Inverse CeO2/CuO catalyst as an alternative to classical direct configurations for preferential oxidation of CO in hydrogen-rich stream.

A novel inverse CeO(2)/CuO catalyst for preferential oxidation of CO in H(2)-rich stream (CO-PROX) has been developed on the basis of a hypothesis extracted from previous work of the group (JACS 2007, 129, 12064). Possible separation of the two competing oxidation reactions involved in the process (of CO and H(2), respectively) is the key to modulation of overall CO-PROX activity and is based on involvement of different sites as most active ones for each of the two reactions. Achievement of large size CuO particles and adequate CeO(2)-CuO interfacial configurations in the inverse catalyst apparently allows appreciable enhancement of the catalytic properties of this kind of system for CO-PROX, constituting an interesting alternative to classic direct configurations so far explored for this process. Reasons for such behavior are analyzed on the basis of operando-XRD, -XAFS, and -DRIFTS studies.

Quantitative earthquake-like statistical properties of the flow of soft materials below yield stress.

The flow behavior of soft materials below the yield stress can be rich and is not fully understood. Here, we report shear-stress-induced reorganization of three-dimensional solid-like soft materials formed by closely packed nematic domains of surfactant micelles and a repulsive Wigner glass formed by anisotropic clay nano-discs having ionic interactions. The creep response of both the systems below the yield stress results in angular velocity fluctuations of the shearing plate showing large temporal burst-like events that resemble seismic foreshocks-aftershocks data measuring the ground motion during earthquake avalanches. We find that the statistical properties of the quake events inside such a burst map on to the scaling relations for magnitude and frequency distribution of earthquakes, given by Gutenberg-Richter and Omori laws, and follow a power-law distribution of the inter-occurrence waiting time. In situ polarized optical microscopy reveals that during these events the system self-organizes to a much stronger solid-like state.

Experimental signatures of a nonequilibrium phase transition near the crossover point of a Langmuir monolayer.

We investigate the response of the two-dimensional (2D) continuous non-particulate film of surfactant sorbitan tristearate confined at the air-water interface under oscillatory shear deformation. The time dependence of various rheological parameters show critical-like behavior at a value of strain amplitude close to the crossover point of elastic ([Formula: see text]) and viscous ([Formula: see text]) shear moduli. Imposing oscillatory shear of different strain amplitudes ([Formula: see text]) above and below the crossover strain amplitude ([Formula: see text]) over a large number of cycles, we quantify the temporal dependence of interfacial viscous modulus, phase angle ([Formula: see text]) as well as higher harmonic components of stress. The number of shear cycles ([Formula: see text]) required for these quantities to reach the steady state value diverges near [Formula: see text]. The steady state values of the third harmonic ([Formula: see text]) show order parameter like behavior indicating the importance of higher order harmonics near the nonequilibrium transition. We further show that the energy dissipation per cycle per unit volume has a marked change near [Formula: see text], consistent with continuum level nonequilibrium shear-transformation-zone model of amorphous viscoplasticity.

Interactions of O(2) with Pd nanoparticles on alpha-Al(2)O(3)(0001) at low and high O(2) pressures.

The interaction of O(2) with small Pd particles (2-10 nm) supported on an alpha-Al(2)O(3)(0001) single crystal under both ultrahigh vacuum (UHV) and high-pressure conditions has been studied by temperature-programmed desorption (TPD), temperature-programmed low-energy ion scattering (TP-LEIS), and X-ray photoelectron spectroscopy (XPS). A low O(2) exposure (30 L) at 500 K leads to surface oxygen adatoms on the Pd nanoparticles, which desorb in TPD as O(2) in a peak at approximately 880 K. Surface O adatoms on the smallest Pd particles move to subsurface sites starting at 400 K, and they almost all move subsurface by approximately 750 K, desorbing mainly at considerably higher temperature. The dominant oxygen species above 700 K is subsurface, implying that it is more stable than oxygen adatoms on Pd. Exposures of the Pd nanoparticles to 25 Torr O(2) at 373-473 K readily convert the Pd to a species whose Pd XPS peak shifts by the same amount as the binding energy difference between bulk Pd and bulk PdO. We attribute this to PdO nanoparticles (or a thin film of PdO on or under the Pd for the larger particles). The decomposition of the PdO on these nanoparticles to Pd in an equilibrium O(2) pressure of 10-7 Torr does not occur until approximately 750 K, or approximately 200 K higher than the equilibrium decomposition of bulk PdO. This is attributed to the higher energy of Pd nanoparticles compared to bulk Pd and, for the larger particles, to the adhesion energy of the PdO film to the Pd, both of which stabilize the PdO on these Pd nanoparticles relative to bulk PdO. This PdO-like film on the larger particles may be similar to the ordered oxide thin film previously reported to form on Pd(111) but may also reside at the alpha-Al(2)O(3) interface and be partially stabilized by adhesion to this interface.

IAEA/WHO TLD postal dose audit service and high precision measurements for radiotherapy level dosimetry. International Atomic Energy Agency/World Health Organization.

Since 1969 the International Atomic Energy Agency (IAEA), together with the World Health Organization (WHO), has performed postal TLD audits to verify calibration of radiotherapy beams in developing countries. The TLD programme also monitors activities of Secondary Standard Dosimetry Laboratories (SSDLs). The programme has checked approximately 4000 clinical beams in over 1100 hospitals. and in many instances significant errors have been detected in the beam calibration. Subsequent follow-up actions help to resolve the discrepancies, thus preventing further mistreatment of patients. The audits for SSDLs check the implementation of the dosimetry protocol in order to assure proper dissemination of dosimetry standards to the end-users. The TLD audit results for SSDLs show good consistency in the basic dosimetry worldwide. New TLD procedures and equipment have recently been introduced by the IAEA that include a modified TLD calibration methodology and computerised tools for automation of dose calculation from TLD readings.

Biosorption of heavy metals by red algae (Palmaria palmata).

The biosorption of heavy metals from aqueous solutions was investigated, using a cheap and abundant dry biomass of red algae P. palmata. The Freundlich, Langmuir and Brunauer Emmer and Teller (BET) models were used to describe the uptake of lead (pb2+), copper (Cu2+), nickel (Ni2+), cadmium (Cd 2+) and zinc (Zn2+) on P. palmata. The good fits of the Langmuir and BET models to the experimental data reflected that the sorption on P. palmata was a multi-layer sorption, in which a Langmuir equation could be applied to each layer. The highest maximum sorption capacity q(max), derived from the Langmuir model was 15.17 mg g(-1) for lead and 6.65 mg g(-1) for copper (dry weight metal/dry weight biosorbent) at a pH of 5.5-6. The affinity of metals for P. palmata was found to decrease in the order: Pb2+ > Cd2+ > Cu2+ > Ni2+. The factors influencing copper and lead uptake were found to be contact time, pH, initial concentration and temperature. Biosorption of copper and lead was a rapid process, with 70% and 100% of the respective uptakes occurring within the first 10 minutes.