Scanning Transmission Electron Microscopy

In this paper we describe the production and investigation of two supported gold catalyst systems prepared by magnetron sputtering: Au on WO 3 and Au on activated carbon. The magnetron sputtering technique entails using an argon plasma to sputter a high purity gold target producing a flux of gold atoms which are deposited onto a constantly tumbling support material. This technique offers a number of advantages over conventional chemical preparation methods. One advantage is the ability to create gold nanoparticles (diameters <3 nm) on unusual support materials, such as WO 3 and carbon, which are generally not accessible using the ubiquitous deposition-precipitation technique. We present data demonstrating the formation of catalytic gold nanoparticles with average diameters of 1.7 nm (Au/C) and 2.1 nm (Au/WO 3 ), as well as a substantial number of single atom species on the Au/C sample. Prototypical carbon monoxide oxidation (Au/WO 3 ) and glycerol oxidation (Au/C) reactions were performed in order to gauge the activity of these catalysts. The WO 3 supported catalyst exhibits substantial catalytic activity from room temperature to 135 8C (0.0018-0.082 mol CO/mol Au s) with an activation energy near 23 kJ/mol. The activity of the Au/C catalyst was compared to a Au/C catalyst prepared from a poly(vinyl alcohol) (PVA) sol. The smaller catalysts prepared by sputtering are more active than the large gold particles prepared using the PVA sol, however the larger gold nanoparticles are substantially more selective towards the production of intermediate products from the oxidation of glycerol. Published by Elsevier B.V.

In soils, mycorrhiza (microscopic fungal hypha) living in symbiosis with plant roots are the biological interface by which plants obtain, from rocks and organic matter, the nutrients necessary for their growth and maintenance. Despite their central role in soils, the mechanism and kinetics of mineral alteration by mycorrhiza are poorly constrained quantitatively. Here, we report in situ quantification of weathering rates from a mineral substrate, (0 0 1) basal plane of biotite, by a surface-bound hypha of Paxillus involutus, grown in association with the root system of a Scots pine, Pinus sylvestris. Four thin-sections were extracted by focused ion beam (FIB) milling along a single hypha grown over the biotite surface. Depth-profile of Si, O, K, Mg, Fe and Al concentrations were performed at the hypha-biotite interface by scanning transmission electron microscopyenergy dispersive X-ray spectroscopy (STEM-EDX). Large removals of K (50-65%), Mg (55-75%), Fe (80-85%) and Al (75-85%) were observed in the topmost 40 nm of biotite underneath the hypha while Si and O are preserved throughout the depth-profile. A quantitative model of alteration at the hypha-scale was developed based on solid-state diffusion fluxes of elements into the hypha and the break-down/mineralogical re-arrangement of biotite. A strong acidification was also observed with hypha bound to the biotite surface reaching pH < 4.6. When consistently compared with the abiotic biotite dissolution, we conclude that the surface-bound mycorrhiza accelerate the biotite alteration kinetics between pH 3.5 and 5.8 to $0.04 lmol biotite m À2 h À1 . Our current work reaffirms that fungal mineral alteration is a process that combines our previously documented bio-mechanical forcing with the lm-scale acidification mediated by surface-bound hypha and a subsequent chemical element removal due to the fungal action. As such, our study presents a first kinetic framework for mycorrhizal alteration at the hypha-scale under close-to-natural experimental conditions.

Microwave heating was applied to synthesize copper colloidal nanoparticles by a polyol method that exploits the chelating and reducing power of a polidentate alcohol (diethylenglycol). The synthesis was carried out in the presence of eco-friendly additives such as ascorbic acid (reducing agent) and polyvinylpirrolidone (chelating polymer) to improve the reduction kinetics and sols stability. Prepared suspensions, obtained with very high reaction yield, were stable for months in spite of the high metal concentration. In order to optimize suspensions, synthesis parameters were modified and the effects on particle size, optical properties, and reaction yield were investigated. XRD analysis, scanning transmission electron microscopy (STEM), and DLS measurements confirmed that prepared sols consist of crystalline metallic copper with a diameter ranging from 45 to 130 nm. Surface plasmon resonance (SPR) of Cu nanoparticles was monitored by UV-Vis spectroscopy and showed both a red shift and a band weakening due to nanoparticle diameter increase. Microwave use provides rapid, uniform heating of reagents and solvent, while accelerating the reduction of metal precursors and the nucleation of metal clusters, resulting in monodispersed nanostructures. The proposed microwave-assisted synthesis, also usable in largescale continuous production, makes process intensification possible.

An upper temperature limit of 450 degrees C has been established for growth of heteroepitaxial Si1-x-yGexCy solid solutions with substitutional C on Si(100) by combined ion and molecular beam deposition (CIMD). At 450 degrees C infrared absorption spectroscopy shows that C is on substitutional sites and no SiC precipitates are detected, whereas at 560 degrees C the substitutional C signal is much smaller but SiC precipitates are still not detected. High resolution transmission electron microscopy shows that Si1-x-yGexCy films deposited at 560 degrees C exhibit Ge deficient, coherent, secondary phase clusters in the cubic diamond matrix, which are not seen in films deposited at 450 degrees C. These observations suggest that the clusters are C-rich, Ge-deficient precursors to SiC, with a lattice which is distorted but free of extended defects. Ion channeling results indicate that the Si1-x-yGexCy films might have a distribution of different bond lengths. (C) 1996

The present work evaluates the influence of the bulk carbon content (0. l, 0.006, and 0.005 wt pct) and tempering temperature (823, 853, and 913 K) on stability, chemical composition, and size of carbide particles in 540 ks tempered states of 2.6Cr-0.7Mo-0.3V steel. The scanning transmission electron microscopy/energy-dispersive X-ray spectroscopy (STEM/EDXS) and electron diffraction methods were used to analyze the carbide particles. A characteristic energydispersive X-ray (EDX) spectrum can be attributed to each of the identified carbides. The MC carbide is stable in all experimental states. The phase stability of Fe-Cr-rich carbides increased in the order e, Fe3C --> M3C --> M7C3, with tempering temperature increasing. In steels with higher carbon content tempered at low temperature, M_~3C~, carbide was also noted. The Mo2C and M6C carbides were not observed. It was shown that the decrease of the bulk carbon content has the same influence on the carbide phases stability as the increase of the bulk vanadium content at the unchanged Cr, Mo, C bulk contents and tempering temperature. Similarly, the decrease of tempering temperature has the same influence on the carbide phases stability as the decrease of the bulk Cr content at the unchanged V, Mo, and C bulk contents.