The introduction of metallic traces into the synthesis of platinum nanocrystals (Pt NCs) has been investigated as a surfactant-independent means of controlling shape. Various nanocrystal morphologies have been produced without modification of the reaction conditions, composition, and concentration other than the presence of cobalt traces (<5%). In the presence of metallic cobalt (a strong reducer for Pt cations) cubic Pt NCs are obtained, while cobalt ions or gold NCs have no effect on the synthesis, and as a result, polypods are obtained. Intermediate shapes such as cemented cubes or cuboctahedron NCs are also obtained under similar conditions. Thus, various NC shapes can be obtained with subtle changes, which illustrates the high susceptibility and mutability of the NC shape to modification of the reaction kinetics during the early reduction process. Our studies help progress toward a general mechanism for nanocrystal shape control.
Magnetostatic (dipolar) interactions between nanoparticles promise to open new ways to design nanocrystalline magnetic materials and devices if the collective magnetic properties can be controlled at the nanoparticle level. Magnetic dipolar interactions are sufficiently strong to sustain magnetic order at ambient temperature in assemblies of closely-spaced nanoparticles with magnetic moments of ≥ 100 μB. Here we use electron holography with sub-particle resolution to reveal the correlation between particle arrangement and magnetic order in self-assembled 1D and quasi-2D arrangements of 15 nm cobalt nanoparticles. In the initial states, we observe dipolar ferromagnetism, antiferromagnetism and local flux closure, depending on the particle arrangement. Surprisingly, after magnetic saturation, measurements and numerical simulations show that overall ferromagnetic order exists in the present nanoparticle assemblies even when their arrangement is completely disordered. Such direct quantification of the correlation between topological and magnetic order is essential for the technological exploitation of magnetic quasi-2D nanoparticle assemblies.
The assembly of magnetic cores into regular structures may notably influence the properties displayed by a magnetic colloid. Here, key synthesis parameters driving the self‐assembly process capable of organizing colloidal magnetic cores into highly regular and reproducible multi‐core nanoparticles are determined. In addition, a self‐consistent picture that explains the collective magnetic properties exhibited by these complex assemblies is achieved through structural, colloidal, and magnetic means. For this purpose, different strategies to obtain flower‐shaped iron oxide assemblies in the size range 25–100 nm are examined. The routes are based on the partial oxidation of Fe(OH)2, polyol‐mediated synthesis or the reduction of iron acetylacetonate. The nanoparticles are functionalized either with dextran, citric acid, or alternatively embedded in polystyrene and their long‐term stability is assessed. The core size is measured, calculated, and modeled using both structural and magnetic means, while the Debye model and multi‐core extended model are used to study interparticle interactions. This is the first step toward standardized protocols of synthesis and characterization of flower‐shaped nanoparticles.
Room temperature syntheses of AuPt heterodimers are reported using a simple protocol. The role of oleylamine and Pt NCs in the reduction and nucleation of Au has been investigated. There are two unique aspects in this synthesis. First, the synthesis was conducted at room temperature, which enabled the heterodimer growth to progress at a slower rate and thus allowed monitoring of the Au nucleation process. Secondly, the presence of Pt NC seeds markedly accelerated the epitaxial growth of Au serving both as nucleation platform and as initial catalytic reducer of the Au +3 precursor. The growth of Au on Pt NCs was monitored at different times by UV-vis, HRTEM and XRD.
Superparamagnetic single crystal single domain Co nanoparticles of 6 nm in diameter evaporated onto highly pyrolytic oriented graphite spontaneously self-assemble into super structures with an elongated shape. These structures have been studied by optical and scanning electron microscopies, atomic and magnetic force microscopy, electron dispersive X-ray analysis, and SQUID magnetometry. We propose that the weak dipolar interactions between superparamagnetic dipoles of the cobalt nanoparticles are responsible for the formation of these structures when the dipolar magnetic interactions are strong enough to influence the general process of self-assembly dominated by van der Waals forces between neighboring nanoparticles and between nanoparticles and the substrate during evaporation of the solvent.
We observe the spontaneous formation of hollow cobalt oxide nanoparticles at room temperature, indicating an enhancement of the solid-state diffusion at the nanoscale. Single crystal cobalt nanoparticles covered by a hydrophobic organic layer were transformed spontaneously into CoO hollow nanoparticles when deposited on the water-air interface in a matter of a few hours. The presence of water modifies the reactivity on the nanoparticle surface favoring the formation of the hollow structure; otherwise Co-CoO core-shell nanoparticles are obtained. The CoO hollow nanoparticles are formed only in an intermediate state, and after a period of time these structures finally undergo disintegration to form minor CoO entities.
Figure S1 in the original Supporting Information has been changed. A revised file with all the Supporting Information content is available.Supporting Information Available. Details on the synthesis, HRTEM and TEM images of the Pt and Co NCs, analysis of the % Co using ICP-MS, EDX spectra, and Vegard's law. This material is available free of charge via the Internet at http:// pubs.acs.org.
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