Synthesis, and crystal and electronic structure of sodium metal phosphate for use as a hybrid capacitor in non-aqueous electrolyte

Energy storage devices based on sodium have been considered as an alternative to traditional lithium based systems because of the natural abundance, cost effectiveness and low environmental impact of sodium. Their synthesis, and crystal and electronic properties have been discussed, because of the importance of electronic conductivity in supercapacitors for high rate applications. The density of states of a mixed sodium transition metal phosphate (maricite, NaMn1/3Co1/3Ni1/3PO4) has been determined with the ab initio generalized gradient approximation (GGA)+Hubbard term (U) method. The computed results for the mixed maricite are compared with the band gap of the parent NaFePO4 and the electrochemical experimental results are in good agreement. A mixed sodium transition metal phosphate served as an active electrode material for a hybrid supercapacitor. The hybrid device (maricite versus carbon) in a nonaqueous electrolyte shows redox peaks in the cyclic voltammograms and asymmetric profiles in the charge-discharge curves while exhibiting a specific capacitance of 40 F g(-1) and these processes are found to be quasi-reversible. After long term cycling, the device exhibits excellent capacity retention (95%) and coulombic efficiency (92%). The presence of carbon and the nanocomposite morphology, identified through X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) studies, ensures the high rate capability while offering possibilities to develop new cathode materials for sodium hybrid devices.

Non-aqueous phase liquid behavior in the subsurface: Transportation, source zone characterization and remediation

Contaminant behaviour in soils and fractured rock is very complex, not least because of the heterogeneity of the subsurface environment. For non-aqueous phase liquids (NAPLs), a liquid density contrast and interfacial tension between the contaminant and interstitial fluid adds to the complexity of behaviour, increasing the difficulty of predicting NAPL behaviour in the subsurface. This paper outlines the need for physical model tests that can improve fundamental understanding of NAPL behaviour in the subsurface, enhance risk assessments of NAPL contaminated sites, reduce uncertainty associated with NAPL source remediation and improve current technologies for NAPL plume remediation. Four case histories are presented to illustrate physical modelling approaches that have addressed problems associated with NAPL transport, remediation and source zone characterization. © 2006 Taylor & Francis Group, London.

Electrolyte electroreflectance spectroscopy studies on the interfacial behavior of the near-surface In0.15Ga0.85As/GaAs quantum well electrode vertical bar non-aqueous electrolyte

Electrolyte electroreflectance spectra of the near-surface strained-layer In0.15Ga0.85As/GaAs double single-quantum-well electrode have been studied at different biases in non-aqueous solutions of ferrocene and acetylferrocene. The optical transitions, the Franz-Keldysh oscillations (FKOs) and the quantum confined Stark effects (QCSE) of In0.15Ga0.85As/GaAs quantum well electrodes are analyzed. Electric field strengths at the In0.15Ga0.85As/GaAs interface are calculated in both solutions by a fast Fourier transform analysis of FKOs. A dip is exhibited in the electric field strength versus bias (from 0 to 1.2 V) curve in ferrocene solution. A model concerning the interfacial tunneling transfer of electrons is used to explain the behavior of the electric field. (C) 2001 Elsevier Science B.V. All rights reserved.

Interfacial behaviour of a quantum well electrode/electrolyte: EER spectra of an SQW GaAs/AlxGa1-xAs electrode in HQ+BQ non-aqueous electrolyte

The quantum-confined Stark effect and the Franz-Keldysh oscillation of a single quantum well (SQW) GaAs/AlxGa1-xAs electrode were studied in non-aqueous hydroquinone + benzoquinone solution with electrolyte electroreflectance spectroscopy. By investigation of the relation of the quantum-confined Stark effect and the Franz-Keldysh oscillation with applied external bias, the interfacial behaviour of an SQW electrode was analysed. (C) 1997 Elsevier Science S.A.

