Polyol technique synthesis of Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> coated on LiFePO<Subscript>4</Subscript> cathode materials for Li-ion storage

A novel approach has been made to tailor Niobium pentoxide (Nb₂O₅) as a coating material on the surface of lithium iron phosphate (LiFePO₄) via a facile polyol technique. The coating content was optimized at 1 wt%. The superficial coating demonstrated superior discharge capacity than the pristine LiFePO₄. However, increasing the coating content further would result in a capacity loss. This may be due to the electrochemical inactiveness that increases with the content of the coating material, and 1 wt% of Nb₂O₅-coated LiFePO₄ sample exhibits initial discharge capacity of 163 mAh g^?1 at a current of 0.1 C and retains a stable discharge capacity of 143 mAh g^?1 up to 400 cycles at 1 C rate with a coulombic efficiency of 98%.

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Shock Processing of Amino Acids Leading to Complex Structures—Implications to the Origin of Life

The building blocks of life, amino acids, are believed to have been synthesized in the extreme conditions that prevail in space, starting from simple molecules containing hydrogen, carbon, oxygen and nitrogen. However, the fate and role of amino acids when they are subjected to similar processes largely remain unexplored. Here we report, for the first time, that shock processed amino acids tend to form complex agglomerate structures. Such structures are formed on timescales of about 2 ms due to impact induced shock heating and subsequent cooling. This discovery suggests that the building blocks of life could have self-assembled not just on Earth but on other planetary bodies as a result of impact events. Our study also provides further experimental evidence for the ‘threads’ observed in meteorites being due to assemblages of (bio)molecules arising from impact-induced shocks.     

Synthesis,Structure, and Highly Efficient Copper‐Catalyzed Aziridination with a Tetraaza‐Bispidine Ligand

The distorted trigonal‐bipyramidal Cu^II complex [Cu(L¹)(NCCH₃)]²⁺ of the novel tetradentate bispidine‐derived ligand L¹ with four tertiary amine donors (L¹=1,5‐diphenyl‐3‐methyl‐7‐(1,4,6‐trimethyl‐1,4‐diazacycloheptane‐6‐yl)diazabicyclo[3.3.1]nonane‐9‐one) is a very efficient catalyst for the aziridination of olefins in the presence of a nitrene source. In agreement with the experimental data (in situ spectroscopy, product distribution, and its dependence on the geometry of the substrate and of the nitrene source), a theoretical analysis based on DFT calculations indicates that the active catalyst has the Cu center in its +II oxidation state, that electron transfer is not involved, and that the conversion of the olefin to an aziridine is a stepwise process involving a radical intermediate. The striking change of efficiency and reaction mechanism between classical copper–bispidine complexes and the novel L¹‐based catalyst is primarily attributed to the structural variation, enforced by the ligand architecture.     

Effect of solvent volume on the physical properties of sprayed fluorine‐doped zinc oxide thin films

Fluorine‐doped zinc oxide (FZO) films were deposited from aged starting solutions having different solvent volumes (10, 20, 30, 40 and 50 ml) using a simplified spray pyrolysis technique. The electrical studies showed that the resistivity is minimum (4.68 × 10^–2 Ω cm) for lowest solvent volume (10 ml) and the value progressively increased with the increase in the solvent volume indicating that the fluorine incorporation increases with solvent volume. The systematic study clearly showed that the spray flux rate plays a crucial role in determining the electrical, optical, surface and structural properties of the FZO films. The optical transparency is found to be gradually increased (from 85 to 95%) as the volume of the solvent increases. The scanning electron microscope images depicted that the decrease in the spray flux rate caused an enhancement in the grain size. The X‐ray diffraction profile clearly showed that all the films have preferential orientation along the (002) plane with hexagonal wurtzite structure. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and electrochemical characterization of olivine-type lithium iron phosphate cathode materials via different techniques

High-potential, eco-friendly LiFePO₄ cathode materials were synthesized by polyol, hydrothermal, and solid-state reaction methods. The polyol technique was carried out without any special atmosphere and postheat treatment. The synthesized samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectrometry (XPS), and charge-discharge and cyclic voltammetry tests. The LiFePO₄ prepared via polyol technique exhibits good electrochemical performance than other method samples do.

