Photodissociation dynamics of the 2-propyl radical, C3H7

The photodissociation of 2-propyl leading to propene+H was investigated with nanosecond time resolution. A supersonic beam of isolated 2-propyl radicals was produced by pyrolysis of 2-bromopopane. The kinetic energy release of the H-atom photofragment was monitored as a function of excitation wavelength by photofragment Doppler spectroscopy via the Lyman-alpha transition. The loss of hydrogen atoms after excitation proceeds in alpha position to the radical center with a rate constant of 5.8x10(7) s-1 at 254 nm. Approximately 20% of the excess energy is deposited as translation in the H-atom photofragment. In contrast 1-propyl does not lose H atoms to a significant extent. The experimental results are compared to simple Rice-Ramsperger-Kassel-Marcus calculations. The possible reaction pathways are examined in hybrid density functional theory calculations.     

Thermodynamic and neutron scattering study of hydrogen adsorption in two mesoporous ordered carbons

Two mesoporous ordered carbon materials (MOCs) have been synthesized from silica templates by using sucrose as the carbon precursor. The textural characterization using Ar, N2, and CO2 adsorption combined with neutron diffraction showed that the two samples exhibit a significant microporous volume close to 0.5 cm3/g and an ordered network of mesopores. For both MCM48 and SBA15 templated carbons, adsorption first proceeds with the filling of micropores and then by the filling of mesopores with an adsorption energy close to the enthalpy of vaporization of bulk hydrogen. The hydrogen isosteric heat of adsorption in the micropores (6-8 kJ/mol) is significantly larger than that on the graphite surface (approximately 4 kJ/mol) but still too small for a reasonable use of these MOCs as hydrogen adsorbents for storage at room temperature. The neutron scattering study showed that the structure at 10 K of the adsorbed deuterium phase is poorly organized; it exhibits short and medium range orders of about 13 angstroms in micropores and about 20 angstroms in mesopores, respectively. The average distance between adsorbed molecules decreases with coverage by about 10%. In the mesopores, the diffracted line is consistent with a pseudohexagonal packing.     

Adsorption of simple gases in MCM-41 materials: the role of surface roughness

This paper reports the development and testing of atomistic models of silica MCM-41 pores. Model A is a regular cylindrical pore having a constant section. Model B has a surface disorder that reproduces the morphological features of a pore obtained from an on-lattice simulation that mimics the synthesis process of MCM-41 materials. Both models are generated using a similar procedure, which consists of carving the pore out of an atomistic silica block. The differences between the two models are analyzed in terms of small angle neutron scattering spectra as well as adsorption isotherms and isosteric heat curves for Ar at 87 K and Xe at 195 K. As expected for capillary condensation in regular nanopores, the Ar and Xe adsorption/desorption cycles for model A exhibit a large hysteresis loop having a symmetrical shape, i.e., with parallel adsorption and desorption branches. The features of the adsorption isotherms for model B strongly depart from those observed for model A. Both the Ar and Xe adsorption branches for model B correspond to a quasicontinuous pore filling that involves coexistence within the pore of liquid bridges and gas nanobubbles. As in the case of model A, the Ar adsorption isotherm for model B exhibits a significant hysteresis loop; however, the shape of the loop is asymmetrical with a desorption branch much steeper than the adsorption branch. In contrast, the adsorption/desorption cycle for Xe in model B is quasicontinuous and quasireversible. Comparison with adsorption and neutron scattering experiments suggests that model B is too rough at the molecular scale but reproduces reasonably the surface disorder of real MCM-41 at larger length scales. In contrast, model A is smooth at small length scales in agreement with experiments but seems to be too ordered at larger length scales.     

Modeling cochlear dynamics: interrelation between cochlea mechanics and psychoacoustics

A model of the cochlea was used to bridge the gap between model approaches commonly used to investigate phenomena related to otoacoustic emissions and more filter-based model approaches often used in psychoacoustics. In the present study, a nonlinear and active one-dimensional transmission line model was developed that accounts for several aspects of physiological data with a single fixed parameter set. The model shows plausible excitation patterns and an input-output function similar to the linear-compressive-linear function as hypothesized in psychoacoustics. The model shows realistic results in a two-tone suppression paradigm and a plausible growth function of the 2f(1)-f(2) component of distortion product otoacoustic emissions. Finestructure was found in simulated stimulus-frequency otoacoustic emissions (SFOAE) with realistic levels and rapid phase rotation. A plausible "threshold in quiet" including finestructure and spontaneous otoacoustic emissions (SOAE) could be simulated. It is further shown that psychoacoustical data of modulation detection near threshold can be explained by the mechanical dynamics of the modeled healthy cochlea. It is discussed that such a model can be used to investigate the representation of acoustic signals in healthy and impaired cochleae at this early stage of the auditory pathway for both, physiological as well as psychoacoustical paradigms.     

