Rubén Mendoza-Cruz

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.

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.

Metallic Two-Dimensional Nanoframes: Unsupported Hierarchical Nickel–Platinum Alloy Nanoarchitectures with Enhanced Electrochemical Oxygen Reduction Activity and Stability

Electrochemical oxygen reduction reaction (ORR) catalysts that have both high activities and long-term stabilities are needed for proton-exchange membrane fuel cells (PEMFCs) and metal-air batteries. Two-dimensional (2D) materials based on graphene have shown high catalytic activities, however, carbon-based materials result in significant catalyst degradation due to carbon oxidation that occurs at high electrochemical potentials. Here, we introduce the synthesis and electrochemical performance of metallic 2D nanoframes which represent a new approach to translate 2D materials into unsupported (carbon-free) electrocatalysts that have both significantly higher ORR catalytic activities and stabilities compared with conventional Pt/carbon electrocatalysts. Metallic Ni-Pt 2D nanoframes were synthesized by controlled thermal treatments of Pt-decorated Ni(OH)2 nanosheets. The nanoframes consist of a hierarchical 2D framework composed of a highly catalytically active Pt-Ni alloy phase with an interconnected solid and pore network that results in three-dimensional molecular accessibility. The inclusion of Ni within the Pt structure resulted in significantly smaller Pt lattice distances compared to those of Pt nanoparticles. On the basis of its unique local and extended structure, the ORR specific activity of Ni-Pt 2D nanoframes (5.8 mA cmPt-2) was an order of magnitude higher than Pt/carbon. In addition, accelerated stability testing at elevated potentials up to 1.3 VRHE showed that the metallic Ni-Pt nanoframes exhibit significantly improved stability compared with Pt/carbon catalysts. The nanoarchitecture and local structure of metallic 2D nanoframes results in high combined specific activity and elevated potential stability. Analysis of the ORR electrochemical reaction kinetics on the Ni-Pt nanoframes supports that at low overpotentials the first electron transfer is the rate-determining step, and the reaction proceeds via a four electron reduction process. The ability to create metallic 2D structures with 3D molecular accessibility opens up new opportunities for the design of high activity and stability carbon-free catalyst nanoarchitectures for numerous electrocatalytic and catalytic applications.

Gold-copper nanostars as photo-thermal agents: Synthesis and advanced electron microscopy characterization

Nanoalloys have emerged as multi-functional nanoparticles with applications in biomedicine and catalysis. This work reports the efficient production and the advanced transmission electron microscopy characterization of gold-copper pentagonal nanostars. The morphology of the branches is controlled by the adequate choice of the capping agent. When oleylamine is used rounded nanostars are produced, while pointed nanostars are obtained by using hexadecylamine. Both types of nanostars were proved to be thermally stable and could therefore be used as therapeutic agents in photo-thermal therapies as confirmed by the near-infrared absorption spectra.

Inhibition of Candida albicans biofilm by pure selenium nanoparticles synthesized by pulsed laser ablation in liquids

Selenoproteins play an important role in the human body by accomplishing essential biological functions like oxido-reductions, antioxidant defense, thyroid hormone metabolism and immune response; therefore, the possibility to synthesize selenium nanoparticles free of any contaminants is exciting for future nano-medical applications. This paper reports the first synthesis of selenium nanoparticles by femtosecond pulsed laser ablation in de-ionized water. Those pure nanoparticles have been successfully used to inhibit the formation of Candida albicans biofilms. Advanced electron microscopy images showed that selenium nanoparticles easily adhere on the biofilm, then penetrate into the pathogen, and consequently damage the cell structure by substituting with sulfur. 50% inhibition of Candida albicans biofilm was obtained at only 25 ppm. Finally, the two physical parameters proved to affect strongly the viability of Candida albicans are the crystallinity and particle size.

Inhibition of E. coli and S. aureus with selenium nanoparticles synthesized by pulsed laser ablation in deionized water

Nosocomial diseases are mainly caused by two common pathogens, Escherichia coli and Staphylococcus aureus, which are becoming more and more resistant to conventional antibiotics. Therefore, it is becoming increasingly necessary to find other alternative treatments than commonly utilized drugs. A promising strategy is to use nanomaterials such as selenium nanoparticles. However, the ability to produce nanoparticles free of any contamination is very challenging, especially for nano-medical applications. This paper reports the successful synthesis of pure selenium nanoparticles by laser ablation in water and determines the minimal concentration required for ~50% inhibition of either E. coli or S. aureus after 24 hours to be at least ~50 ppm. Total inhibition of E. coli and S. aureus is expected to occur at 107±12 and 79±4 ppm, respectively. In this manner, this study reports for the first time an easy synthesis process for creating pure selenium to inhibit bacterial growth.