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The mechanism of the (bispidine)copper(II)-catalyzed aziridination of styrene: a combined experimental and theoretical study

Experimental and DFT-based computational results on the aziridination mechanism and the catalytic activity of (bispidine)copper(I) and -copper(II) complexes are reported and discussed (bispidine=tetra- or pentadentate 3,7-diazabicyclo[3.1.1]nonane derivative with two or three aromatic N donors in addition to the two tertiary amines). There is a correlation between the redox potential of the copper(II/I) couple and the activity of the catalyst. The most active catalyst studied, which has the most positive redox potential among all (bispidine)copper(II) complexes, performs 180 turnovers in 30 min. A detailed hybrid density functional theory (DFT) study provides insight into the structure, spin state, and stability of reactive intermediates and transition states, the oxidation state of the copper center, and the denticity of the nitrene source. Among the possible pathways for the formation of the aziridine product, the stepwise formation of the two N-C bonds is shown to be preferred, which also follows from experimental results. Although the triplet state of the catalytically active copper nitrene is lowest in energy, the two possible spin states of the radical intermediate are practically degenerate, and there is a spin crossover at this stage because the triplet energy barrier to the singlet product is exceedingly high.     

Highly conducting and crystalline doubly doped tin oxide films fabricated using a low-cost and simplified spray technique

Doubly doped (simultaneous doping of antimony and fluorine) tin oxide films (SnO₂:Sb:F) have been fabricated by employing an inexpensive and simplified spray technique using perfume atomizer from aqueous solution of SnCl₂ precursor. The structural studies revealed that the films are highly crystalline in nature with preferential orientation along the (2 0 0) plane. It is found that the size of the crystallites of the doubly doped tin oxide films is larger (69 nm) than that (27 nm) of their undoped counterparts. The dislocation density of the doubly doped film is lesser (2.08×10¹⁴ lines/m²) when compared with that of the undoped film (13.2×10¹⁴ lines/m²), indicating the higher degree of crystallinity of the doubly doped films. The SEM images depict that the films are homogeneous and uniform. The optical transmittance in the visible range and the optical band gap of the doubly doped films are 71% and 3.56 eV respectively. The sheet resistance (4.13 Ω/□) attained for the doubly doped film in this study is lower than the values reported for spray deposited fluorine or antimony doped tin oxide films prepared from aqueous solution of SnCl₂ precursor (without using methanol or ethanol).     

Base-mediated reaction of the Bestmann-Ohira reagent with nitroalkenes for the regioselective synthesis of phosphonylpyrazoles

1,3-Dipolar cycloaddition of the anion of diethyl 1-diazomethylphosphonate, generated in situ from diethyl 1-diazo-2-oxopropylphosphonate (Bestmann-Ohira reagent), with conjugated nitroalkenes provides regioisomerically pure phosphonylpyrazoles in moderate to good yield. These pyrazoles are formed in one pot via spontaneous elimination of the nitro group. However, nitropyrazoles could be synthesized by the same strategy using alpha-bromonitroalkenes. The methodology works for the synthesis of phosphonylpyrazoles fused to other carbo- and heterocycles as well. [reaction: see text]     

Coordination diversity in palladium(II)-picolinamide ligand complexes: structural and quantum chemical studies

The separation of different metal ions can be successfully accomplished by using picolinamide-based ligands. We herein report the first X-ray structure of picolinamide-based ligands of the type C₅H₄NCONR₂ (where R=ⁱC₃H₇ (L1) and ⁱC₄H₉ (L2)) and C₅H₄NCONHR (R=^tC₄H₉ (L3)) with palladium(II) ion. We have synthesized and characterized the structures of two palladium complexes, [PdCl₂(L1)₂] (1) and [PdCl₂L3] (3). In 1, ligand L1 forms a 2?:?1 complex with palladium(II) chloride, whereas in 3, the ligand L3 forms a 1?:?1 complex. Further, in 1, the ligand L1 acts as a monodentate ligand and is bound only through pyridyl-N atom, whereas in 3, the ligand L3 acts as a bidentate chelating ligand and is bound through both the pyridyl-N and amido-O atoms to the Pd(II) center. Electronic structure calculations are carried out to understand the experimental coordination diversity in the Pd complexes. Our calculations clearly suggest that a combination of steric hindrance of the ligand and the electronic effect of metal ions may modulate the coordination preferences.     

Electronic charge distribution in the intermetallic compound MnHg

The Electron Density Distribution (EDD) of the Mn and Hg atoms in MnHg has been elucidated for the first time using the statistical approach MEM (Maximum Entropy Method). Reported powder X‐ray data have been used for the present analysis. Presently, MEM studies are gaining momentum because of the feasibility of mapping the refined electron densities with very high accuracy, well resolved and clear electron density distributions obtainable from this method, etc. Moreover, the MEM results resemble very nearly the true structure/electron densities unlike the conventional Fourier methods, which give biased information due to many reasons, the major one being the series termination error. In the present analysis, the bonding between Mn and Hg, and the electron content for different radii of the two atoms has been investigated. The thermal vibration of the two atoms has also been analyzed and reported. The thermal parameter of Hg has been more accurately determined than that of Mn, which is in consistent with the electron density distribution of the atoms.