Structure and dynamics of the fast lithium ion conductor "Li7La3Zr2O12"

The solid lithium-ion electrolyte "Li(7)La(3)Zr(2)O(12)" (LLZO) with a garnet-type structure has been prepared in the cubic and tetragonal modification following conventional ceramic syntheses routes. Without aluminium doping tetragonal LLZO was obtained, which shows a two orders of magnitude lower room temperature conductivity than the cubic modification. Small concentrations of Al in the order of 1 wt% were sufficient to stabilize the cubic phase, which is known as a fast lithium-ion conductor. The structure and ion dynamics of Al-doped cubic LLZO were studied by impedance spectroscopy, dc conductivity measurements, (6)Li and (7)Li NMR, XRD, neutron powder diffraction, and TEM precession electron diffraction. From the results we conclude that aluminium is incorporated in the garnet lattice on the tetrahedral 24d Li site, thus stabilizing the cubic LLZO modification. Simulations based on diffraction data show that even at the low temperature of 4 K the Li ions are blurred over various crystallographic sites. This strong Li ion disorder in cubic Al-stabilized LLZO contributes to the high conductivity observed. The Li jump rates and the activation energy probed by NMR are in very good agreement with the transport parameters obtained from electrical conductivity measurements. The activation energy E(a) characterizing long-range ion transport in the Al-stabilized cubic LLZO amounts to 0.34 eV. Total electric conductivities determined by ac impedance and a four point dc technique also agree very well and range from 1 × 10(-4) Scm(-1) to 4 × 10(-4) Scm(-1) depending on the Al content of the samples. The room temperature conductivity of Al-free tetragonal LLZO is about two orders of magnitude lower (2 × 10(-6) Scm(-1), E(a) = 0.49 eV activation energy). The electronic partial conductivity of cubic LLZO was measured using the Hebb-Wagner polarization technique. The electronic transference number t(e-) is of the order of 10(-7). Thus, cubic LLZO is an almost exclusive lithium ion conductor at ambient temperature.     

Peroxy radical isomerization in the oxidation of isoprene

We report experimental evidence for the formation of C(5)-hydroperoxyaldehydes (HPALDs) from 1,6-H-shift isomerizations in peroxy radicals formed from the hydroxyl radical (OH) oxidation of 2-methyl-1,3-butadiene (isoprene). At 295 K, the isomerization rate of isoprene peroxy radicals (ISO2?) relative to the rate of reaction of ISO2? + HO2 is k(isom)(295)/(k(ISO2?+HO2)(295)) = (1.2 ± 0.6) x 10(8) mol cm(-3), or k(isom)(295) ? 0.002 s(-1). The temperature dependence of this rate was determined through experiments conducted at 295, 310 and 318 K and is well described by k(isom)(T)/(k(ISO2?+HO2)(T)) = 2.0 x 10(21) exp(-9000/T) mol cm(-3). The overall uncertainty in the isomerization rate (relative to k(ISO2?+HO2)) is estimated to be 50%. Peroxy radicals from the oxidation of the fully deuterated isoprene analog isomerize at a rate ～15 times slower than non-deuterated isoprene. The fraction of isoprene peroxy radicals reacting by 1,6-H-shift isomerization is estimated to be 8-11% globally, with values up to 20% in tropical regions.     

Acoustofluidics 1: Governing equations in microfluidics

In Part 1 of the thematic tutorial series "Acoustofluidics--exploiting ultrasonic standing waves forces and acoustic streaming in microfluidic systems for cell and particle manipulation", we establish the governing equations in microfluidics. Examples of basic flow solutions are presented, and equivalent circuit modeling for determining flow rates in microfluidic networks is introduced.     

A Theory of <Emphasis Type="Italic">L</Emphasis><Superscript>1</Superscript>-Dissipative Solvers for Scalar Conservation Laws with Discontinuous Flux

We propose a general framework for the study of L ¹ contractive semigroups of solutions to conservation laws with discontinuous flux:

Electronic structure and electron dynamics at the GaSb(0 0 1) surface studied by femtosecond pump-and-probe pulsed laser photoemission spectroscopy

Transiently excited electron states at the GaSb(0 0 1) surface have been studied by means of time- and angle-resolved photoemission spectroscopy based on a femtosecond laser system. A normally unpopulated surface electron state has been found at ∼250 meV above the valence band maximum with a strong confinement at the center of the surface Brillouin zone. The lifetime of transiently excited carriers at the intergap surface states has been found to be ∼11 ps, associated with rapid carrier diffusion.     

Exact results for the persistent current in an aharonov-bohm ring with a quantum impurity

We consider the problem of a persistent current in a one-dimensional mesoscopic ring with the electrons coupled by a spin exchange to a magnetic impurity. We show that this problem can be mapped onto an integrable model with a quadratic dispersion (with the latter property allowing for an unambiguous definition of the persistent current). We have solved the model exactly by a Bethe ansatz and found that the current is insensitive to the presence of the impurity. We conjecture that this result holds for any integrable quantum impurity model with an electronic dispersionε(k) that is an even function ofk.     

Unconditionally Stable Methods for Hamilton–Jacobi Equations

We present new numerical methods for constructing approximate solutions to the Cauchy problem for Hamilton–Jacobi equations of the form u_t+H(D_xu)=0. The methods are based on dimensional splitting and front tracking for solving the associated (non-strictly hyperbolic) system of conservation laws p_t+D_xH(p)=0, where p=D_xu. In particular, our methods depend heavily on a front tracking method for one-dimensional scalar conservation laws with discontinuous coefficients. The proposed methods are unconditionally stable in the sense that the time step is not limited by the space discretization and they can be viewed as “large-time-step” Godunov-type (or front tracking) methods. We present several numerical examples illustrating the main features of the proposed methods. We also compare our methods with several methods from the literature.     

Novel organic catalysts for the direct enantioselective α-oxidation of carbonyl compounds

The proline-derived N-sulfonylcarboxamide-catalyzed direct enantioselective α-oxidation of ketones and aldehydes with nitrosobenzene is presented. The reactions proceed smoothly furnishing the corresponding α-aminoxylated compounds in good yields with up to >99% ee. The proline-derived N-sulfonylcarboxamides were also found to be excellent catalysts for the direct enantioselective nitroso Diels-Alder-type reaction between nitrosobenzene and α,β-unsaturated cyclic ketones yielding the corresponding bicyclic Diels-Alder adduct products with up to >99% ee. The proline-derived N-sulfonylcarboxamides represent a readily available and highly modular novel type of organic catalyst.     

Surface properties and photocatalytic activity of nanocrystalline titania films

In this work the efficiency and physicochemical details of a thin film produced by help of a microwave assisted sol gel technique is compared to different commercial powders (Degussa P25 and Hombikat UV100) deposited on glass substrates. Furthermore, a supercritical produced TiO₂ powder (SC 134) was included in the comparison.The prepared TiO₂ films were characterized using XRD, XPS, AFM, DSC and DLS. The photocatalytic activity was determined using stearic acid as a model compound. Investigation of the prepared films showed that the Degussa P25 film and the sol–gel film were the most photocatalytic active films. The activity of the films was found to be related to the crystallinity of the TiO₂ film and the amount of surface area and surface hydroxyl groups. Based on the XPS investigation of the films before and after UV irradiation it was suggested that the photocatalytic destruction of organic matter on TiO₂ films proceeds partly through formation of hydroxyl radicals which are formed from surface hydroxyl groups created by interactions between adsorbed water and vacancies on the TiO₂ surface. Furthermore a correlation between the amount of OH groups on the surface of the different TiO₂ films and the photocatalytic activity was found.