Galyna Shul

The electrochemical ion-transfer reactivity of porphyrinato metal complexes in 4-(3-phenylpropyl)pyridine | water systems

The transfer of ions between an aqueous and an organic phase is driven electrochemically at a triple phase junction graphite | 4-(3-phenylpropyl)pyridine | aqueous electrolyte. Tetraphenylporphyrinato (TPP) metal complexes (MnTPP+, FeTPP+, CoTPP) and hemin readily dissolve in the organic 4-(3-phenylpropyl)pyridine phase and undergo oxidation/reduction processes which are coupled to liquid | liquid ion transfer. In order to maintain charge neutrality, each one-electron oxidation (reduction) process is coupled to the transfer of one anion (here PF6−, ClO4−, SCN−, NO3−, OCN−, or CN−) from the aqueous (organic) into the organic (aqueous) phase. The range of anions studied allows effects of hydrophobicity and complex formation (association of the anion to the metal center) to be explored. A preliminary kinetic scheme is developed to quantify complex formation, facilitated anion transfer, and competing cation transfer processes. The effects of the organic solvent on the ion transfer processes are explored. Very strong binding and specific effects are observed for the reversible cyanide transfer process.

Kinetics of Electroless Deposition: The Copper-Dimethylamine Borane System

A kinetic study of the electroless deposition of copper on gold, using dimethylamine borane (DMAB) as a reducing agent, has been carried out. The copper deposition rate in the electroless bath was determined to be 50 nm min(-1), through electrochemical stripping of the copper deposits as well as from direct measurements of the film thickness using atomic force microscopy (AFM). Comparison with a galvanic cell setup, where the two half-reactions were physically separated, yielded a lower deposition rate of 30 nm min(-1). An important kinetic effect of the surface on the oxidation of the reducing agent, and thus on the overall process, was therefore revealed. The efficiency of the process was measured over time, revealing the contribution of side reactions in the cathodic half-cell, particularly during the initial stages of the electroless process.

Correction to “Electrochemical Formation of an Ultrathin Electroactive Film from 1,10-Phenanthroline on a Glassy Carbon Electrode in Acidic Electrolyte”

The electrochemical reduction of 1,10-phenanthroline in aqueous acidic electrolyte at a glassy carbon electrode led to the covalent modification of the electrode. Thereafter, the deposited film can be switched to an electroactive form by electrochemical oxidation. An electroactive film can be also generated by alternate reductive and oxidative voltammetric cycling in a 1,10-phenanthroline/aqueous sulfuric acid solution. First, the electrochemical procedure for the formation of a film is presented. Second, the morphology and chemical structure of 1,10-phenanthroline coatings were investigated by atomic force microscopy, time-of-flight secondary ion mass spectrometry, X-ray photoelectron spectroscopy, and electrochemical techniques. The ultrathin (<15 nm) electrodeposited films consist of oligomeric species. The coatings deposited in alternate and/or continuous reductive and oxidative steps contain oxygen atoms incorporated into the oligomer backbone. The preliminary results point out the formation of a dio...

Solid electrolyte based on silicate matrix functionalised with tetraalkylammonium group solvated by organic solvent

Solid electrolyte composed of hybrid organic–inorganic silicate matrix functionalised with tetraalkylammonium group, solvated by viscous organic polar solvent (propylene carbonate (PC) or sulpholane (TMS)), was prepared by the sol–gel method under controlled drying conditions. Tetramethoxysilane (TMOS), N-trimethoxysilylpropyl-N,N,N-tributylammonium chloride (TMOSPTBACl) and organic solvent were principal sol components. Gel formed within 2 h and 2 days depending on substrate ratio and the solvent additive. The obtained material was transparent and it loosed about 15% of its mass during first 30 days of ageing. It was characterised by thermogravimetry (TGA), differential scanning calorimetry (DSC), NMR, FT-IR spectroscopy, small angle X-ray scattering (SAXS), and impedance spectroscopy. The transport of redox active molecules was studied by electrochemical methods. The porosity of samples dried in supercritical CO2 was also estimated. The shape of TGA and DSC curve appeared to be similar to that of pure solvent. The IR spectra indicated the silicate network formation with some silanol groups left. The NMR spectrum of the solution used to wash crushed sample indicated that all organic substrate is embedded in silicate matrix. The magnitude of electrical conductivity was close to 10 −4 to 10 −5 Sc m −1 , i.e. least more than one order of magnitude larger than that of TMOS based silicate matrix modified with a pure solvent. This conductivity is high enough for electrochemical experiments. Both conductivity and diffusion coefficient of redox probe-ferrocene (Fc) depended on time elapsed after gelation. Their most substantial decrease was observed during first 10 days after gelation and it correlated with mass loss.