J. Jesús Velázquez-Salazar

Electrum, the Gold–Silver Alloy, from the Bulk Scale to the Nanoscale: Synthesis, Properties, and Segregation Rules

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.

Experimental evidence of icosahedral and decahedral packing in one-dimensional nanostructures.

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 affects the chemical and structural properties of the material and, hence, its potential applications. This report describes the experimental formation of 5-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 5-fold symmetry. These icosahedral nanowire structures are similar to those of quasicrystals, which 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.

Trimetallic nanostructures: the case of AgPd–Pt multiply twinned nanoparticles

We report the synthesis, structural characterization, and atomistic simulations of AgPd-Pt trimetallic (TM) nanoparticles. Two types of structure were synthesized using a relatively facile chemical method: multiply twinned core-shell, and hollow particles. The nanoparticles were small in size, with an average diameter of 11 nm and a narrow distribution, and their characterization by aberration corrected scanning transmission electron microscopy allowed us to probe the structure of the particles at an atomistic level. In some nanoparticles, the formation of a hollow structure was also observed, that facilitates the alloying of Ag and Pt in the shell region and the segregation of Ag atoms on the surface, affecting the catalytic activity and stability. We also investigated the growth mechanism of the nanoparticles using grand canonical Monte Carlo simulations, and we have found that Pt regions grow at overpotentials on the AgPd nanoalloys, forming 3D islands at the early stages of the deposition process. We found very good agreement between the simulated structures and those observed experimentally.

Procedures for the synthesis and capping of metal nanoparticles.

The increasing impact of metallic nanoparticles in life sciences has stimulated the development of new techniques and multiple improvements of the existing methods of manufacturing nanoparticles with tailored properties. Nanoparticles can be synthesized through a variety of physical and chemical methods. The choice of preparation procedure will depend on the physical and chemical characteristics required on the final product, such as size, dispersion, chemical miscibility, optical properties, among others. Here we review basic practical procedures used for the preparation of protected and unprotected metallic nanoparticles and describe a number of experimental procedures based on colloidal chemistry methods. These include gold nanoparticle synthesis by reduction with trisodium citrate, ascorbic acid, or sugars in aqueous phase; nanoparticle passivation with alkanethiols, cetyltrimethylammonium bromide, or bovin serum albumin. We also describe microwave-assisted synthesis, nanoparticle synthesis in ethylene glycol, template-assisted synthesis with dendrimers and briefly describe how to control nanoparticle shape (star-shaped and branched nanoparticles).

Highly monodisperse multiple twinned AuCu–Pt trimetallic nanoparticles with high index surfaces

Trimetallic nanoparticles possess different properties than their mono- and bi-metallic counterparts, opening a wide range of possibilities for diverse potential applications with the notion to study possible morphology, atomic ordering, reduce precious metal consumption and many others. In this paper, we present a comprehensive experimental study on AuCu-Pt trimetallic nanoparticles with an average diameter of 15 ± 1.0 nm, synthesized in a one-pot synthesis method and characterized by the Cs-corrected scanning transmission electron microscopy technique that allowed us to probe the structure at the atomic level resolution. A new way to control the nanoparticle morphology by the presence of third metal (Pt) is also discussed by the overgrowth of Pt on the as prepared AuCu core by Frank-van der Merwe (FM) layer-by-layer and Stranski-Krastanov (SK) island-on-wetting-layer growth modes. With the application of this research, we are now a step closer to produce optimum catalysts in which the active phase forms only surface monolayers. In addition, the nanoalloy exhibits high index facet surfaces with {211} and {321} families that are highly open-structure surfaces and are interesting for the catalytic applications.

