramic micropowders (10 g/L), sulfate solution (0.2 mol/L), rate of adding reactants (3 mL/min) and pH value were optimized by a trial-and-error method. Powders of the precursors and the resulting coating of γ-FeNi with grain size below 40 nm on alumina, graphite and cenosphere microspheres were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The magnetic properties of the nanosize γ-FeNi-coated alumina, graphite and cenosphere microspheres were measured by vibrating sample magnetometer (VSM). The results show that the core–shell structural γ-FeNi-coated ceramic microspheres exhibited higher coercivity than pure γ-FeNi powders, indicating that these materials can be used for high-performance functional materials and devices.     

Mesoporous composite of LiFePO4 and carbon microspheres as positive-electrode materials for lithium-ion batteries

Mesoporous LiFePO₄/C microspheres consisting of LiFePO₄ nanoparticles are successfully fabricated by an eco-friendly hydrothermal approach combined with high-temperature calcinations using cost-effective LiOH and Fe³⁺ salts as raw materials. In this strategy, pure mesoporous LiFePO₄ microspheres, which are composed of LiFePO₄ nanoparticles, were uniformly coated with carbon (∼1.5 nm). Benefiting from this unique architecture, these mesoporous LiFePO₄/C microspheres can be closely packed, having high tap density. The initial discharge capacity of LiFePO₄/C microspheres as positive-electrode materials for lithium-ion batteries could reach 165.3 mAh/g at 0.1 C rate, which is notably close to the theoretical capacity of LiFePO₄ due to the large BET surface area, which provides for a large electrochemically available surface for the active material and electrolyte. The material also exhibits high rate capability (∼100 mAh/g at 8 C) and good cycling stability (capacity retention of 92.2% after 400 cycles at 8 C rate).     

Metallic iron nanoparticles: Flame synthesis,characterization and magnetic properties

Metallic iron (Fe) nanoparticles (NPs) with a typical core–shell structure have been prepared by a simple and continuous flame spray pyrolysis (FSP) method, which are stabilized by the corresponding Fe₃O₄ shell with a thickness of 4–6 nm. The size of metallic Fe cores is about 30–80 nm. The core–shell structured iron NPs show an air stability as long as one month as a result of the protection of oxide shell. Through the control of the residence time of materials in flame and flame atmosphere, metallic Fe and iron oxides are obtained, showing a better external magnetic field responsibility. It is concluded that the evolution of morphology and composition of flame-made magnetic NPs could be attributed to the competition mechanism between reduction and oxidation reactions of in situ flame combustion, which offers more choices and better effective design strategy for the synthesis of advanced functional materials via FSP techniques.     

Facile aqueous synthesis and thermal insulating properties of low-density glass/TiO2 core/shell composite hollow spheres

Anatase TiO₂ shells assembled on hollow glass microspheres (HGM) with tunable morphologies were successfully prepared through a controllable chemical precipitation method with urea as the precipitator. Thus, glass/TiO₂ core/shell composite hollow spheres with low particle density (0.40 g/cm³) were fabricated. The phase structures, morphologies, particle sizes, shell thicknesses, and chemical compositions of the composite microspheres were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). The morphology of the TiO₂ shell can be tailored by properly monitoring the reaction system component and parameters. The probable growth mechanism and fabrication process of the core/shell products involving the nucleation and oriented growth of TiO₂ nanocrystals on hollow glass microspheres was proposed. A low infrared radiation study revealed that the radiation properties of the products are greatly influenced by the unique product shell structures. A thermal conductivity study showed that the TiO₂/HGM possess low thermal conductivity that is similar to that of the pristine HGMs. This work provides an additional strategy to prepare low-density thermal insulating particles with tailored morphologies and properties.     

Modification of silica with PMMA via ultrasonic irradiation and its application for reinforcement of polyacrylates

Polymethyl methacrylate （PMMA） encapsulated silica nanocomposite particles were prepared by ultra- sonically induced in situ polymerization of methyl methacrylate （MMA） on the surface of silica sol. The nanoparticles were characterized by Fourier transform infrared spectroscopy （FFIR）, transmission electron microscopy （TEM）, thermogravimetry （TG）, scanning electron microscopy （SEM）. The results showed that core-shell structure nanocomposite particles with an average size of 36 nm were obtained, and the thickness of polymer encapsulating layer was about 8 nm. The pretreatment of silica sol with tert-butyl hydroperoxide （TBHP） and the addition of ~-methacryloxypropyl trimethoxysilane （MAPTS） significantly enhanced the encapsulation effect. Modified by the polymer layer, the silica particles could be well dispersed in matrices and utilized to improve the mechanical performance of polyacrylates.     

