Physical and electrochemical properties of thioether-functionalized ionic liquids

The preparation and characterization of a series of ionic liquids based on S-alkyl thiolonium, S-alkyl thiotetrazolium, or S-alkyl thiobenzolium cations coupled with bis(trifluoromethanesulfonyl)amide, trifluoromethanesulfonate, alkyl phosphate, chloride, and hexafluorophosphate anions are reported. All are liquid at room temperature, except the chloride salt, which has a melting point of 92 °C. The electrochemical characteristics of this class of ionic liquid have been determined by cyclic voltammetry. Potential windows of the ionic liquids have been obtained at glassy carbon, platinum, and gold electrodes and found to be the largest at glassy carbon, but are limited by oxidation of the thioether-functionalized cation. The voltammetry of IUPAC reference potential scale systems, ferrocene/ferrocenium, cobaltocenium/cobaltocene, and decamethylferrocene/decamethylferrocenium have been evaluated, with the last being most widely applicable. Nonadditivity of Faradaic current is found in the voltammograms of decamethylferrocene in the presence of ferrocene and cobaltocenium. Diffusion coefficient, viscosity, ionic conductivity, double layer capacitance, and other physical properties have also been measured. The dependence of the diffusion coefficient vs viscosity follows the Stokes−Einstein relationship. The properties of the ionic liquids are compared with the related imidazolium family of ionic liquids.

Simultaneous control of spectroscopic and electrochemical properties in functionalised electrochemiluminescent tris(2,2'-bipyridine)ruthenium(II) complexes

Using a combination of electrochemical, spectroscopic and computational techniques, we have explored the fundamental properties of a series of ruthenium diimine complexes designed for coupling with other molecules or surfaces for electrochemiluminescence (ECL) sensing applications. With appropriate choice of ligand functionality, it is possible to manipulate emission wavelengths while keeping the redox ability of the complex relatively constant. DFT calculations show that in the case of electron withdrawing substituents such as ester or amide, the excited state is located on the substituted bipyridine ligand whereas in the case of alkyl functionality it is localised on a bipyridine. The factors that dictate annihilation ECL efficiency are interrelated. For example, the same factors that determine ΔG for the annihilation reaction (i.e. the relative energies of the HOMO and LUMO) have a corresponding effect on the energy of the excited state product. As a result, most of the complexes populate the excited state with an efficiency (Φex) of close to 80% despite the relatively wide range of emission maxima. The quantum yield of emission (Φp) and the possibility of competing side reactions are found to be the main determinants of ECL intensity.

Electrochemical properties and applications of ionic liquids

This book presents the latest research in electrochemical properties and applications of ionic liquids. While there is no universally agreed upon definition, an ionic liquid may be conveniently described as a compound composed entirely of ions that is a liquid at temperatures less than 100 °C. However, this is an arbitrary definition employed to distinguish ionic liquids from classically well-known molten salts. This book addresses a comprehensive overview of the area, because it is obvious that ionic liquids have the ability to offer many advantages, but also some disadvantages, over traditional molecular solvent (electrolyte) media in the field of electrochemistry.

Effect of zwitterions on electrochemical properties of oligoether-based electrolytes

Solid polymer electrolytes show great potential in electrochemical devices. Poly(ethylene oxide) (PEO) has been studied as a matrix for solid polymer electrolytes because it has relatively high ionic conductivity. In order to investigate the effect of zwitterions on the electrochemical properties of poly(ethylene glycol) dimethyl ether (G5)/lithium bis(fluorosulfonyl) amide (LiFSA) electrolytes, a liquid zwitterion (ImZ2) was added to the G5-based electrolytes. In this study, G5, which is a small oligomer, was used as a model compound for PEO matrices. The thermal properties, ionic conductivity, and electrochemical stability of the electrolytes with ImZ2 were evaluated. The thermal stabilities of all the G5-based electrolytes with ImZ2 were above 150 °C, and the ionic conductivity values were in the range of 0.8–3.0 mS cm−1 at room temperature. When the electrolytes contained less than 5.5 wt% ImZ2, the ionic conductivity values were almost the same as that of the electrolyte without ImZ2. The electrochemical properties were improved with the incorporation of ImZ2. The anodic limit of the electrolyte with 5.5 wt% ImZ2 was 5.3 V vs. Li/Li+, which was over 1 V higher than that of G5/LiFSA.