CuS2-Passivated Au-Core, Au3Cu-Shell Nanoparticles Analyzed by Atomistic-Resolution Cs-Corrected STEM

Au-core, Au3Cu-alloyed shell nanoparticles passivated with CuS2 were fabricated by the polyol method, and characterized by Cs-corrected scanning transmission electron microscopy. The analysis of the high-resolution micrographs reveals that these nanoparticles have decahedral structure with shell periodicity, and that each of the particles is composed by Au core and Au3Cu alloyed shell surrounded by CuS2 surface layer. X-ray diffraction measurements and results from numerical simulations confirm these findings. From the atomic resolution micrographs, we identified edge dislocations at the twin boundaries of the particles, as well as evidence of the diffusion of Cu atoms into the Au region, and the reordering of the lattice on the surface, close to the vertices of the particle. These defects will impact the atomic and electronic structures, thereby changing the physical and chemical properties of the nanoparticles. On the other hand, we show for the first time the formation of an ordered superlattice of Au3Cu and a self-capping layer made using one of the alloy metals. This has significant consequences on the physical mechanism that form multicomponent nanoparticles.

Synthesis, characterization, and growth simulations of Cu–Pt bimetallic nanoclusters

Summary Highly monodispersed Cu–Pt bimetallic nanoclusters were synthesized by a facile synthesis approach. Analysis of transmission electron microscopy (TEM) and spherical aberration (C s)-corrected scanning transmission electron microscopy (STEM) images shows that the average diameter of the Cu–Pt nanoclusters is 3.0 ± 1.0 nm. The high angle annular dark field (HAADF-STEM) images, intensity profiles, and energy dispersive X-ray spectroscopy (EDX) line scans, allowed us to study the distribution of Cu and Pt with atomistic resolution, finding that Pt is embedded randomly in the Cu lattice. A novel simulation method is applied to study the growth mechanism, which shows the formation of alloy structures in good agreement with the experimental evidence. The findings give insight into the formation mechanism of the nanosized Cu–Pt bimetallic catalysts.

Growth mechanism of nanoparticles: theoretical calculations and experimental results

We report a combined theoretical and experimental study on the growth mechanism of silver and gold nanoparticles. We introduce for the first time the grand-canonical Monte Carlo method to study the growth/dissolution steps of nanoparticle growth mediated by seeds. In particular we found that small changes on the chemical potential, i.e. the activity of the metal ions, produce significant changes on the size and morphologies of the nanoparticles. We have found very good agreements between simulated structures with those observed experimentally by means of scanning electron microscopy.

Helical Growth of Ultrathin Gold-Copper Nanowires

In this work, we report the synthesis and detailed structural characterization of novel helical gold-copper nanowires. The nanowires possess the Boerdijk-Coxeter-Bernal structure, based on the pile up of octahedral, icosahedral, and/or decahedral seeds. They are self-assembled into a coiled manner as individual wires or into a parallel-ordering way as groups of wires. The helical nanowires are ultrathin with a diameter of less than 10 nm and variable length of several micrometers, presenting a high density of twin boundaries and stacking faults. To the best of our knowledge, such gold-copper nanowires have never been reported previously.

Analysis of cytotoxic effects of silver nanoclusters on human peripheral blood mononuclear cells 'in vitro'.

The antimicrobial properties of silver nanoparticles (AgNPs) have made these particles one of the most used nanomaterials in consumer products. Therefore, an understanding of the interactions (unwanted toxicity) between nanoparticles and human cells is of significant interest. The aim of this study was to assess the in vitro cytotoxicity effects of silver nanoclusters (AgNC, < 2 nm diameter) on peripheral blood mononuclear cells (PBMC). Using flow cytometry and comet assay methods, we demonstrate that exposure of PBMC to AgNC induced intracellular reactive oxygen species (ROS) generation, DNA damage and apoptosis at 3, 6 and 12 h, with a dose‐dependent response (0.1, 1, 3, 5 and 30 µg ml–1). Advanced electron microscopy imaging of complete and ultrathin‐sections of PBMC confirmed the cytotoxic effects and cell damage caused by AgNC. The present study showed that AgNC produced without coating agents induced significant cytotoxic effects on PBMC owing to their high aspect ratio and active surface area, even at much lower concentrations (<1 µg ml–1) than those applied in previous studies, resembling what would occur under real exposure conditions to nanosilver‐functionalized consumer products. Copyright