Gold–copper (Au–Cu) phases were employed already by pre-Columbian civilizations, essentially in decorative arts, whereas nowadays, they emerge in nanotechnology as an important catalyst. The knowledge of the phase diagram is critical to understanding the performance of a material. However, experimental determination of nanophase diagrams is rare because calorimetry remains quite challenging at the nanoscale; theoretical investigations, therefore, are welcomed. Using nanothermodynamics, this paper presents the phase diagrams of various polyhedral nanoparticles (tetrahedron, cube, octahedron, decahedron, dodecahedron, rhombic dodecahedron, truncated octahedron, cuboctahedron, and icosahedron) at sizes 4 and 10 nm. One finds, for all the shapes investigated, that the congruent melting point of these nanoparticles is shifted with respect to both size and composition (copper enrichment). Segregation reveals a gold enrichment at the surface, leading to a kind of core–shell structure, reminiscent of the historical artifacts. Finally, the most stable structures were determined to be the dodecahedron, truncated octahedron, and icosahedron with a Cu-rich core/Au-rich surface. The results of the thermodynamic approach are compared and supported by molecular-dynamics simulations and by electron-microscopy (EDX) observations.
We performed a study on bimetallic Au/Pd nanoparticles using aberration corrected electron microscopy along with molecular dynamics simulations to investigate the features of specific atomic sites at the surface, which can be related to the high catalytic activity properties of the particles. The calculations mimic the growth of nanoparticles through a cooling process from a molten solid to a crystalline structure at room temperature. We found that the final structure for the alloy particles is neither a cuboctahedral nor an icosahedral, but a complex structure that has a very rough surface and unique isolated Pd sites surrounded by Au atoms. We also found that there is predominance of three specific Pd sites at the surface, which can be directly related to the catalytic activity of the nanoparticles.
The packing of spheres is a subject that has drawn the attention of mathematicians and philosophers for centuries, and that currently attracts the interest of the scientific community in several fields. At the nanoscale, the packing of atoms affect the chemical and structural properties of the material, and hence, its potential applications. This report describes the experimental formation of five-fold nanostructures by the packing of interpenetrated icosahedral and decahedral units. These nanowires, formed by the reaction of a mixture of metal salts (Au and Ag) in the presence of oleylamine, are obtained when the chemical composition is specifically Ag/Au=3/1. The experimental images of the icosahedral nanowires have a high likelihood with simulated electron micrographs of structures formed by two or three Boerdijk-Coxeter-Bernal helices roped on a single structure, whereas for the decahedral wires, simulations using a model of adjacent decahedra match the experimental structures. To our knowledge, this is the first report of the synthesis of nanowires formed by the packing of structures with five-fold symmetry. These icosahedral nanowire structures remind those of quasicrystals that can only be formed if at least two atomic species are present and in which icosahedral and decahedral packing has been found for bulk crystals.
Surprisingly oxidation resistant icosahedral FePt nanoparticles showing hard-magnetic properties have been fabricated by an inert-gas condensation method with in-flight annealing. High-resolution transmission electron microscopy (HRTEM) images with sub-Angstrom resolution of the nanoparticle have been obtained with focal series reconstruction, revealing noncrystalline nature of the nanoparticle. Digital dark-field method combined with structure reconstruction as well as HRTEM simulations reveal that these nanoparticles have icosahedral structure with shell periodicity. Localized lattice relaxations have been studied by extracting the position of individual atomic columns with a precision of about (0.002 nm. The lattice spacings of (111) planes from the surface region to the center of the icosahedra are found to decrease exponentially with shell numbers. Computational studies and energy-filtered transmission electron microscopy analyses suggest that a Pt-enriched surface layer is energetically favored and that site-specific vacancies are formed at the edges of facettes, which was experimentally observed. The presence of the Pt-enriched shell around an Fe/Pt core explains the environmental stability of the magnetic icosahedra and strongly reduces the exchange coupling between neighboring particles, thereby possibly providing the highest packing density for future magnetic storage media based on FePt nanoparticles.
Several series of molecular dynamics runs were performed to simulate the melting transition of bimetallic cuboctahedral nanoparticles of gold-palladium at different relative concentrations to study their structural properties before, in, and after the transition. The simulations were made in the canonical ensemble, each series covering a range of temperatures from 300 to 980 K, using the Rafii-Tabar version of the Sutton and Chen interatomic potential for metallic alloys. We found that the melting transition temperature has a strong dependence on the relative concentrations of the atomic species. We also found that, previous to the melting transition, the outer layer of the nanoparticle gets disordered in what can be thought as a premelting stage, where Au atoms near the surface migrate to the surface and remain there after the particle melts as a whole. The melting of the surface below T m is consistent with studies of the interaction of a TEM electron beam with Au and Au-Pd nanoparticles.
Gold/Palladium nanoparticles were fabricated by inert-gas condensation on a sputtering reactor. With this method, by controlling both the atmosphere on the condensation chamber and the magnetron power, it was possible to produce nanoparticles with a high degree of monodispersity in size. The structure and size of the Au/Pd nanoparticles were determined by mass spectroscopy, and confirmed by atomic force microscopy and electron transmission microscopy measurements. The chemical composition was analyzed by X-ray microanalysis. From these measurements we confirmed that with the sputtering technique we are able to produce particles of 1, 3, and 5 nm on size, depending on the choice of the synthesis conditions. From TEM measurements made both in the regular HREM, as well as in STEM-HAADF mode, we found that the particles are icosahedral in shape, and the micrographs show no evidence of a core-shell structure, in contrast to what is observed in the case of nanoparticles prepared by chemical synthesis.
Aberration-corrected imaging is employed under the scanning transmission electron microscopy (STEM) mode to precisely determine the chemical ordering of Au/Pd nanoparticles. These colloids exhibit a core-shell structure with a three-layer arrangement that surprisingly presents alloying events in the observed layers. Aberration-corrected imaging is employed under the scanning transmission electron microscopy (STEM) mode to precisely determine the chemical ordering of Au/Pd nanoparticles. These colloids exhibit a coreshell structure with a three-layer arrangement that surprisingly presents alloying events in the observed layers. The study of nanomaterials can be greatly improved with the use of aberration-corrected transmission electron microscopy (TEM), which provides image resolutions at the level of 1 Å and lower. Sub-Å ngströ m image resolution can yield a new level of understanding of the behavior of matter at the nanoscale. For example, bimetallic nanoparticles are extremely important in catalysis applications; the addition of a second metal in many cases produces much-improved catalysts. In this paper, we study the structure and morphology of Au/Pd bimetallic particles using primarily the high-angle annular dark-field (HAADF) imaging mode in an aberration-corrected STEM/TEM. It is well established that, when recorded under appropriate illumination and collection geometries, incoherent HAADF-STEM images are compositionally sensitive and provide direct information on atomic positions. We matched the experimental intensities of atomic columns with theoretical models of three-layer Au/Pd nanoparticles, in different orientations. Our findings indicate that the surface layer of the nanoparticle contains kinks, terraces and steps at the nanoscale. The effect of adding a second metal induces the formation of such defects, which might very likely promote the well-known improved catalytic activity of this system.
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