Acidity of edge surface sites of montmorillonite and kaolinite

Peer reviewedPreprin

Three-terminal devices to examine single molecule conductance switching

We report electronic transport measurements of single-molecule transistor devices incorporating bipyridyl-dinitro oligophenylene-ethynylene dithiol (BPDN-DT), a molecule known to exhibit conductance switching in other measurement configurations. We observe hysteretic conductance switching in 8% of devices with measurable currents, and find that dependence of the switching properties on gate voltage is rare when compared to other single-molecule transistor devices. This suggests that polaron formation is unlikely to be responsible for switching in these devices. We discuss this and alternative switching mechanisms.Comment: 5 pages, 4 figures. Supporting material available upon reques

Hydrogen Bond Dynamics Near A Micellar Surface: Origin of the Universal Slow Relaxation at Complex Aqueous Interfaces

The dynamics of hydrogen bonds among water molecules themselves and with the polar head groups (PHG) at a micellar surface have been investigated by long molecular dynamics simulations. The lifetime of the hydrogen bond between a PHG and a water molecule is found to be much longer than that between any two water molecules, and is likely to be a general feature of hydrophilic surfaces of organized assemblies. Analyses of individual water trajectories suggest that water molecules can remain bound to the micellar surface for more than a hundred picosecond. The activation energy for such a transition from the bound to a free state for the water molecules is estimated to be about 3.5kcal/mole.Comment: 12 pages. Phys. Rev. Lett. (Accepted) (2002

Nonflammable Lithium Metal Full Cells with Ultra-high Energy Density Based on Coordinated Carbonate Electrolytes

Coupling thin Li metal anodes with high-capacity/high-voltage cathodes such as LiNi0.8Co0.1Mn0.1O2 (NCM811) is a promising way to increase lithium battery energy density. Yet, the realization of high-performance full cells remains a formidable challenge. Here, we demonstrate a new class of highly coordinated, nonflammable carbonate electrolytes based on lithium bis(fluorosulfonyl)imide (UFSI) in propylene carbonate/fluoroethylene carbonate mixtures. Utilizing an optimal salt concentr ation (4 M LiFSI) of the electrolyte results in a unique coordination structure of Li+-FSI-solvent cluster, which is critical for enabling the formation of stable interfaces on both the thin Li metal anode and high-voltage NCM811 cathode. Under highly demanding cell configuration and operating conditions (Li metal anode = 35 mu m, areal capacity/charge voltage of NCM811 cathode = 4.8 mAh cm(-2)/4 .6 V, and anode excess capacity [relative to the cathode] = 0.83), the Li metal-based full cell provides exceptional electrochemical performance (energy densities = 679 Wh kg(cell)(-1)/1,024 Wh L-cell(-1)) coupled with nonflammability

The influence of process gas type on the enamel surface condition of a high power diode laser generated single-stage ceramic tile grout seal

Almost all laser materials processing operations require the simultaneous use of an process or assist gas. This paper examines the use of O2, Ar, N2 and He as process gasses during the firing of a vitreous enamel to form a single-stage ceramic tile grout seal with a high power diode laser (HPDL) and the effects thereof on the surface condition of the glaze. The findings revealed marked differences in the surface condition of the HPDL generated enamel glaze depending upon the process gas used. The use of O2 as the process gas was seen to result in glazes with far fewer microcracks and porosities than those generated with any of the other three gasses, particularly He. Such differences were found to be due to the ability of the smaller O2 gas molecules to dissolve molecularly into the open structure of the HPDL generated enamel glaze and also, the inherent reactiveness of O2 which consequently effects exothermic reactions when it is used as a process gas. Both occurrences were seen, in turn, to affect the cooling rate and therefore the tendency of the molten glaze to generate microcracks when cooled

Molybdenum (VI) imido complexes derived from chelating phenols : Synthesis, characterization and ɛ-Caprolactone ROP capability

Reaction of the bulky bi-phenols 2,2′-RCH[4,6-(t-Bu)₂C₆H₂OH]₂ (R = Me L¹ᵐᵉH₂, Ph L¹ᵖʰH₂) with the bis(imido) molybdenum(VI) tert-butoxides [Mo(NR¹)(NR²)(Ot-Bu)₂] (R¹ = R² = 2,6-C₆H₃-i-Pr₂; R¹ = t-Bu, R² = C₆F₅) afforded, following the successive removal of tert-butanol, the complexes [Mo(NC₆H₃ᵢ-Pr₂-2,6)₂L¹ᵐᵉ] (1), [Mo(NC₆H₃i-Pr₂-2,6)₂L¹ᵖʰ] (2) and [Mo(Nt-Bu)(μ-NC₆F₅)(L¹ᵐᵉ)]₂ (3). Similar use of the tri-phenol 2,6-bis(3,5-di-tert-butyl-2-hydroxybenzyl)-4-methylphenol (L²H₃) with [Mo(NC₆H₃ᵢ-Pr₂-2,6)₂(Ot-Bu)₂] afforded the oxo-bridged product [Mo(NC₆H₃i-Pr₂-2,6)(NCMe)(μ-O)L2H]₂ (4), whilst use of the tetra-phenols α,α,α′,α′-tetrakis(3,5-di-tert-butyl-2-hydroxyphenyl)-p- or -m-xylene L³ᵖH₄/L³ᵐH₄ led to {[Mo(NC₆H₃ᵢ-Pr₂-2,6)₂]₂(μ-L³ᵖ)} (5) or {[Mo(NC₆H₃ᵢ-Pr₂-2,6)₂]₂(μ-L³ᵐ)} (6), respectively. Similar use of [Mo(NC₆F₅)₂(Ot-Bu)₂] with L³ᵖH₄ afforded, after work-up, the complex {[Mo(NC₆F₅)(Ot-Bu)₂]₂(μ-L³ᵖ)}·6MeCN (7·6MeCN). Molecular structures of 1, 2·CH₂Cl₂, 3, 4·6MeCN, 6·2C₆H₁₄, and 7·6MeCN are reported and these complexes have been screened for their ability to ring open polymerize (ROP) ε-caprolactone; for comparative studies the precursor complex [Mo(NC₆H₃ᵢ-Pr₂-2,6)₂Cl₂(DME)] (DME = 1,2-dimethoxyethane) has also been screened. Results revealed that good activity is only achievable at temperatures of ≥100 °C over periods of 1 h or more. Polymer polydispersities were narrow, but observed molecular weights (Mn) were much lower than calculated values

The application of synchrotron radiation and in particular X-ray absorption spectroscopy to matrix isolated species

This review provides comprehensive coverage of the application of X-ray absorption spectroscopy (XAS, XAFS, EXAFS, and XANES) to matrix isolated species. As X-ray absorption spectroscopy provides structural data without the need for long range order it has been applied to a large number of systems to yield unique structural data about both the matrix isolated species, and their interactions with the matrix host. To put the work into perspective there is a tutorial introduction to the theoretical background of X-ray absorption spectroscopy, data content, processing and analysis. In addition there is brief coverage of the use of other synchrotron radiation techniques for the study of matrix isolated species, and a consideration of future perspectives