Trichloroisocyanuric acid: A convenient oxidation reagent for phase-transfer catalytic epoxidation of enones under non-aqueous conditions

Trichloroisocyanuric acid (TCCA) is a cheap, safe and readily available alternative to the commonly used hydrogen peroxide and hypochlorite for the phase-transfer catalytic epoxidation of alpha,beta-enones under non-aqueous conditions. A variety of chalcone derivatives give the corresponding epoxides with quantitative conversion and satisfactory yields in just a few hours under mild conditions. An asymmetric variant of the epoxidation can be carried out in the presence of chiral N-anthracenylmethylcinchonidine bromide catalyst giving 73-93% ees and 76-94% yields.

Efficient preparation of silver nanoplates assisted by non-polar solvents

In the paper, we report an efficient method to prepare high yield (up to 97%) of silver nanoplates. Synthesis of silver nanoplates was carried Out in a binary solvent system of N,N-dimethylformamide (DMF) and toluene, in which DMF served as the reductant and polyvinylpyrrolidone (PVP) as the capping agent. By increasing the ratio of toluene to DMF to 7:6, silver nanoplates can be Successfully synthesized; otherwise other shaped nanoparticles would be the major products. The nanoplate sample was characterized by TEM, HRTEM, SAED, XRD, AFM and UV-visible spectroscopy, proving the high nanoplate purity of this sample. The influence of toluene content, other solvents, AgNO3 concentration, preparation temperature and chloride ions was also examined, which suggests that the function of nonpolar solvents in this system is to enhance the PVP coverage on silver surface and, furthermore, to facilitate the preferential adsorption of PVP on two (I I I) facets of silver nanoplates.

Separation of phenothiazines in aqueous and non-aqueous capillary electrophoresis

Four phenothiazines, promethazine, dioxypromethazine, chlorpromazine, and trifluoperazine have been separated by capillary electrophoresis using N, N, -dimethylformamide (DMF) as separation medium with UV absorbance detection. High voltage and concentrated buffer were used with small current and low electroosmosis. Good resolution and high column efficiency were obtained. Separation selectivity in DMI; was different from that in water because of the different solvation interactions. The influence of buffer composition on separation selectivities and electroosmosis were also studied.

Stability of 5-aminolevulinic acid in novel non-aqueous gel and patch-type systems intended for topical application.

Aminolevulinic acid (ALA) stability within topical formulations intended for photodynamic therapy (PDT) is poor due to dimerisation to pyrazine-2,5-dipropionic acid (PY). Most strategies to improve stability use low pH vehicles, which can cause cutaneous irritancy. To overcome this problem, a novel approach is investigated that uses a non-aqueous vehicle to retard proton-induced charge separation across the 4-carbonyl group on ALA and lessen nucleophilic attack that leads to condensation dimerisation. Bioadhesive anhydrous vehicles based on methylvinylether-maleic anhydride copolymer patches and poly(ethyleneglycol) or glycerol thickened poly(acrylic acid) gels were formulated. ALA stability fell below pharmaceutically acceptable levels after 6 months, with bioadhesive patches stored at 5°C demonstrating the best stability by maintaining 86.2% of their original loading. Glycerol-based gels maintained 40.2% in similar conditions. However, ALA loss did not correspond to expected increases in PY, indicating the presence of another degradative process that prevented dimerisation. Nuclear magnetic resonance (NMR) analysis was inconclusive in respect of the mechanism observed in the patch system, but showed clearly that an esterification reaction involving ALA and both glycerol and poly(ethyleneglycol) was occurring. This was especially marked in the glycerol gels, where only 2.21% of the total expected PY was detected after 204 days at 5°C. Non-specific esterase hydrolysis demonstrated that ALA was recoverable from the gel systems, further supporting esterified binding within the gel matrices. It is conceivable that skin esterases could duplicate this finding upon topical application of the gel and convert these derivatives back to ALA in situ, provided skin penetration is not affected adversely.