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.
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.
Currently, antibiotic resistance and cancer are two of the most important public health problems killing more than ∼1.5 million people annually, showing that antibiotics and current chemotherapeutics are not as effective as they were in the past. Nanotechnology is presented here as a potential solution. However, current protocols for the traditional physicochemical synthesis of nanomaterials are not free of environmental and social drawbacks, often involving the use of toxic catalysts. This article shows the production of pure naked selenium nanoparticles (SeNPs) by a novel green process called pulsed laser ablation in liquids (PLAL). After the first set of irradiations, another set was performed to reduce the size below 100 nm, which resulted in a colloidal solution of spherical SeNPs with two main populations having sizes around ∼80 and ∼10 nm. The particles after the second set of irradiations also showed higher colloidal stability. SeNPs showed a dose-dependent antibacterial effect toward both standard and antibioticresistant phenotypes of Gram-negative and Gram-positive bacteria at a range of concentrations between 0.05 and 25 ppm. Besides, the SeNPs showed a low cytotoxic effect when cultured with human dermal fibroblasts cells at a range of concentrations up to 1 ppm while showing an anticancer effect toward human melanoma and glioblastoma cells at the same concentration range. This article therefore introduces the possibility of using totally naked SeNPs synthesized by a new PLAL protocol as a novel and efficient nanoparticle fabrication process for biomedical applications.
Due to the lack of experimental values concerning some material properties at the nanoscale, it is interesting to evaluate this theoretically. Through a “top–down” approach, a universal equation is developed here which is particularly helpful when experiments are difficult to lead on a specific material property. It only requires the knowledge of the surface area to volume ratio of the nanomaterial, its size as well as the statistic (Fermi–Dirac or Bose–Einstein) followed by the particles involved in the considered material property. Comparison between different existing theoretical models and the proposed equation is done.
Bimetallic nanoparticles like Cu-Ni are particularly attractive due to their magnetic and catalytic properties; however, their properties depend strongly on the structure of the alloy i.e. mixed, core-shell or Janus. To predict the alloy structure, this paper investigates the size and shape effects as well as the surface segregation effect on the Cu-Ni phase diagram. Phase maps have been plotted to determine the mixing/demixing behavior of this alloy according the particle shape. Cu-Ni nanoalloy can form a mixed particle or a Janus one depending on the synthesis temperature. Surface segregation is also considered and reveals a nickel surface-enrichment. Finally, this paper provides a useful roadmap for experimentalists.
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