Highly dispersed gold on activated carbon fibers for low temperature CO oxidation

Gold nanoparticles of 2–5 nm supported on woven fabrics of activated carbon fibers (ACF) were effective during CO oxidation at room temperature. To obtain a high metal dispersion, Au was deposited on ACF from aqueous solution of ethylenediamine complex [Au(en)2]Cl3 via ion exchange with protons of surface functional groups. The temperature-programmed decomposition method showed the presence of two main types of functional groups on the ACF surface: the first type was associated with carboxylic groups easily decomposing to CO2 and the second one corresponded to more stable phenolic groups decomposing to CO. The concentration and the nature of surface functional groups was controlled using HNO3 pretreatment followed by either calcination in He (300–1273 K) or by iron oxide deposition. The phenolic groups are able to attach Au3+ ions, leading to the formation of small Au nanoparticles (9 nm) Au agglomerates after reduction by H2. These catalysts demonstrated lower activity as compared to the ones containing mostly small Au nanoparticles. Complete removal of surface functional groups rendered an inert support that would not interact with the Au precursor. The oxidation state of gold in the Au/ACF catalysts was controlled by X-ray photoelectron spectroscopy before and after the reduction in H2. The high-temperature reduction in H2 (673–773 K) was necessary to activate the catalyst, indicating that metallic gold nanoparticles are active during catalytic CO oxidation

Speciation and reactivity of uranium products formed during in situ bioremediation in a shallow alluvial aquifer

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxiation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans

Transmission electron microscopy of Ca oxide nano- and microcrystals in alpha-tricalcium phosphate prepared by sintering of beta-tricalcium phosphate

Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to study the porous and non-porous alpha-tricalcium phosphate (alpha-Ca-3(PO4)(2), alpha-TCP) prepared through a sintering procedure at 1200-1400 degrees C of beta-tricalcium phosphate (beta-Ca-3(PO4)(2), beta-TCP). The interpretation of experimental and calculated X-ray and electron diffraction patterns showed that the final product at 1400 degrees C was primarily alpha-TCP but roughly 3.0-8.0 wt.% of the starting beta-TCP phase and up to 8.0 wt.% of CaO were in the final product. TEM images and electron diffraction patterns showed that the CaO phase - formed by decomposition of TCP - exists as micron-sized areas of various oriented nanocrystals embedded into the bulk alpha-TCP material and also as self-standing spherulite particles of a few microns in size. Surprisingly, formation of CaO from TCP decomposition occurred at temperatures below those predicted from the phase diagram of the CaO-P2O5 system. (C) 2009 Elsevier Ltd. All rights reserved

Structure of precipitates and orientation relationships in Al, Ge, Mo-doped higher manganese silicide crystals

The structure of Al, Ge, Mo-doped Higher Manganese Silicide (HMS) crystals with the general formulas Mn(Si0.99Ge0.01)(1.75), Mn(Si0.995Ge0.005)(1.75) and (Mn0.98Mo0.02)[(Si0.98Ge0.02)(1.75)](0.99)Al-0.01 was investigated by scanning and transmission electron microscopy, electron diffraction and X-ray energy dispersive spectrometry in a wide scale range from a few mm to several angstrom. Several secondary phases were identified in the Mn4Si7 matrix: Ge1-xSix (0.1 < x < 0.9) solid solution precipitates with Ge concentration ranging from 5 at. % up to 93 at.%, MoSi2 platelets, MnSi and Mn5Si3 precipitates. Their morphology, structure and crystallographic relationships with the HMS matrix were determined. Mostly local strains in the matrix and precipitates due to lattice misfits at interfaces derived from crystallographic relationships were found two orders of magnitude higher than deformation induced by thermal expansion mismatch. Only a few exceptions of specific relationships were found when the lattice misfit and thermal mismatch have close values. The largest misfit of about 22% was observed between MnSi and Mn4Si7 what led to big and numerous cracks in crystals. Therefore, doping can improve the material performance (1) by preventing the formation of MnSi precipitates with metallic properties and (2) by reduction of cracking and crack propagation because of larger MnSi/Mn4Si (7) lattice misfit compared to Ge1-xSix/Mn4Si7 or MoSi2/Mn4Si7 misfits

Mechanism of formation of silver nanoparticles in MAG-DMAEMA copolymer aqueous solutions

Dispersed Ag nanoparticles were prepared in aqueous solutions in the presence of pure poly[2-(dimethylamino)ethyl methacrylate] (poly-DMAEMA), poly[2-deoxy-2-methacrylamido-d-glucose] (poly-MAG), and their copolymers of poly[MAG–DMAEMA] with different mole fractions. Polymers contributed to the silver reduction, formation of nanoparticles, and stabilization of suspensions. No agglomerations of nanoparticles are formed. For each sample, more than one thousand silver particles were measured by transmission and scanning transmission electron microscopy to determine their number vs diameter and volume versus diameter distributions. The samples with the smallest nanoparticle mode diameter of 2.3 nm were formed in DMAEMA homopolymer suspension, while the mode diameter increased up to 13.3 nm in copolymers depending on the mole fraction of DMAEMA. A model of Ag nanoparticles’ growth taking into account the structure of the copolymers and the amount of reducing centers per monomer is proposed. The volume fraction of large Ag particles (>15–20 nm) in the tail of distributions was determined to estimate the part of less efficient nanoparticles assuming that only surface atoms are active. The largest volume occupied by big particles is measured in the solution with pure poly-MAG. Figures of merit, as the ratio of particle area to total volume of particles, were compared for five systems of Ag NPs/polymer. They can be understood from an economical point of view as the total silver investment compared to efficiency. © 2015, Springer Science+Business Media Dordrecht

Structure, Oxygen Content and Electric Properties of Titanium Nitride Electrodes in TiN_x/La:HfO₂/TiN_x Stacks Grown by PEALD on SiO₂/Si

This work reports experimental results of the quantitative determination of oxygen and band gap measurement in the TiNx electrodes in planar TiNx top/La:HfO2/TiNx bottom MIM stacks obtained by plasma enhanced atomic layer deposition on SiO2. Methodological aspects of extracting structural and chemical information from (scanning) transmission electron microscopy imaging (bright field and high angular annular dark field), energy dispersive X-ray spectrometry and electron energy loss spectroscopy are thoroughly considered. The study shows that the oxygen concentration is higher in the TiNxOy bottom electrode (about 14.2 ± 0.1 at. %) compared to the TiNxOy top electrode (about 11.4 ± 0.5 at. %). The following average stoichiometric formulas are TiN0.52O0.20 top and TiN0.54O0.26 bottom for top and bottom electrodes, respectively. The amount of oxygen incorporated into TiNx during PEALD because of oxygen impurities in the plasma is minor compared to that because of diffusion from SiO2 and HfO2. This asymmetry, together with results on a sample grown on a Si substrate, shows that incorporating oxygen impurity from the plasma itself is a minor part compared to diffusion from the SiO2 substrate and HfO2 dielectric during the PEALD growth. We observe the presence of TiO2 at the interface between the Hf oxide layer and the Ti nitride electrodes as well as at the SiO2 interface. EELS analysis led to a band gap ranging from 2.2 to 2.5 eV for the bottom TiNxOy and 1.7–2.2 eV for the top TiNxOy, which is in fair agreement with results obtained on the top TiNx electrode (1.6 ± 01 eV) using optical absorption spectra. Measurement of sheet resistance, resistivity and temperature coefficient of resistance by a four-point probe on the top TiNxOy electrode from 20 to 100 °C corresponds to the typical values for semiconductors