Physicochemical, spectroscopic and electrochemical characterization of magnesium ion-conducting, room temperature, ternary molten electrolytes

Room temperature, magnesium ion-conducting molten electrolytes are prepared using a combination of acetamide, urea and magnesium triflate or magnesium perchlorate. The molten liquids show high ionic conductivity, of the order of mS cm(-1) at 298 K. Vibrational spectroscopic studies based on triflate/perchlorate bands reveal that the free ion concentration is higher than that of ion-pairs and aggregates in the melt. Electrochemical reversibility of magnesium deposition and dissolution is demonstrated using cyclic voltammetry and impedance studies. The transport number of Mg2+ ion determined by means of a combination of d.c. and ac. techniques is similar to 0.40. Preliminary studies on the battery characteristics reveal good capacity for the magnesium rechargeable cell and open up the possibility of using this unique class of acetamide-based room temperature molten electrolytes in secondary magnesium batteries. (C) 2010 Elsevier B.V. All rights reserved.

Synergistic use of thermogravimetric and electrochemical techniques for thermodynamic study of TiOx (1.67 <= x <= 2.0) at 1573 K

A thermodynamic study of the Ti-O system at 1573 K has been conducted using a combination of thermogravimetric and emf techniques. The results indicate that the variation of oxygen potential with the nonstoichiometric parameter delta in stability domain of TiO2-delta with rutile structure can be represented by the relation, Delta mu o(2) = -6RT In delta - 711970(+/-1600) J/mol. The corresponding relation between non-stoichiometric parameter delta and partial pressure of oxygen across the whole stability range of TiO2-delta at 1573 K is delta proportional to P-O2(-1/6). It is therefore evident that the oxygen deficient behavior of nonstoichiometric TiO2-delta is dominated by the presence of doubly charged oxygen vacancies and free electrons. The high-precision measurements enabled the resolution of oxygen potential steps corresponding to the different Magneli phases (Ti-n O2n-1) up to n = 15. Beyond this value of n, the oxygen potential steps were too small to be resolved. Based on composition of the Magneli phase in equilibrium with TiO2-delta, the maximum value of n is estimated to be 28. The chemical potential of titanium was derived as a function of composition using the Gibbs-Duhem relation. Gibbs energies of formation of the Magneli phases were derived from the chemical potentials of oxygen and titanium. The values of -2441.8(+/-5.8) kJ/mol for Ti4O7 and -1775.4(+/-4.3) kJ/mol for Ti3O5 Obtained in this study refine values of -2436.2(+/-26.1) kJ/mol and-1771.3(+/-6.9) kJ/mol, respectively, given in the JANAF thermochemical tables.

Electrochemical reduction of Cu(II)-CyDTA complex at dropping mercury electrode. An impedance approach

The electrochemical reduction of Cu(II)-CyDTA (CyDTA — trans 1,2-cyclohexanediamine N, N, N′, N′ tetraacetic acid) by impedance method reveals the unusual behaviour of complex plane polarograms owing to potential dependence of double layer capacitance. The impedance plane plots by frequency variation method indicates the quasi-reversible nature of the system. From these plots the chargetransfer resistance at various potentials was evaluated. The standard rate constant was evaluated which complements the prediction of impedance plots for the quasireversible behaviour of the system.

Electrochemical reduction of Cu(II)-EDTA complex at dropping mercury electrode. An impedance approach

The study of electrochemical reduction of Cu(II)-EDTA system by phase sensitive a.c. impedance method at dropping mercury electrode reveals several interesting features. The complex plane polarograms exhibit loop like shape in contrast to the classical zinc ion reduction where crest like shape is found. Again, the relative placement of peaks of in-phase and quadrature components, and the relative placement of portions before and after the peaks of complex plane polarograms are different from that of zinc ion reduction. The complex plane plots suggest that electrochemical reduction of Cu-EDTA is charge transfer controlled.

