Pseudocapacitive effect and Li+ diffusion coefficient in three-dimensionally ordered macroporous vanadium oxide for energy storage

In order to act as extrinsic pseudocapacitor materials, nanoscale vanadium oxides are required to simultaneously exhibit a capacitance-based high power density and an intercalation-based high energy density. We have fabricated a three-dimensionally ordered macroporous (3DOM) structure with a wall thickness of 14 nm that fulfills the above requirements. The 3DOM vanadium oxide film exhibits high rate performance with 355 F g^− 1 at 0.5 A g^− 1 and 125 F g^− 1 at 15 A g^− 1. The enhanced pesudocapacitive effect and Li-ion diffusion coefficient based on the 3DOM nanostructure, also contributes to the high rate capability of vanadia, which can be confirmed by cyclic voltammetry and chronoamperometry.     

Pd‐initiated polymerization of diazo compounds bearing dialkoxyphosphinyl group and hydrolysis of the resulting polymers and oligomers to afford phosphonic acid‐containing products

Pd‐initiated polymerization and oligomerization of diazo compounds containing a dialkoxyphosphinyl group are described. Polymerization of 2‐dialkoxyphosphinylethyl diazoacetates with π‐allylPdCl‐based initiating systems afforded C? C main chain polymers bearing phosphonate on each main chain carbon atom. The quantitative transformation of the side chain phosphonate to phosphonic acid resulted in the formation of water soluble polymers having the acid groups accumulated around their main chains, although the carbonyl ester linkage in the side chain was cleaved via intramolecular acid‐assisted hydrolysis in water at 80 °C. Pd‐initiated oligomerization of diethyl diazomethylphosphonate yielded an oligomeric product bearing diethoxyphosphiny groups directly attached to its main chain carbons, with unexpected incorporation of azo group in the main chain framework. Hydrolysis of the phosphonate of the oligomer afforded a water‐soluble product, which was revealed to show higher proton conductivity than poly(vinylphosphonic acid) under certain conditions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1742–1751     

A novel self activated K2XV2O7 (X = Mg and Zn) pyrovanadate green phosphor: Systematic characterization and time resolved photoluminescence

Novel self activated green phosphors; K₂ZnV₂O₇ (KZV) and K₂MgV₂O₇ (KMV) have been prepared and characterized in details. Both KZV and KMV were prepared by solid state reaction and systematically characterized by a number of techniques like X-ray diffraction (XRD), Fourier transformed Infrared (FTIR), Raman spectroscopy, Scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), diffuse reflectance spectroscopy (DRS) and time resolved photoluminescence spectroscopy (TRPLS). XRD studies confirm tetragonal melilite type layered phase for both of them. The presence of pyrovanadate group in both is supported by FTIR and Raman spectroscopic investigations. Raman bands of KMV are blue shifted w.r.t to KZV which may be due to shorter bond lengths of MgO compared to ZnO and lower atomic weight of magnesium compared to zinc. DRS measurements indicated the optical band gap of KMV and KZV are 3.14 and 3.12 eV, respectively. Optical measurements on these samples show the emission of green color on ultra violet light irradiation. The origin of such emission is attributed to electronic transition (charge transfer) from filled 2p orbital of oxygen ion (O²⁻) to vacant 3d orbital of vanadium ion (V⁵⁺). In KZV there are dual emission band (PL1 and PL2) which are respectively attributed to ³T₂ → ¹A₁ and ³T₁ → ¹A₁transition, and the emission zone varies slightly compared to KMV. KZV emits bluish green (cool green) where KMV emits in yellowish green (warm green) region. This is indeed an important step towards realization of cost effective rare earth free luminescence material. It is also oberved that PL intensity of KZV is very high compared to KMV which is supported by the lifetime measurements.     

Tailorable PC71BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High‐Performance Polymer Solar Cells

Despite being widely used as electron acceptor in polymer solar cells, commercially available PC₇₁BM (phenyl‐C₇₁‐butyric acid methyl ester) usually has a “random” composition of mixed regioisomers or stereoisomers. Here PC₇₁BM has been isolated into three typical isomers, α‐, β₁‐ and β₂‐PC₇₁BM, to establish the isomer‐dependent photovoltaic performance on changing the ternary composition of α‐, β₁‐ and β₂‐PC₇₁BM. Mixing the isomers in a ratio of α/β₁/β₂=8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC₇₁BM as photoactive layer (PTB7=poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]]). The three typical PC₇₁BM isomers, even though sharing similar LUMO energy levels and light absorption, render starkly different photovoltaic performances with average‐performing PCE of 1.28–7.44 % due to diverse self‐aggregation of individual or mixed PC₇₁BM isomers in the otherwise same polymer solar cells.     

Shear-induced nonisothermal crystallization of two grades of PLA

Shear-induced nonisothermal crystallization of two commercial polylactides (PLAs) differing in optical purity was studied. The molten polymers were sheared at selected temperatures (T_s) and subsequently cooled. The crystallization was followed by a light depolarization method, whereas the specimens were analysed ex-situ by DSC, 2D-WAXS and SEM after etching. It was found that the effect of shear, especially on the crystallinity developed during post-shearing cooling, intensified with a decrease of T_s from 160 to 146 ^°C, and with increasing shear rate and strain. Moreover, the effect of shear on PLA1.5 with d-lactide content of 1.5% was stronger than PLA2.8 with 2.8% of d-lactide, although maximum crystallinity of both polymers was practically the same. A decrease of cooling rate from 30 to 10 ^°C/min increased crystallinity of both PLAs, except for those shearing conditions which induced high crystallinity even during faster cooling. Although SEM examination revealed some row-nucleated forms, no significant crystal orientation was detected by 2D-WAXS, indicating that, under the experimental conditions, the shear induced predominantly point-like nuclei.     

Magnetic behaviors and multitransition temperatures in a nanoisland

A nanoisland consists of center spin-5/2 and perimeter spin-3/2 atoms, which is described by transverse Ising model with single-ion anisotropy. Magnetic behaviors of the nanoisland are studied by the effective-field theory with correlations and the differential operator technique. The formulas of the magnetization and the phase transition of the system are given. The numerical results of the phase transition, the magnetization, the initial susceptibility and the internal energy have been discussed. Some interesting phenomena, such as a new reentrant, are found. Namely there are multitransition temperatures dependent on competition among the single-ion anisotropies, the transverse field and the interlayer coupling. These results can provide some guidance to structure design in the nanoislands.