Synthesis and Properties of the Self-Assembly of Gold–Copper Nanoparticles into Nanoribbons

We report the efficient wet-chemical production of self-assembled gold-copper bimetallic nanoparticles (diameter of ∼2 nm) into two-dimensional flexible ribbonlike nanostructures. The direct observation of a layered arrangement of particles into nanoribbons was provided through high-resolution transmission electron microscopy and electron tomography. These nanoribbons showed photoluminesce and efficient photocatalytic activity for the conversion of 4-nitrophenol. The thermal stability of the nanoribbons was also measured by in situ heat treatment in the electron microscope, confirming that the self-assembled gold-copper nanoribbons efficiently supported up to 350 °C. The final morphology of the nanoparticles and their ability to self-assemble into flexible nanoribbons were dependent on concentration and the ratio of precursors. Therefore, these experimental factors were discussed. Remarkably, the presence of copper was found to be critical to triggering the self-assembly of nanoparticles into ordered layered structures. These results for the synthesis and stability of self-assemblies of metallic nanoparticles present a potential extension of the method to producing materials with catalytic applications.

A novel one-pot room-temperature synthesis route to produce very small photoluminescent silicon nanocrystals

AbstractA novel strategy to synthesize photoluminescent silicon nanocrystals (SiNCs) from a reaction between tetraethylorthosilicate (TEOS) and trimethyl-hexadecyl-ammonium borohydride (CTABH4) in organic solvent is presented. The formation reaction occurs spontaneously at room temperature in homogeneous phase. The produced silicon nanocrystals are characterized by using their photoluminescent properties and via HRTEM. In addition, theoretical calculations of the optical absorption spectrum of silicon quantum dots in vacuum with different sizes and surface moieties were performed in order to compare with the experimental findings. The new chemical reaction is simple and can be implemented to produce silicon nanocrystal with regular laboratory materials by performing easy and safe procedures. Graphical abstractᅟ

Integrative structural and advanced imaging characterization of manganese oxide nanotubes doped with cobaltite

Manganese oxide nanotubes (MnO2) were efficiently produced through a hydrothermal method, using SiO2 powder as nucleation points, then doped with cobaltite (Co3O4) nanoparticles uniformly deposited along the surface of the MnO2 nanotubes. An integrative approach using advanced analytical electron microscopy techniques (UHR FE-SEM, HR-TEM, and BF/HAADF-STEM, coupled with EDX) in combination with spectroscopy allowed the determination of the structural characteristics of this composite nanomaterial. Advanced imaging clearly revealed the tubular structure of the MnO2 nanotubes (diameter of 30–80 nm and length of 3–5 μm) and the arrangement of the discrete Co3O4 deposits (10–40 nm). Remarkably, high-resolution and spherical aberration-corrected STEM imaging allowed for the determination of the crystalline arrangement of the nanomaterials, particularly at the interface between MnO2 and Co3O4 particles with high spatial sub-Angstrom resolution, revealing the distribution and high structural consistency of the novel composite materials produced. Furthermore, X-ray diffraction and Raman spectroscopy confirmed that MnO2 corresponded to the crystallographic phase cryptomelane (K2-xMn8O16), while the dopant cobalt nanoparticles adopted a cobaltite (Co3O4) phase. We demonstrated the catalytic properties of the composite MnO2–Co3O4 nanotubes as an electrocatalyst material for oxygen evolution, where it showed superior behaviour, with a significantly higher catalytic activity (6.8 times) than pure MnO2 in the OER region.

Copper complexes within the supramolecular solid structure of cyanuric acid and melamine

ABSTRACT A complex of copper sulfate was formed by impregnation of the cyanuric acid melamine adduct (CAM) with a solution of copper (II) sulfate. A thermal treatment at 250°C of the dried compound delivered a greenish powder. The UV-Vis spectroscopy showed that an absorption around 700 nm is compatible with a copper (II) sulfate complex coordinated inside the supramolecular structure of CAM. No copper or copper oxide particles were found by means of either transmission or scanning electron microscopy. X-ray photoelectron spectroscopy showed that on the surface there was a considerable amount of Cu(I) (66%) probably coordinated also inside the CAM channels. A brief catalytic test showed the ability of the copper complexes to oxidize sucrose to gluconic acid.