Carbon nanotubes coated with platinum nanoparticles as anode of biofuel cell

A hybrid system of carbon nanotubes (CNTs) coated with poly (amidoamine) (PAMAM) dendrimer-encapsulated platinum nanoparticles (Pt-DENs) and glucose oxidase (GOx) was prepared through the layer-by-layer (LbL) self-assembly approach and then used as anode in enzyme-based biofuel cells (BFCs). The assembly process was monitored by ζ-potential measurement, and the as-resulted Pt-DENs/CNTs nanocomposites were characterized by transmission electron microscopy (TEM). The performance of electrodes modified by Pt-DENs/CNTs was also investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). We found that the Pt-DENs/CNTs could enhance the electron transfer between the redox centers in enzyme and the electrode surfaces. Furthermore, by employing the Pt-DENs/CNTs modified electrodes as anode, the enzyme-based BFCs operated in a solution containing glucose generated an open-circuit voltage of approximately 640.0 mV and a maximum current density of about 90.0 μA/cm², suggesting that Pt-DENs/CNTs may serve as an alternative anode to previously used noble metals in BFC applications.     

Chemically modified magnetic chitosan microspheres for Cr(VI) removal from acidic aqueous solution

A bioadsorbent composed of magnetic silica nanoparticles encapsulated by chitosan microspheres was prepared by the emulsion cross-linking method, and it was then modified with quaternary ammonium groups by reaction with ethylenediamine and glycidyl trimethylammonium chloride. Characterization of the bioadsorbent indicated that it was highly acid resistant and magnetically responsive. The bioadsorbent was then used to remove Cr(VI) from acidic aqueous solution. The results of batch experiments indicated that the optimal pH value was 2.5, and the adsorbent exhibited low pH dependence. The maximum adsorption capacity was 233.1 mg/g at pH 2.5 and 25 °C, and the equilibrium time was determined to be 40–120 min depending on the initial Cr(VI) concentration. The adsorbent could be effectively regenerated using a mixture of 0.3 mol/L NaOH and 0.3 mol/L NaCl with a desorption efficiency of 95.6%, indicating high reusability. In conclusion, the bioadsorbent shows potential for Cr(VI) removal from acidic wastewater.     

Highly dispersed Mn2O3 microspheres: Facile solvothermal synthesis and their application as Li-ion battery anodes

Nanostructured transition metal oxides are promising alternative anodes for lithium ion batteries. Li-ion storage performance is expected to improve if high packing density energy particles are available. Herein, Mn₂O₃ microspheres with a ca. 18 μm diameter and a tapped density of 1.33 g/cm³ were synthesized by a facile solvothermal–thermal coversion route. Spherical MnCO₃ precursors were obtained through solvothermal treatment and they decomposed and converted into Mn₂O₃ microspheres at an annealing temperature of 700 °C. The Mn₂O₃ microspheres consisted of Mn₂O₃ nanoparticles with an average 40 nm diameter. These porous Mn₂O₃ microspheres allow good electrolyte penetration and provide an ion buffer reservoir to ensure a constant electrolyte supply. The Mn₂O₃ microspheres have reversible capacities of 590 and 320 mAh/g at 50 and 400 mA/g, respectively. We thus report an efficient route for the fabrication of energy particles for advanced energy storage.     

Large-scale synthesis of hierarchical MnO2 for benzene catalytic oxidation

Hierarchical sea-urchin-shaped manganese oxide microspheres were synthesized via a facile method based on the reaction between KMnO₄ and MnSO₄ in HNO₃ solution at 50 °C. The average diameter of the microspheres is ∼850 nm. The microspheres consist of a core of diameter of ∼800 nm and nanorods of width ∼50 nm. The nanorods exist at the edge of the core. The Brunauer–Emmett–Teller surface area of the sea-urchin-shaped microspheres is 259.4 m²/g. A possible formation mechanism of the hierarchical sea-urchin-shaped microspheres is proposed. The temperature for 90% conversion of benzene (T_90%) on the hierarchical urchin-shaped MnO₂ microspheres is about 218 °C.     

Electrosynthesis and catalytic properties of silver nano/microparticles with different morphologies

Electrosynthesis of powdery silver particles can be effectively carried out with an H₂O–oleic acid or an H₂O–glycerol mix solvent (volume ratio 1:1) as the electrolytic medium and AgNO₃ as the supporting electrolyte. Experimental results indicate that the presence or absence of the surfactant sodium dodecyl sulfate (SDS) and the choice of electrolytic medium have a significant impact on the shape and size of the prepared Ag particles. With H₂O–glycerol as the electrolytic medium, spherical Ag nanoparticles can be obtained in the presence of SDS (0.6 g/L), while an Ag sample electrodeposited without SDS has a dendritic microcrystalline structure. For the reduction of methyl orange (MO) and methylene blue (MB) with NaBH₄ as the reducing agent, the spherical Ag nanoparticles exhibit much better catalytic activity than the dendritic Ag microparticles. Further investigations show that surface modification by an oleic acid medium could greatly improve the catalytic activity of the electrodeposited Ag particles for the reduction of MO and MB.     