Nature of nitrogen adsorbed on transition metal surfaces as revealed by electron spectroscopy and cognate techniques

The nature of the chemisorbed states of nitrogen on various transition metal surfaces is discussed comprehensively on the basis of the results of electron spectroscopic investigations augmented by those from other techniques such as LEED and thermal desorption. A brief discussion of the photoemission spectra of free N2, a comparison of adsorbed N2 and CO as well as of physisorption of N2 on metal surfaces is also presented. We discuss the chemisorption of N2 on the surfaces of certain metals (e.g. Ni, Fe, Ru and W) in some detail, paying considerable attention to the effect of electropositive and electronegative surface modifiers. Features of the various chemisorbed states (one or more weakly chemisorbed gamma-states, strongly chemisorbed alpha-states with bond orders between 1 and 2. and dissociative chemisorbed beta-states) on different surfaces are described and relations between them indicated. While the gamma-state could be a precursor of the alpha-state, the alpha-state could be the precursor of the beta-state and this kind of information is of direct relevance to ammonia synthesis. The nature of adsorption of N2 on the surfaces of some metals (e.g. Cr, Co) deserves further study and such investigations might as well suggest alternative catalysts for ammonia synthesis.

An investigation of well-characterized small gold clusters by photoelectron spectroscopy, tunneling spectroscopy, and cognate techniques

After microscopic characterization of the size distributions of gold clusters, deposited on carbon substrates by vacuum evaporation or by soft landing, Au(4f') binding energy of the clusters has been measured as a function of the mean cluster size. Similar measurements have been carried out on Au clusters prepared from sols by chemical means and high-nuclearity cluster compounds. In general, small clusters with a mean diameter of $2 nm show significantly larger binding energies than the bulk metal value, due to the onset of nonmetallicity. Nonmetallicity manifests itself in terms of a tunneling conductance gap only in clusters of diameter ;5 1 nm containing 40 atoms or fewer.

Self-assembled molecular films of tetraamino metal (Co, Cu, Fe) phthalocyanines on gold and silver. Electrochemical and spectroscopic characterization

The formation of molecular films of 2,9,16,23-tetraamino metal phthalocyanines [TAM(II)Pc; M (II) = Co, Cu, and TAM(III)Pc; M = Fe] by spontaneous adsorption on gold and silver surfaces is described. The properties of these films have been investigated by cyclic voltammetry, impedance, and FT-Raman spectroscopy. The charge associated with Co(II) and Co(I) redox couple in voltammetric data leads to a coverage of (0.35+/-0.05) x 10(-10) mol cm(-2), suggesting that the tetraamino cobalt phthalocyanine is adsorbed as a monolayer with an almost complete coverage. The blocking behavior of the films toward oxygen and Fe(CN)(6)(3-/4-) redox couple have been followed by cyclic voltammetry and impedance measurements. This leads to an estimate of the coverage of about 85 % in the case of copper and the iron analogs. FT-Raman studies show characteristic bands around 236 cm(-1) revealing the interaction between the metal substrate and the nitrogen of the -NH2 group on the phthalocyanine molecules.

Enhanced Raman Spectroscopy of Molecules Adsorbed on Carbon-Doped TiO2 Obtained from Titanium Carbide: A Visible-Light-Assisted Renewable Substrate

Titanium carbide (TiC) is an electrically conducting material with favorable electrochemical properties. In the present studies, carbon-doped TiO2 (C-TiO2) has been synthesized from TiC particles, as well as TiC films coated on stainless steel substrate via thermal annealing under various conditions. Several C-TiO2 substrates are synthesized by varying experimental, conditions and characterized by UV-visible spectroscopy, photoluminescence, X-ray diffraction and X-ray photoelectron spectroscopic techniques. C-TiO2 in the dry state (in powder form as well as in film form) is subsequently used as a substrate for enhancing Raman signals corresponding to 4-mercaptobenzoic acid and 4-nitrothiophenol by utilizing chemical enhancement based on charge-transfer interactions. Carbon, a nonmetal dopant in TiO2, improves the intensities of Raman signals, compared, to undoped TiO2. Significant dependence of Raman intensity on carbon doping is observed. Ameliorated performance obtained using C-TiO2 is attributed to the presence of surface defects that originate due to carbon as a dopant, which, in turn,, triggers charge transfer between TiO2 and analyte. The C-TiO2 substrates are subsequently regenerated for repetitive use by illuminating an analyte-adsorbed substrate with visible light for a period of 5 h.

