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  • Owen Katz posted an update 2 weeks, 1 day ago

    In this work, the nucleophilic substitution reactions of the cyclotetraphosphazene, tetramer, (1) (N4P4Cl8) with the disodium salt of 1,2-ethanediol in THF solution at different mole ratios were demonstrated. Surprisingly, one double bridged (2) and three ansa derivatives [bis (3), tris (4) and tetrakis (5)] were formed demonstrating two competing pathways in these reactions. The new type cyclotetraphosphazene compounds (2-5) consisting of multiple rings were characterized by elemental analysis, mass spectrometry, 1H and 31P NMR spectroscopy and X-Ray crystallography. Although 1,2-ethanediol, a short chain diol, can only produce spiro type products with cyclotriphosphazene, (N3P3Cl6), it was able to give ansa type products with cyclotetraphosphazene which suggests the role of the ring flexibility of 1. Crystallographic evidence shows the distortion of the cyclotetraphosphazene ring.In this study, we experimentally measured the viscosity, η, and ionic conductivity, σ, of the electrolyte solutions of 1 mol kg-1 of LiPF6 or LiFSA dissolved in the binary mixture solvent of EC and DMC in a temperature range of 288 ≤ T/K ≤ 328 by varying the EC content from 0 to 60 vol%, which translates into the molar fraction of EC of 0 ≤ xEC ≤ 0.7. OX04528 The diffusion coefficient, D, of each species, Li+, PF6-, FSA-, EC and DMC, was determined by pulse gradient spin-echo NMR. The state of molecules around Li+ was examined using the Raman spectra of the solvents and anions; the quantitative analysis suggests that EC is about twice as much preferred as DMC in the solvation shell at low xEC, while the EC-preference decreases with an increase in xEC. The classical Stokes-Einstein relation still quantitatively holds when evaluating the hydrodynamic radius, rSt, of transporting entities from D and η, in that (i) rSt,EC and rSt,DMC without the solute do not significantly differ from those in the solution; (ii) rSt,Li roughly coincides with the size estimated from the solvation number determined by Raman spectroscopy, which implies that rSt,Li reflects the solvation shell size; and (iii) rSt,anion is close to the static size, suggesting that anions are little solvated. The increase in xEC results in a decrease in rSt for all species, among which anions are most influenced, which is consistent with the view that the highly Li+-solvating EC, with its better dielectric shielding effect than DMC, liberates the anions from Li+, whereby enhancing the anion transfer that positively contributes to the ionic conductivity until the viscosity prevails at high xEC.Fe(iii) is a common pollutant released into our ecosystem from various industrial and anthropogenic activities which when in excess interferes with human health. A plethora of sensors based on various designs and working principles are being continuously synthesized and improvised for its facile detection. In the present review, we have provided a brief overview of the developments made in the field of metal organic framework (MOF) based optical sensors for Fe3+. MOFs have exponentially emerged in the field of research due to their high porosity, modular construction and easy tunability. These inorganic-organic hybrid porous materials are being essentially promoted as optical sensors because of their unique photophysical properties and potential sensing applications.Transition metal selenides have attracted enormous research attention as anodes for lithium-ion batteries (LIBs) due to their high theoretical specific capacities. Nevertheless, the low electronic conductivity and dramatic volume variation in electrochemical reaction processes result in rapid capacity fading and poor rate capability. Herein, a metal-organic framework is used as a template to in situ synthesize Sb2Se3 nanoparticles encapsulated in N-doped carbon nanotubes (N-CNTs) grafted on reduced graphene oxide (rGO) nanosheets. The synergistic effects of N-doped carbon nanotubes and reduced graphene oxide nanosheets are beneficial for providing good electrical conductivity and maintaining the structural stability of electrode materials, leading to stable cycling performance and superior rate performance. Kinetic analysis suggests that the electrochemical reaction kinetics is dominated by pseudocapacitive contribution. Notably, a high discharge capacity of 451.1 mA h g-1 at a current density of 2.0 A g-1 is delivered after 450 cycles. Even at a high current density of 10.0 A g-1, a discharge capacity of 192.6 mA h g-1 is maintained after 10 000 cycles. When coupled with a commercial LiFePO4 cathode, the full batteries show an excellent discharge specific capacity of 534.5 mA h g-1 at 0.2 A g-1. This work provides an effective strategy for constructing high-performance anodes for Li+ storage.The on-surface synthesis of non-planar nanographenes is a challenging task. Herein, with the aid of bond-resolving scanning tunneling microscopy (BRSTM) and density functional theory (DFT) calculations, we present a systematic study aiming at the fabrication of corannulene-based nanographenes via intramolecular cyclodehydrogenation on a Au(111) surface. The formation of non-planar targeted products is confirmed to be energetically unfavorable compared to the formation of planar/quasi-planar undesired competing monomer products. In addition, the activation of intermolecular coupling further inhibits the formation of the final targeted product. Although it was not possible to access the corannulene moiety by means of on-surface synthesis, partial cyclodehydrogenation of the molecular precursors was demonstrated.Three new isostructural quaternary tellurides, Ba2Ln1-xMn2Te5 (Ln = Pr, Gd, and Yb), have been synthesized by the molten-flux method at 1273 K. The single-crystal X-ray diffraction studies at 298(2) K showed that Ba2Ln1-xMn2Te5 crystallize in the space group -C2/m of the monoclinic crystal system. There are six unique crystallographic sites in this structure’s asymmetric unit one Ba site, one Ln site, one Mn site, and three Te sites. The Ln site in the Ba2Ln1-xMn2Te5 structure is partially filled, which leaves about one-third of the Ln sites vacant (□) for Pr and Gd compounds. These structures do not contain any homoatomic or metallic bonding and can be charge-balanced as (Ba2+)2(Gd/Pr3+)2/3(Mn2+)2(Te2-)5. The refined composition for the Yb compound is Ba2Yb0.74(1)Mn2Te5 and can be charge-balanced with a mixed valence state of Yb2+/Yb3+. The crystal structures of Ba2Ln1-xMn2Te5 consist of complex layers of [Ln1-xMn2Te5]4- stacked along the [100] direction, with Ba2+ cations separating these layers. The Ln atoms are bound to six Te atoms that form a distorted octahedral geometry around the central Ln atom.