Electrum, the Gold–Silver Alloy, from the Bulk Scale to the Nanoscale: Synthesis, Properties, and Segregation Rules
| Autor: | José Luis Rodríguez-López, José Antonio Robledo-Torres, J. Jesús Velázquez-Salazar, Rafael Mendoza-Perez, Miguel Jose-Yacaman, Rubén Mendoza-Cruz, Lourdes Bazán-Díaz, Robert L. Whetten, Grégory Guisbiers, Juan Martín Montejano-Carrizales |
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| Rok vydání: | 2015 |
| Předmět: |
optical properties
Silver Materials science Cuboctahedron Alloy Regular solution surface segregation Metal Nanoparticles General Physics and Astronomy Nanotechnology noble metals 02 engineering and technology polyhedra engineering.material 010402 general chemistry 01 natural sciences Article Phase Transition Microscopy Electron Transmission Phase (matter) Alloys General Materials Science Particle Size Nanoscopic scale Phase diagram nanothermodynamics thermal properties Temperature General Engineering Surface Plasmon Resonance 021001 nanoscience & nanotechnology phase diagram 0104 chemical sciences Rhombic dodecahedron Chemical physics engineering Thermodynamics Gold Cube 0210 nano-technology aberration corrected electron microscopy |
| Zdroj: | ACS Nano |
| ISSN: | 1936-086X 1936-0851 |
| DOI: | 10.1021/acsnano.5b05755 |
| Popis: | The alloy Au-Ag system is an important noble bimetallic phase, both historically (as "Electrum") and now especially in nanotechnology, as it is applied in catalysis and nanomedicine. To comprehend the structural characteristics and the thermodynamic stability of this alloy, a knowledge of its phase diagram is required that considers explicitly its size and shape (morphology) dependence. However, as the experimental determination remains quite challenging at the nanoscale, theoretical guidance can provide significant advantages. Using a regular solution model within a nanothermodynamic approach to evaluate the size effect on all the parameters (melting temperature, melting enthalpy, and interaction parameters in both phases), the nanophase diagram is predicted. Besides an overall shift downward, there is a "tilting" effect on the solidus-liquidus curves for some particular shapes exposing the (100) and (110) facets (cube, rhombic dodecahedron, and cuboctahedron). The segregation calculation reveals the preferential presence of silver at the surface for all the polyhedral shapes considered, in excellent agreement with the latest transmission electron microscopy observations and energy dispersive spectroscopy analysis. By reviewing the nature of the surface segregated element of different bimetallic nanoalloys, two surface segregation rules, based on the melting temperatures and surface energies, are deduced. Finally, the optical properties of Au-Ag nanoparticles, calculated within the discrete dipole approximation, show the control that can be achieved in the tuning of the local surface plasmon resonance, depending of the alloy content, the chemical ordering, the morphology, the size of the nanoparticle, and the nature of the surrounding environment. |
| Databáze: | OpenAIRE |
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