Carbonaceous nickel oxide nano-composites: as electrode materials in electrochemical capacitor applications

Carbonaceous nickel oxide powder samples have been synthesized from an adducted nickel beta-ketoester complex used as a ``single source precursor'' through a solution-based microwave-assisted chemical route. Comprehensive analysis of the resulting powder material has been carried out using various characterization techniques. These analysis reveal that, depending on the solvent used, either NiO/C or Ni/NiO/C composites are formed, wherein Ni and/or NiO nanocrystals are enveloped in amorphous carbon. As the components emerge from the same molecular source, the composites are homogeneous on a fine scale, making them promising electrode materials for supercapacitors. Electrochemical capacitive behavior of these oxide composites is studied in a three-electrode configuration. With a specific capacitance of 113 F g(-1), Ni/NiO/C is superior to NiO/C as capacitor electrode material, in 0.1 M Na2SO4 electrolyte. This is confirmed by impedance measurements, which show that charge-transfer resistance and equivalent series resistance are lower in Ni/NiO/C than in NiO/C, presumably because of the presence of metallic nickel in the former. The cyclic voltammograms are nearly rectangular and the electrodes display excellent cyclability in different electrolytes: Na2SO4, KOH and Ca(NO3)(2)center dot 4H(2)O. Specific capacitance as high as 143 F g(-1), is measured in Ca(NO3)(2)center dot 4H(2)O electrolyte.

Electrochemical exfoliation of graphite to produce graphene using tetrasodium pyrophosphate

An electrochemical exfoliation based synthetic methodology to produce graphene is provided. An eco-friendly and non-toxic tetrasodium pyrophosphate solution in which the pyrophosphate anion acts as an intercalating ion was used as the electroactive media. Five different ion intercalation potentials were used. Characterization by microscopy, X-ray diffraction, Raman spectroscopy and UV-Visible spectroscopic techniques confirmed that all the potentials produced nano to micrometer sized graphene sheets. No trace of graphene oxide was detected. It was observed that (i) an increase in the intercalation potential increased the graphene yield and (ii) the defect density of graphene did not change significantly with a change in the intercalation potential.

Electrochemical, spectroscopic and SPM evidence for the controlled formation of self-assembled monolayers and organised multilayers of ferrocenyl alkyl thiols on Au(111)

Organised multilayers were formed from the controlled self-assembly of ferrocene alkyl thiols on Au(111) surfaces. The control was accomplished by increasing the concentration of the thiol solutions used for the assembly. Cyclic voltammetry, ellipsometry, scanning probe microscopy (STM and AFM) and in situ FTIR spectroscopy were used to probe the differences between mono- and multilayers of the same compounds. Electrochemical desorption studies confirmed that the multilayer structure is attached to the surface via one monolayer. The electrochemical behaviour of the multilayers indicated the presence of more than one controlling factor during the oxidation step, whereas the reduction was kinetically controlled which contrasts with the behaviour of monolayers, which exhibit kinetic control for the oxidation and reduction steps. Conventional and imaging ellipsometry confirmed that multilayers with well-defined increments in thickness could be produced. However, STM indicated that at the monolayer stage, the thiols used promote the mobility of Au atoms on the surface. It is very likely that the multilayer structure is held together through hydrogen bonding. To the best of out knowledge, this is the first example of a controlled one-step growth of multilayers of ferrocenyl alkyl thiols using self-assembly techniques.

Evaluation of bioelectrical impedance analysis and Fulton’s condition factor as nonlethal techniques for estimating short-term responses in postsmolt Atlantic salmon (Salmo salar) to food availabili

We evaluated measures of bioelectrical impedance analysis (BIA) and Fulton’s condition factor (K) as potential nonlethal indices for detecting short-term changes in nutritional condition of postsmolt Atlantic salmon (Salmo salar). Fish reared in the laboratory for 27 days were fed, fasted, or fasted and then refed. Growth rates and proximate body composition (protein, fat, water) were measured in each fish to evaluate nutritional status and condition. Growth rates of fish responded rapidly to the absence or reintroduction of food, whereas body composition (% wet weight) remained relatively stable owing to isometric growth in fed fish and little loss of body constituents in fasted fish, resulting in nonsignificant differences in body composition among feeding treatments. The utility of BIA and Fulton’s K as condition indices requires differences in body composition. In our study, BIA measures were not significantly different among the three feeding treatments, and only on the final day of sampling was K of fasted vs. fed fish significantly different. BIA measures were correlated with body composition content; however, wet weight was a better predictor of body composition on both a content and concentration (% wet weight) basis. Because fish were growing isometrically, neither BIA nor K was well correlated with growth rate. For immature fish, where growth rate, rather than energy reserves, is a more important indicator of fish condition, a nonlethal index that reflects shortterm changes in growth rate or the potential for growth would be more suitable as a condition index than either BIA measures or Fulton