Preparation and electrochemical performance of carbon-coated LiFePO4/LiMnPO4-positive material for a Li-ion battery

Lithium iron phosphate (LiFePO₄)/lithium manganese phosphate (LiMnPO₄)-positive material was successfully prepared through ball milling and high-temperature sintering using manganese acetate, lithium hydroxide, ammonium dihydrogen phosphate, and ferrous oxalate as raw materials. The as-prepared samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, a constant current charge–discharge test, cyclic voltammetry, and electrochemical impedance spectroscopy. The effects of lithium iron phosphate coating were also discussed. Because of its special core–shell structure, the as-prepared LiMn_0.7Fe_0.3PO₄–LiFePO₄–C exhibits excellent electrochemical performance. The discharge capacity reached 136.6 mAh/g and the specific discharge energy reached 506.9 Wh/kg at a rate of 0.1 C.     

Open-pore LiFePO4/C microspheres with high volumetric energy density for lithium ion batteries

LiFePO₄/C microspheres with different surface morphologies and porosities were prepared from different carbon sources. The effects of the surface morphology and pore structure of the microspheres on their electrochemical properties and electrode density were investigated. The electrochemical performance and electrode density depended on the morphology and pore structure of the LiFePO₄/C microspheres. Open-pore LiFePO₄/C microspheres with rough surfaces exhibited good adhesion with current collectors and a high electrode density (2.6 g/cm³). They also exhibited high performance in a half cell and full battery with a high volumetric energy density.     

Green synthesis and enhanced photocatalytic activity of Ce-doped TiO2 nanoparticles supported on porous glass

A facile and green method to prepare Ce-doped TiO₂ nanoparticles supported on porous glass beads is reported. An ion exchange process and subsequent calcination yielded Ce-doped TiO₂ nanoparticles with a mean size of 4.8 ± 0.3 nm. The nanoparticles were dispersed on the surface of porous glass beads. The addition of Ce enhanced the visible light absorption of the TiO₂ nanoparticles in the 400–500 nm spectral window. The band gap of the as-prepared catalyst was 2.80 eV. The Ce-doped TiO₂ nanoparticles immobilized on porous glass beads exhibited excellent photocatalytic activity for the visible-light-degradation of methyl orange (MO) and rhodamine B (RhB); with rate constants of 0.095 and 0.230 min⁻¹; respectively. The effects of Ce dosage; reaction duration; and initial solution pH on the conversion of MO and RhB dyes were investigated. The green synthesis and favorable photocatalytic activity makes the Ce-doped TiO₂ nanoparticles immobilized on porous glass an attractive alternative for the efficient degradation of organic pollutants.     

Preparation of nanosized hollow silica spheres from Na2SiO3 using Fe3O4 nanoparticles as templates

Nanosized hollow silica spheres with average diameters from 43 to 70 nm were prepared by removal of Fe₃O₄ templates with hydrochloric acid from silica-coated Fe₃O₄ core–shell composites. The shells of the hollow silica spheres had nanopores with average diameters of 0.92–1.25 nm. When the silica-coated Fe₃O₄ core–shell composites were prepared at a high pH value or with a low mole ratio of Na₂SiO₃ to Fe₃O₄, the resulting hollow silica spheres consisted of highly porous shells. When the silica-coated Fe₃O₄ core–shell composites were prepared with a high mole ratio of Na₂SiO₃ to Fe₃O₄, the resulting hollow silica spheres had large diameters and thick shells. The release rate of herbicide, ammonium glyphosate, could be tuned by using hollow silica spheres with different shell thicknesses.     

Interaction between Weibull parameters and mechanical strength reliability of industrial-scale water gas shift catalysts

A fundamental step in the production of an industrial catalyst is its crushing strength assessment. Limited literature exists in which the strength reliability of supported catalysts is investigated from production to their application in a reactor. In this work, cylindrical supports were prepared by pelletizing high porosity γ-alumina powder, and Cu–Zn/γ-Al₂O₃ catalysts were prepared by impregnation of the pelletized γ-alumina supports with an aqueous solution of copper and zinc nitrates. The support-forming variables, such as binder concentration, compaction pressure, calcination temperature, and drying procedure were investigated. The Weibull method was used to analyze the crushing strength data of the supports, and the fresh and used catalysts before and after the low-temperature water gas shift reaction. Support formation at a 50 wt% binder concentration, 1148 MPa compaction pressure, 500 °C calcination temperature, and rapid drying (100 °C, 8 h) led to the maximum support mechanical reliability. The most reliable catalyst with respect to simultaneous appropriate catalytic performance and mechanical strength was prepared from a support with the lowest mean crushing strength (26.25 MPa). This work illustrates the importance of the Weibull modulus as a useful mechanical reliability index in manufacturing a supported solid catalyst.     

