Gilles R. Bourret

1D Cu(OH)2 Nanomaterial Synthesis Templated in Water Microdroplets

For many applications, micro- and nanostructured materials show a strong correlation between their geometry and their function. We report here the interfacial precipitation of a copper/alkylamine complex to form Cu(OH)(2) nanofibers in a two-phase system (H(2)O/CH(2)Cl(2)). Their aggregation results in porous microbeads. This mesoscale aggregation is due to the formation of a water-in-oil (W/O) emulsion. The fibers formed at the H(2)O/CH(2)Cl(2) interface adsorb on the water droplet surface leading to spherical networks of Cu(OH)(2) fibers. Our preparation technique is rapid (less than 1 h) and benefits from the simplicity and the tunability of emulsions.To our knowledge, this is the first demonstration of the in situ synthesis of 1D nanostructures that self-assemble at both the surface and the inside of emulsion droplets. We report the successful control over the chemical nature of the synthesized material, its size, and morphology at both the mesoscale (completely hollow versus porous) and the nanoscale (nanoribbons versus nanofibers) by the addition of a short chain alcohol. The transformation of these materials into porous CuO spheres has several potential applications, including a demonstrated sensitive response to visible light (measured photocurrent/dark current ratio of 2.22).

Modification of Charge Trapping at Particle/Particle Interfaces by Electrochemical Hydrogen Doping of Nanocrystalline TiO2

Particle/particle interfaces play a crucial role in the functionality and performance of nanocrystalline materials such as mesoporous metal oxide electrodes. Defects at these interfaces are known to impede charge separation via slow-down of transport and increase of charge recombination, but can be passivated via electrochemical doping (i.e., incorporation of electron/proton pairs), leading to transient but large enhancement of photoelectrode performance. Although this process is technologically very relevant, it is still poorly understood. Here we report on the electrochemical characterization and the theoretical modeling of electron traps in nanocrystalline rutile TiO2 films. Significant changes in the electrochemical response of porous films consisting of a random network of TiO2 particles are observed upon the electrochemical accumulation of electron/proton pairs. The reversible shift of a capacitive peak in the voltammetric profile of the electrode is assigned to an energetic modification of trap states at particle/particle interfaces. This hypothesis is supported by first-principles theoretical calculations on a TiO2 grain boundary, providing a simple model for particle/particle interfaces. In particular, it is shown how protons readily segregate to the grain boundary (being up to 0.6 eV more stable than in the TiO2 bulk), modifying its structure and electron-trapping properties. The presence of hydrogen at the grain boundary increases the average depth of traps while at the same time reducing their number compared to the undoped situation. This provides an explanation for the transient enhancement of the photoelectrocatalytic activity toward methanol photooxidation which is observed following electrochemical hydrogen doping of rutile TiO2 nanoparticle electrodes.

Hydration of magnesia cubes: a helium ion microscopy study

Summary Physisorbed water originating from exposure to the ambient can have a strong impact on the structure and chemistry of oxide nanomaterials. The effect can be particularly pronounced when these oxides are in physical contact with a solid substrate such as the ones used for immobilization to perform electron or ion microscopy imaging. We used helium ion microscopy (HIM) and investigated morphological changes of vapor-phase-grown MgO cubes after vacuum annealing and pressing into foils of soft and high purity indium. The indium foils were either used as obtained or, for reference, subjected to vacuum drying. After four days of storage in the vacuum chamber of the microscope and at a base pressure of p < 10−7 mbar, we observed on these cubic particles the attack of residual physisorbed water molecules from the indium substrate. As a result, thin magnesium hydroxide layers spontaneously grew, giving rise to characteristic volume expansion effects, which depended on the size of the particles. Rounding of the originally sharp cube edges leads to a significant loss of the morphological definition specific to the MgO cubes. Comparison of different regions within one sample before and after exposure to liquid water reveals different transformation processes, such as the formation of Mg(OH)2 shells that act as diffusion barriers for MgO dissolution or the evolution of brucite nanosheets organized in characteristic flower-like microstructures. The findings underline the significant metastability of nanomaterials under both ambient and high-vacuum conditions and show the dramatic effect of ubiquitous water films during storage and characterization of oxide nanomaterials.