Accelerating Oxygen‐Reduction Catalysts through Preventing Poisoning with Non‐Reactive Species by Using Hydrophobic Ionic Liquids

Developing cost‐effective electrocatalysts for the oxygen reduction reaction (ORR) is a prerequisite for broad market penetration of low‐temperature fuel cells. A major barrier stems from the poisoning of surface sites by nonreactive oxygenated species and the sluggish ORR kinetics on the Pt catalysts. Herein we report a facile approach to accelerating ORR kinetics by using a hydrophobic ionic liquid (IL), which protects Pt sites from surface oxidation, making the IL‐modified Pt intrinsically more active than its unmodified counterpart. The mass activity of the catalyst is increased by three times to 1.01 A mg^?1_Pt@0.9 V, representing a new record for pure Pt catalysts. The enhanced performance of the IL‐modified catalyst can be stabilized after 30 000 cycles. We anticipate these results will form the basis for an unprecedented perspective in the development of high‐performing electrocatalysts for fuel‐cell applications.     

Zwitterionic and anionic multinuclear pentacoordinate silicon(IV) complexes with bridging (R,R)-tartrato(4-) ligands and SiO5 skeletons: synthesis and reactivity in aqueous solution

Two nutrients in one molecule: A zwitterionic λ(5)Si,λ(5)Si'-disilicate (1) was synthesized and characterized. It contains ligands that exclusively derive from natural products ((R,R)-tartaric acid, choline). Hydrolysis of 1 yields 2, which shows a remarkable kinetic stability in water. Upon dissolution of 1 and 2 in water, the nutrients choline and orthosilicic acid are formed by hydrolysis.     

Interplay of low-energy phonons and magnetic excitations in the Kondo insulator YbB12

Peculiarities in the lattice dynamics of the Kondo insulator Y bB(12) have been studied by inelastic neutron scattering. Selected phonon modes were traced above and below the temperature region (T ~ 50 K) where the gap opens in the electron density of states. The intensities of some low-energy modes exhibit an anomalous temperature dependence for q vectors close to the Brillouin zone boundary, suggesting a renormalization of the phonon eigenvectors. This effect is thought to arise from a coupling with magnetic excitations of the same symmetry, which exist at nearby energies. It is argued that this magnetovibrational coupling may in turn play a role in the steep temperature crossover existing in Y bB(12) between the low-temperature (Kondo insulator) and high-temperature (incoherent spin-fluctuation) regimes, which is rapidly suppressed by lighter Zr substitution.     

The economics of a closed-loop supply chain with remanufacturing

This study deals with joint decisions on pricing and production lot-sizing in a closed-loop supply chain consisting of manufacturing and remanufacturing operations. This study emphasizes the economic analysis of this hybrid system with substitution between the new and the remanufactured versions of the same product. We develop analytical models under a newsvendor framework bearing the following questions in mind. Can a hybrid system operate cost-effectively? Can it outperform the manufacturing-only system? If yes, to what extent and under what conditions? If not, what are the key factors that cause underperformance? This study formulates a multi-variable optimization problem and performs mathematical and numerical analysis. Results show that the hybrid system does not outperform the manufacturing-only system under a generic setting, but achieves better performance under conditions with a higher degree of substitution and/or a lower remanufacturing cost. In this scenario, participating in remanufacturing is not only an issue of environmental responsibility, but a profit-boosting option.     

Effect of the primary particle morphology on the micromechanical properties of nanostructured alumina agglomerates

Depending on the application of nanoparticles, certain characteristics of the product quality such as size, morphology, abrasion resistance, specific surface, dispersibility and tendency to agglomeration are important. These characteristics are a function of the physicochemical properties, i.e. the micromechanical properties of the nanostructured material. The micromechanical properties of these nanostructured agglomerates such as the maximum indentation force, the plastic and elastic deformation energy and the strength give information on the product properties, e.g. the efficiency of a dispersion process of the agglomerates, and can be measured by nanoindentation. In this study a Berkovich indenter tip was used for the characterisation of model aggregates out of sol–gel produced silica and precipitated alumina agglomerates with different primary particle morphologies (dimension of 15–40 nm). In general, the effect of the primary particle morphology and the presence or absence of solid bonds can be characterised by the measurement of the micromechanical properties via nanoindentation. The micromechanical behaviour of aggregates containing solid bonds is strongly affected by the elastic–plastic deformation behaviour of the solid bonds and the breakage of solid bonds. Moreover, varying the primary particle morphology for similar particle material and approximately isotropic agglomerate behaviour the particle–particle interactions within the agglomerates can be described by the elementar breaking stress according to the formula of Rumpf.     

Gas storage valuation applying numerically constructed recombining trees

The liberalization of European natural gas markets forces market participants to base their decisions on market prices. For owners and operators of natural gas storage facilities it is therefore necessary to take market prices into account for their decisions. In this framework this paper provides a new approach for the valuation of natural gas storage facilities. Using stochastic dynamic programming on multinomial recombining trees, the optimal storage strategy and value are determined. For this we (i) estimate the deterministic and random impacts on natural gas prices, (ii) simulate gas prices considering the results of the first step, (iii) construct numerically the recombining tree using the simulation results, (iv) determine the optimal storage strategy and value. Besides the determination of the optimal storage value and operation schedule the value quantiles are calculated. Via the quantiles relevant risk measures like value at risk and conditional value at risk are determined.