Lionel C. Gontard

Resolving the Structure of Active Sites on Platinum Catalytic Nanoparticles

Accurate understanding of the structure of active sites is fundamentally important in predicting catalytic properties of heterogeneous nanocatalysts. We present an accurate determination of both experimental and theoretical atomic structures of surface monatomic steps on industrial platinum nanoparticles. This comparison reveals that the edges of nanoparticles can significantly alter the atomic positions of monatomic steps in their proximity, which can lead to substantial deviations in the catalytic properties compared with the extended surfaces.

A simple algorithm for measuring particle size distributions on an uneven background from TEM images.

Nanoparticles have a wide range of applications in science and technology. Their sizes are often measured using transmission electron microscopy (TEM) or X-ray diffraction. Here, we describe a simple computer algorithm for measuring particle size distributions from TEM images in the presence of an uneven background. The approach is based on adaptive thresholding, making use of local threshold values that change with spatial coordinate. The algorithm allows particles to be detected and characterized with greater accuracy than using more conventional methods, in which a global threshold is used. Its application to images of heterogeneous catalysts is presented.

Dual Enlargement of Gold Nanoparticles: From Mechanism to Scanometric Detection of Pathogenic Bacteria

A mechanism of dual enlargement of gold nanoparticles (AuNPs) comprising two steps is described. In the first step, the AuNPs are enlarged by depositing Au atoms on their crystalline faces. In this process, the particles are not only enlarged but they are also observed to multiply: new Au nuclei are formed by the budding and division of the enlarged particles. In the second step, a silver enhancement is subsequently performed by the deposition of silver atoms on the enlarged and newly formed AuNPs to generate bimetallic Au@Ag core-shell structures. The dual nanocatalysis greatly enhances the electron density of the nanostructures, leading to a stronger intensity for colorimetric discrimination as well as better sensitivity for quantitative measurement. Based on this, a simple scanometric assay for the on-slide detection of the food-born pathogen Campylobacter jejuni is developed. After capturing the target bacteria, gold-tagged immunoprobes are added to create a signal on a solid substrate. The signal is then amplified by the dual enlargement process, resulting in a strong color intensity that can easily be recognized by the unaided eye, or measured by an inexpensive flatbed scanner. In this paper, dual nanocatalysis is reported for the first time. It provides a valuable mechanistic insight into the development of a simple and cost-effective detection format.

Magnetic and microscopic characterization of magnetite nanoparticles adhered to clay surfaces

Abstract When suspended in solution, clay platelets coated with nanometer-scale magnetite particles behave as magnetorheologic fluids that are important to a variety of industrial applications. Such dual-phase assemblages are also similar to natural aggregates that record the direction and intensity of the Earth’s magnetic field in lake and marine depositional environments. This study characterizes the mineralogical structure and magnetic behavior of montmorillonite platelets coated with aggregates of nanometerscale magnetite crystals. The distribution of magnetite crystal sizes in three different clay-magnetite assemblages was directly measured using conventional transmission electron microscopy and agrees within error with estimates derived from magnetic hysteresis measurements. Magnetic hysteresis and low field susceptibility measurements combined with electron holography experiments indicate that all three samples behave superparamagnetically at room temperature, and show increasing levels of single domain behavior as the samples are cooled to liquid nitrogen temperatures. At such low temperatures, magnetostatic interactions are observed to partially stabilize otherwise superparamagnetic grains in flux closure structures.

Three-dimensional shapes and structures of lamellar-twinned fcc nanoparticles using ADF STEM

Small particles with face-centred cubic structures can have non-single-crystallographic shapes. Here, an approach based on annular dark-field scanning transmission electron microscopy (STEM) is used to obtain information about the crystal sub-units that make up supported and unsupported twinned Pt, Pt alloy and Au nanoparticles. The three-dimensional shapes of two types of lamellar-twinned particles (LTPs) of Pt are obtained using high-angle annular dark-field STEM. Possible growth mechanisms of the LTPs and origins for the contrast features in the recorded images are discussed.