Enzyme adsorption-induced activity changes: a quantitative study on TiO2 model agglomerates

BackgroundActivity retention upon enzyme adsorption on inorganic nanostructures depends on different system parameters such as structure and composition of the support, composition of the medium as well as enzyme loading. Qualitative and quantitative characterization work, which aims at an elucidation of the microscopic details governing enzymatic activity, requires well-defined model systems.ResultsVapor phase-grown and thermally processed anatase TiO2 nanoparticle powders were transformed into aqueous particle dispersions and characterized by dynamic light scattering and laser Doppler electrophoresis. Addition of β-galactosidase (β-gal) to these dispersions leads to complete enzyme adsorption and the generation of β-gal/TiO2 heteroaggregates. For low enzyme loadings (~4% of the theoretical monolayer coverage) we observed a dramatic activity loss in enzymatic activity by a factor of 60–100 in comparison to that of the free enzyme in solution. Parallel ATR-IR-spectroscopic characterization of β-gal/TiO2 heteroaggregates reveals an adsorption-induced decrease of the β-sheet content and the formation of random structures leading to the deterioration of the active site.ConclusionsThe study underlines that robust qualitative and quantitative statements about enzyme adsorption and activity retention require the use of model systems such as anatase TiO2 nanoparticle agglomerates featuring well-defined structural and compositional properties.

Hydroxylation Induced Alignment of Metal Oxide Nanocubes.

Water vapor is ubiquitous under ambient conditions and may alter the shape of nanoparticles. How to utilize water adsorption for nanomaterial functionality and structure formation, however, is a yet unexplored field. Herein, we report the use of water vapor to induce the self-organization of MgO nanocubes into regularly staggered one-dimensional structures. This transformation evolves via an initial alignment of the MgO cubes, the formation of intermediate elongated Mg(OH)2 structures, and their reconversion into MgO cubes arranged in staggered structures. Ab initio DFT modelling identifies surface-energy changes associated with the cube surface hydration and hydroxylation to promote the uncommon staggered stacked assembly of the cubes. This first observation of metal oxide nanoparticle self-organization occurring outside a bulk solution may pave novel routes for inducing texture in ceramics and represents a great test-bed for new surface-science concepts.

Confined Etching within 2D and 3D Colloidal Crystals for Tunable Nanostructured Templates: Local Environment Matters

We report the isotropic etching of 2D and 3D polystyrene (PS) nanosphere hcp arrays using a benchtop O2 radio frequency plasma cleaner. Unexpectedly, this slow isotropic etching allows tuning of both particle diameter and shape. Due to a suppressed etching rate at the point of contact between the PS particles originating from their arrangement in 2D and 3D crystals, the spherical PS templates are converted into polyhedral structures with well-defined hexagonal cross sections in directions parallel and normal to the crystal c-axis. Additionally, we found that particles located at the edge (surface) of the hcp 2D (3D) crystals showed increased etch rates compared to those of the particles within the crystals. This indicates that 2D and 3D order affect how nanostructures chemically interact with their surroundings. This work also shows that the morphology of nanostructures periodically arranged in 2D and 3D supercrystals can be modified via gas-phase etching and programmed by the superlattice symmetry. To show the potential applications of this approach, we demonstrate the lithographic transfer of the PS template hexagonal cross section into Si substrates to generate Si nanowires with well-defined hexagonal cross sections using a combination of nanosphere lithography and metal-assisted chemical etching.

Investigation of Mass-Produced Substrates for Reproducible Surface-Enhanced Raman Scattering Measurements over Large Areas

Surface-enhanced Raman scattering (SERS) is a versatile spectroscopic technique that suffers from reproducibility issues and usually requires complex substrate fabrication processes. In this article, we report the use of a simple mass production technology based on Blu-ray disc manufacturing technology to prepare large area SERS substrates (∼40 mm2) with a high degree of homogeneity (±7% variation in Raman signal) and enhancement factor of ∼6 × 106. An industrial high throughput injection molding process was used to generate periodic microstructured polymer substrates coated with a thin Ag film. A short chemical etching step produces a highly dense layer of Ag nanoparticles at the polymer surface, which leads to a large and reproducible Raman signal. Finite difference time domain simulations and cathodoluminescence mapping experiments suggest that the sample microstructure is responsible for the generation of SERS active nanostructures around the microwells. Comparison with commercial SERS substrates demonstrates the validity of our method to prepare cost-efficient, reliable, and sensitive SERS substrates.

