Iron, the most ubiquitous of the transition metals and the fourth most plentiful element in the Earth's crust, is the structural backbone of our modern infrastructure. It is therefore ironic that as a nanoparticle, iron has been somewhat neglected in favor of its own oxides, as well as other metals such as cobalt, nickel, gold, and platinum. This is unfortunate, but understandable. Iron's reactivity is important in macroscopic applications (particularly rusting), but is a dominant concern at the nanoscale. Finely divided iron has long been known to be pyrophoric, which is a major reason that iron nanoparticles have not been more fully studied to date. This extreme reactivity has traditionally made iron nanoparticles difficult to study and inconvenient for practical applications. Iron however has a great deal to offer at the nanoscale, including very potent magnetic and catalytic properties. Recent work has begun to take advantage of iron's potential, and work in this field appears to be blossoming.
A microfluidic device has been developed that can adsorb proteins from solution, hold them with negligible denaturation, and release them on command. The active element in the device is a 4-nanometer-thick polymer film that can be thermally switched between an antifouling hydrophilic state and a protein-adsorbing state that is more hydrophobic. This active polymer has been integrated into a microfluidic hot plate that can be programmed to adsorb and desorb protein monolayers in less than 1 second. The rapid response characteristics of the device can be manipulated for proteomic functions, including preconcentration and separation of soluble proteins on an integrated fluidics chip.
Lithiation-delithiation cycles of individual aluminum nanowires (NWs) with naturally oxidized Al(2)O(3) surface layers (thickness 4-5 nm) were conducted in situ in a transmission electron microscope. Surprisingly, the lithiation was always initiated from the surface Al(2)O(3) layer, forming a stable Li-Al-O glass tube with a thickness of about 6-10 nm wrapping around the NW core. After lithiation of the surface Al(2)O(3) layer, lithiation of the inner Al core took place, which converted the single crystal Al to a polycrystalline LiAl alloy, with a volume expansion of about 100%. The Li-Al-O glass tube survived the 100% volume expansion, by enlarging through elastic and plastic deformation, acting as a solid electrolyte with exceptional mechanical robustness and ion conduction. Voids were formed in the Al NWs during the initial delithiation step and grew continuously with each subsequent delithiation, leading to pulverization of the Al NWs to isolated nanoparticles confined inside the Li-Al-O tube. There was a corresponding loss of capacity with each delithiation step when arrays of NWs were galvonostatically cycled. The results provide important insight into the degradation mechanism of lithium-alloy electrodes and into recent reports about the performance improvement of lithium ion batteries by atomic layer deposition of Al(2)O(3) onto the active materials or electrodes.
In this work, the synthesis and physiochemical characterization of titanium oxide nanoparticle-graphene oxide (TiO 2 -GO) and titanium oxide nanoparticle-reduced graphene oxide (TiO 2 -RGO) composites was undertaken. TiO 2 -GO materials were prepared via the hydrolysis of TiF 4 at 60 °C for 24 h in the presence of an aqueous dispersion of graphene oxide (GO). The reaction proceeded to yield an insoluble material that is composed of TiO 2 and GO. Composites were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), Raman spectroscopy, N 2 adsorption-desorption, and thermal gravimetric analysis/differential thermal analysis (TGA/DTA). This approach yielded highly faceted anatase nanocrystals with petal-like morphologies on and embedded between the graphene sheets. At higher GO concentrations with no stirring of the reaction media, a long-range ordered assembly for TiO 2 -GO sheets was observed due to self-assembly. GO-TiO 2 composites formed colloidal dispersions at low concentrations (∼0.75 mg/mL) in water and ethanol but were not amenable to forming graphene papers via filtration through Anodisc membranes (0.2 µM pore diameter) due to their high titania concentration. Zeta potential measurements and particle size distributions from dynamic light scattering (DLS) experiments on these materials explain the stability of the TiO 2 -GO colloidal solutions. Chemical and thermal methods were also used to reduce TiO 2 -GO to give TiO 2 -RGO materials.
The synthesis of well-defined nanoparticle materials has been an area of intense investigation, but size control in nanoparticle syntheses is largely empirical. Here, we introduce a general method for fine size control in the synthesis of nanoparticles by establishing steady state growth conditions through the continuous, controlled addition of precursor, leading to a uniform rate of particle growth. This approach, which we term the "Extended LaMer Mechanism" allows for reproducibility in particle size from batch to batch, as well as the ability to predict nanoparticle size by monitoring the early stages of growth. We have demonstrated this method by applying it to a challenging synthetic system: magnetite nanoparticles. To facilitate this reaction, we have developed a reproducible method for synthesizing an iron oleate precursor that can be used without purification. We then show how such fine size control affects the performance of magnetite nanoparticles in magnetic hyperthermia.
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