Chemical Preparation of Bimetallic Fe/Ag Core/Shell Composite Nanoparticles.

Bimetallic iron/silver (Fe/Ag) core/shell nanoparticles were prepared by chemical reduction from ferrous sulfate in the presence of sodium borohydride as a reducing agent in water, followed then by redox transmetalation with addition of silver nitrate (AgNO3) solution. When the reduction temperature was increased from room temperature to 85 °C, Fe nanoparticles with a reduced crystallite size ranging from 5.5 to 2.0 nm resulted. The particles changed from spherical to plate-like morphology as the temperature reached 85 °C. Addition of trisodium citrate was able to protect the precipitated Fe nanoparticles from oxidation; nonetheless, the citrate would facilitate chelation of the Fe clusters so that dense Fe aggregates with a mean diameter greater than 100 nm were found as the concentration of trisodium citrate exceeded 3.33 mM. A continuous Ag film was formed on the Fe surface by the redox transmetalation. This Ag film became a raspberry structure involving preferential deposition of particulate Ag on the Fe particles when the AgNO3 concentration exceeded 76.9 mM. Magnetic saturation was found to reduce with the increasing Ag concentration in the bimetallic composite nanoparticles.

Enhanced room-temperature NO2 gas sensing with TeO2/SnO2 brush- and bead-like nanowire hybrid structures.

We have synthesized two highly sensitive, room-temperature operating TeO2/SnO2 gas sensors with hierarchical nanowire structures. One is a brush-like nanostructure, from a two-step thermal vapor-transport route, and the other one is a TeO2/SnO2 bead-like nanostructure, from annealing of the former. The TeO2/SnO2 nanostructures exhibit a greatly enhanced room-temperature gas-sensing response compared to pristine TeO2 nanowires in the sequence: TeO2/SnO2 bead-like structure > brush-like structure > pristine TeO2 nanowire. The response of the TeO2/SnO2 bead-like structure is in a range of 10 to 20 against NO2 gas of ppm levels (3-100 ppm) at room temperature. This compares favorably to the response, smaller than 2, for the pristine TeO2 nanowires. Interestingly, the TeO2/SnO2 bead-like structure exhibits a typical n-type gas-sensing behavior, in contrast to the p-type behavior from the brush-like and the pristine TeO2 structures. Possible hybrid growth and sensing mechanisms are discussed.

Synthesis of nanoporous Al2O3 membranes from polybutyl methacrylate functionalized SiO2 particles as a sacrificial template.

SiO2 surface is first modified with 3-trimethoxysilyl propyl methacrylate (MPS) in order to graft with polymerized butyl methacrylate (BMA) to form SiO2@MPS-BMA core--shell hybrid particles. The polymeric BMA shell enables anchoring of aluminum ions in tetrachloroethylene solvent, results in SiO2 @Al2O3 composite particles upon subjected to calcination. Removal of the SiO2 core by acid etching forms nanoporous gamma-Al2O3 membrane with a Horvath-Kawazoe (HK) pore size of 1.4 nm and a Brunauer-Emmett-Teller (BET) surface area of 78.6 m2 x g(-1). Transmission electron microscopy reveals formation of interconnected pore channels in the membrane. It is interesting to note that the Al2O3 membrane remains at a reasonably high surface area (53.9 m2 x g(-1)) after an isothermal holding at 1200 degrees C, when gamma-Al2O3 changed into predominately alpha-Al2O3. The process is indeed general and can be extended to the synthesis of other inorganic porous solids.

Synthesis, characterization, and antibacterial activity of silver-doped silica nanocomposite particles.

Silver nanoparticles were adsorbed preferentially on silica surface to form composite particles using a reverse micelle process that stabilizes the silver particles by an anionic sodium bis(2-ethylhexyl) sulfosuccinate (AOT) surfactant in isooctane solvent together with the silica particles in which their surface being mediated by a cationic poly(allylamine hydrochloride) (PAH) polyelectrolyte. The heterogeneous adsorption was rendered by both electrostatic attraction and hydrophilic/hydrophobic interaction, and was carried out in multiple deposition cycles. The resulting nanocomposite particles were characterized by zeta-potential measurement, electron microscopy, X-ray diffractometry, field-emission electron spectroscopy for chemical analysis (ESCA), and inductively coupled plasma analysis, respectively. In addition, antibacterial activity of the composite particles was examined against Escherichia coli (E. coli) in aqueous environment.

Aging effect on the phase evolution of water-based sol-gel hydroxyapatite.

In a number of recent reports on the synthesis of sol-gel hydroxyapatite, aging of the precursor solution has been found to be critical in developing an apatitic phase. Critical aging time is required to complete reaction between Ca and P molecular precursors to form a desired intermediate complex that permits a further transformation to apatite phase under appropriate thermal treatment. In this investigation, we employed a water-based sol-gel process recently developed to fabricate hydroxyapatite at relatively low temperatures. The aging effect on apatite formation was systematically studied in terms of aging time and temperature. Experimental results show that the aging time is considerably reduced as aging temperature rises. Long-term thermal aging was unfavorable for apatite formation. The optimal aging parameters for apatite formation were experimentally determined, which was further consolidated into a phase evolution map. Aging kinetic was investigated by monitoring the variation of solution pH, following the determination of an apparent activation energy, which has a value as high as 10.35 kcal/mol, for the chemical reaction occurring upon aging. Optimal solution chemistry was elucidated based on the corresponding phase evolution map.

Structural evolution of sol-gel-derived hydroxyapatite.

Structural evolution upon transformation of sol to gel, and gel to final ceramic during the synthesis of hydroxyapatite is investigated using Fourier transform infrared (FTIR) analysis, X-ray diffraction (XRD), thermal behavior (DTA and TGA), and electron microscopy examination (SEM/TEM). The sol was first thermally aged at 45 C for various time periods up to 120 min. The colloidal sol, which may have an oligomeric structure, was relatively stable against coagulation. Upon drying, the sol particles consolidated into dry gel through van der Waals attraction, and showed X-ray amorphous phosphate structure. The solid gels showed a particulate microstructure, composed of primary particles of about 8-10 nm in diameter. The amorphous gel transformed into crystalline apatite at temperatures > 300 C. The calcined gels showed a nano-scale microstructure, with grains of 20-50 nm in diameter. Through an appropriate heat treatment between 300 and 400d degrees C. the apatite prepared using current process exhibits a nano-scale, low-crystallinity, carbonated apatitic structure, which closely resembles that of human bone apatite.

BiFeO3/α-Fe2O3 core/shell composite particles for fast and selective removal of methyl orange dye in water.

BiFeO3/α-Fe2O3 core/shell composite particles featuring fast removal, selective adsorption, and magnetic recycle capability on anionic methyl orange (MO) dye in water was synthesized by a two-step chemical route. A discontinuous and rough shell consisting of the α-Fe2O3 nanoparticles was deposited on the BiFeO3 core surface preferentially, forming raspberry-like core/shell particle morphology. The core/shell particles demonstrated a pronounced adsorption to the MO molecules when compared with particulate mixtures of the same molar ratio. At an initial MO concentration of 2.5×10(-5) M, nearly 80% of the dye molecules were captured by the core/shell particles within 5 min at an acidic pH of 5.2. Desorption of the MO dye could be made easily when the solution pH was adjusted to 9.5. This together with a minute adsorption capacity (<2%) from solutions consisting of cationic methylene blue (MB) dye suggests that the adsorption selectivity was in part due to electrostatic interactions between the dye molecules and the core/shell particles.