High-resolution TEM and the application of direct and indirect aberration correction

Aberration correction leads to a substantial improvement in the directly interpretable resolution of transmission electron microscopes. Correction of the aberrations has been achieved electron-optically through a hexapole-based corrector and also indirectly by computational analysis of a focal or tilt series of images. These direct and indirect methods are complementary, and a combination of the two offers further advantages. Materials characterization has benefitted from the reduced delocalization and higher resolution in the corrected images. It is now possible, for example, to locate atomic columns at surfaces to higher accuracy and reliability. This article describes the JEM-2200FS in Oxford, which is equipped with correctors for both the image-forming and probe-forming lenses. Examples of the use of this instrument in the characterization of nanocrystalline catalysts are given together with initial results combining direct and indirect methods. The double corrector configuration enables direct imaging of the corrected probe, and a potential confocal imaging mode is described. Finally, modifications to a second generation instrument are outlined.

Photogrammetry of the three-dimensional shape and texture of a nanoscale particle using scanning electron microscopy and free software

We apply photogrammetry in a scanning electron microscope (SEM) to study the three-dimensional shape and surface texture of a nanoscale LiTi2(PO4)3 particle. We highlight the fact that the technique can be applied non-invasively in any SEM using free software (freeware) and does not require special sample preparation. Three-dimensional information is obtained in the form of a surface mesh, with the texture of the sample stored as a separate two-dimensional image (referred to as a UV Map). The mesh can be used to measure parameters such as surface area, volume, moment of inertia and center of mass, while the UV map can be used to study the surface texture using conventional image processing techniques. We also illustrate the use of 3D printing to visualize the reconstructed model.

Three-dimensional fabrication and characterisation of core-shell nano-columns using electron beam patterning of Ge-doped SiO2

A focused electron beam in a scanning transmission electron microscope (STEM) is used to create arrays of core-shell structures in a specimen of amorphous SiO2 doped with Ge. The same electron microscope is then used to measure the changes that occurred in the specimen in three dimensions using electron tomography. The results show that transformations in insulators that have been subjected to intense irradiation using charged particles can be studied directly in three dimensions. The fabricated structures include core-shell nano-columns, sputtered regions, voids, and clusters.

Tomographic Heating Holder for In Situ TEM: Study of Pt/C and PtPd/Al2O3 Catalysts as a Function of Temperature

A tomographic heating holder for transmission electron microscopy that can be used to study supported catalysts at temperatures of up to ~1,500°C is described. The specimen is placed in direct thermal contact with a tungsten filament that is oriented perpendicular to the axis of the holder without using a support film, allowing tomographic image acquisition at high specimen tilt angles with minimum optical shadowing. We use the holder to illustrate the evolution of the active phases of Pt nanoparticles on carbon black and PtPd nanoparticles on γ-alumina with temperature. Particle size distributions and changes in active surface area are quantified from tilt series of images acquired after subjecting the specimens to increasing temperatures. The porosity of the alumina support and the sintering mechanisms of the catalysts are shown to depend on distance from the heating filament.

Direct observation of doping incorporation pathways in self-catalytic GaMnAs nanowires

Doping mechanisms of Mn in GaAs nanowires (NWs) that have been grown self-catalytically at 600 degrees C by molecular beam epitaxy (MBE) are investigated using advanced electron microscopy techniques and atom probe tomography, Mn is found to be incorporated primarily in the form of non-magnetic tetragonal Ga0.82Mn0.18 nanocrystals in Ga catalyst droplets at the ends of the NWs, while trace amounts of Mn (22 +/- 4 at. ppm) are also distributed randomly in the NW bodies without forming clusters or precipitates. The nanocrystals are likely to form after switching off the reaction in the MBE chamber, since they are partially embedded in neck regions of the NWs. The Ga0.82Mn0.18 nanocrystals and the low Mn concentration in the NW bodies are insufficient to induce a ferromagnetic phase transition, suggesting that it is difficult to have high Mn contents in GaAs even in 1-D NW growth via the vapor-liquid-solid process.