Ultrasonic irradiation and solvent effects on destabilization of colloidal suspensions of platinum nanoparticles

In this work, ultrasonic irradiation and destabilizer solvent were used for destabilizing colloidal platinum dispersions. The stabilized platinum nanoparticles were prepared in w/o microemulsion systems composed of sodium bis-(2-ethylhexyl) sulfosuccinate (AOT) and four different solvents, namely, cyclohexane, n-hexane, n-heptane, and n-nonane. The recovery process of Pt nanoparticles from the colloidal systems was performed by exposing the colloidal samples to ultrasonic irradiation and applying various destabilizing solvents. Analysis of UV–visible spectra confirms that the quantity of Pt nanoparticles removed from the suspension depends on the length of time of the ultrasonic irradiation and the nature of the microemulsion oil phase. A critical time for the ultrasonic irradiation has been introduced for the phase separation of colloidal systems. To perform the solvent study, four destabilizer solvents, namely, dioxane, ethyl acetate, diethyl ether, and tetrahydrofuran, were used for breaking the colloidal suspension of platinum nanoparticles. Based on the ‘good solvent’ and ‘poor solvent’ idea, it is verified that the effect of the destabilizer solvents on the aggregation process follows the following order: tetrahydrofuran > ethyl acetate > dioxane > diethyl ether.     

Viscosity of alumina nanoparticles dispersed in car engine coolant

The present paper, describes our experimental results on the viscosity of the nanofluid prepared by dispersing alumina nanoparticles (<50 nm) in commercial car coolant. The nanofluid prepared with calculated amount of oleic acid (surfactant) was tested to be stable for more than 80 days. The viscosity of the nanofluids is measured both as a function of alumina volume fraction and temperature between 10 and 50 °C. While the pure base fluid display Newtonian behavior over the measured temperature, it transforms to a non-Newtonian fluid with addition of a small amount of alumina nanoparticles. Our results show that viscosity of the nanofluid increases with increasing nanoparticle concentration and decreases with increase in temperature. Most of the frequently used classical models severely under predict the measured viscosity. Volume fraction dependence of the nanofluid viscosity, however, is predicted fairly well on the basis of a recently reported theoretical model for nanofluids that takes into account the effect of Brownian motion of nanoparticles in the nanofluid. The temperature dependence of the viscosity of engine coolant based alumina nanofluids obeys the empirical correlation of the type: log (μ_nf) = A exp(BT), proposed earlier by Namburu et al.     

Magnetic and electrochemical behavior of rhombohedral α-Fe2O3 nanoparticles with (1 0 4) dominant facets

Uniform rhombohedral α-Fe₂O₃ nanoparticles, ～60 nm in size, were synthesized via a triphenylphosphine-assisted hydrothermal method. Scanning electron micrograph (SEM) and transmission electron micrograph (TEM) analyses showed that the as-synthesized rhombohedral nanoparticles were enclosed by six (1 0 4) planes. The concentration of triphenylphosphine played an important role in morphological evolution of the α-Fe₂O₃ nanoparticles. The as-prepared rhombohedral nanoparticles possessed remanent magnetization M_r of 2.6 × 10^?3 emu/g and coercivity H_C of 2.05 Oe, both lower than those of other α-Fe₂O₃ particles with similar size, indicating their potential applications as superparamagnetic precursor materials. Furthermore, these rhombohedral α-Fe₂O₃ nanoparticles exhibited good sensor capability toward H₂O₂ with a linear response in the concentration range of 2–20 mM.     

Preparation of FeCo-, FeNi- and NiCo-alloy coated cenosphere composites by heterogeneous precipitation

Precursors of binary alloy (Fe_1/2Co_1/2, Fe_1/2Ni_1/2, Ni_1/2Co_1/2, hereinafter referred to as FeCo, FeNi, NiCo) coated cenospheres were prepared by heterogeneous precipitation under optimized conditions. Magnetic binary alloy coated cenosphere composites with core–shell structure were subsequently obtained by thermal reduction of the as-prepared precursors at 700 °C for 2 h under H₂/N₂ atmosphere. The results showed that the alloy coatings were uniform and the binary alloy coated cenosphere composites basically retained the spherical morphology, suggesting that the thickness of the alloy coating could be adjusted to fabricate core–shell composites with multilayer structures. The composites exhibited higher coercivity than the pure alloy powders, and could therefore be used for high-performance functional materials and devices.