Potential controlled electrochemical conversion of AgCN and Cu(OH)2 nanofibers into metal nanoparticles, nanoprisms, nanofibers, and porous networks.

Nanowires are expected to provide considerable advances in the use of smaller and more efficient sensing, electronic, and photovoltaic devices. Good electrical connections of the nanowires within devices can, however, be problematic. We present here a new method that takes advantage of the available large-scale and reproducible wet-chemical syntheses of non-zero-valent anisotropic nanomaterials. The electrochemical reduction of preformed solid AgCN and Cu(OH)2 nanofibers (NFs) on surfaces allows one to form metallic nanostructures that are integrated in electrical junctions with excellent electrical contacts. Some fundamental aspects of the electrochemical reduction of AgCN NF are presented, including their redox potential and propagation of the metal boundary formed during the electrochemical reduction process. The clear connection between native (unreduced) AgCN NF and reduced Ag0 nanostructures is shown. The reduction potential, the nature of the supporting substrate (conductive vs insulating), and the size of the original fibers strongly influence the morphology and dimensions of the Ag0 nanostructures thus produced. A number of different Ag0 nanostructures are electrosynthesized, including nanoprisms, nanoparticles (NPs), and NFs, made from the aggregation of nanoprisms and NPs, and continuous fibers, whose width is tunable between 90 and 500 nm. We report the formation of excellent electrical contact via the electrochemical reduction of metal/Mz+ NF/metal junctions. This technique is simple, fast, and applicable to other materials such as Cu(OH)2 NF. It allows for the formation of electrically connected metallic networks with new interesting geometries, which could be applied to a form of electrochemical welding.

Microstructure and mechanical properties of high strength Al—Mg—Si—Cu profiles for safety parts

Aluminium extrudate used for safety parts in cars need to exhibit high yield strength and ductility, a combination that is not easily achieved. In this work, the mechanical properties and microstructure of profiles with a yield strength greater than 280MPa achieved by two different artificial ageing treatments were studied. Profiles from one of the heat treatments performed well in quasi-static compression testing while those from the other heat treatment clearly failed. The batch of profiles that failed showed higher uniform elongation in tensile testing but a lower reduction in area. However, the difference in bending angles in the three-point-bending test were not as pronounced. Microscopic investigation of polished sections and fracture surfaces revealed that failure is dominated by the fracture of intermetallic phases resulting in voids. The growth and coalescence of these voids is facilitated by another population of smaller voids within the matrix, presumably nucleating at secondary phases.

Three-Dimensional Electrochemical Axial Lithography on Si Micro- and Nanowire Arrays

A templated electrochemical technique for patterning macroscopic arrays of single-crystalline Si micro- and nanowires with feature dimensions down to 5 nm is reported. This technique, termed three-dimensional electrochemical axial lithography (3DEAL), allows the design and parallel fabrication of hybrid silicon nanowire arrays decorated with complex metal nano-ring architectures in a flexible and modular approach. While conventional templated approaches are based on the direct replication of a template, our method can be used to perform high-resolution lithography on pre-existing nanostructures. This is made possible by the synthesis of a porous template with tunable dimensions that guides the deposition of well-defined metallic shells around the Si wires. The synthesis of a variety of ring architectures composed of different metals (Au, Ag, Fe, and Ni) with controlled sequence, height, and position along the wire is demonstrated for both straight and kinked wires. We observe a strong enhancement of the Raman signal for arrays of Si nanowires decorated with multiple gold rings due to the plasmonic hot spots created in these tailored architectures. The uniformity of the fabrication method is evidenced by a homogeneous increase in the Raman signal throughout the macroscopic sample. This demonstrates the reliability of the method for engineering plasmonic fields in three dimensions within Si wire arrays.