Preparation of size-selective Mn3O4 hexagonal nanoplates with superior electrochemical properties for pseudocapacitors

Porous Mn3O4 hexagonal nanoplates were synthesized through annealing the hydrohausmannite precursor obtained by a one-pot hydrothermal process and by precisely controlling the concentrations of potassium hydroxide and glucose. The effect of potassium hydroxide and glucose on the growth of hexagonal nanoplates was investigated, and a growth mechanism was also proposed. Due to its abundant pores, the pure Mn3O4-based electrode exhibits excellent cycling stability with 100% capacity retention after 5000 cycles. The asymmetric supercapacitor exhibited high performance with an energy density of 17.276 W h kg^-1 at a power density of 207.3 W kg^-1 in a wide potential window of 1.5 V.

Iridium(III) N-heterocyclic carbene complexes: an experimental and theoretical study of structural, spectroscopic, electrochemical and electrogenerated chemiluminescence properties

Four cationic heteroleptic iridium(III) complexes have been prepared from methyl- or benzyl-substituted chelating imidazolylidene or benzimidazolylidene ligands using a Ag(I) transmetallation protocol. The synthesised iridium(III) complexes were characterised by elemental analysis, (1)H and (13)C NMR spectroscopy and the molecular structures for three complexes were determined by single crystal X-ray diffraction. A combined theoretical and experimental investigation into the spectroscopic and electrochemical properties of the series was performed in order to gain understanding into the factors influencing photoluminescence and electrochemiluminescence efficiency for these complexes, with the results compared with those of similar NHC complexes of iridium and ruthenium. The N^C coordination mode in these complexes is thought to stabilise thermally accessible non-emissive states relative to the case with analogous complexes with C^C coordinated NHC ligands, resulting in low quantum yields. As a result of this and the instability of the oxidised and reduced forms of the complexes, the electrogenerated chemiluminescence intensities for the compounds are also low, despite favourable energetics. These studies provide valuable insights into the factors that must be considered when designing new NHC-based luminescent complexes.

Structure and capacitive properties of porous nanocrystalline VN produced by NH3 reduction of V2O5

Vanadium nitride (VN) is currently one of the most promising materials for electrodes of supercapacitors. The structure and electrochemical properties of VN synthesized by temperature-programmed NH₃ reduction of V₂O₅ are analyzed in this paper. Vanadium nitride produced via this route has distinctive structural characteristics. VN mimics the shape of the initial V₂O₅ precursor indicating a pronounced direct attachment of nitride grains. The particles have domains of grains with a preferential orientation (texture). The large volume of pores in VN is represented by the range of 15−110 nm. VN demonstrates capacitive properties in three different types of aqueous electrolytes, 1 M KOH, 1 M H₂SO₄, and 3 M NaCl. The material has an acceptable rate capability in all electrolytes, showing about 80% of its maximal capacitance at a current load of 1 A/g in galvanostatic charging/discharging experiments. The capacitance of 186 F/g is observed in 1 M KOH electrolyte at 1 A/g. The previously reported negative effect of material loading on the capacitance is significantly suppressed. The observed electrochemical characteristics related to the application of this material in supercapacitors can be correlated with the crystalline structure of the nitride and the composition of its surface layer.

Electrochemical impedance spectroscopy and surface characterization techniques to study carbon dioxide corrosion product scales

Electrochemical impedance spectroscopy (EIS) was used to study carbon dioxide (CO2) corrosion product scales and their effects on further CO2 corrosion. Objectives were to determine the suitability of EIS for studying corrosion scales and to investigate the influence of environmental factors on scale formation. EIS provided useful information about protective abilities and electrochemical properties of corrosion scales. CO2 corrosion scales formed at high-temperature and pressure provided better protection than those formed at low-temperature and pressure. The level of protection of the scale formed at higher temperature and pressure increased with exposure time. EIS results were compared with coupon weight-loss measurements. Scales were analyzed using a combination of Fourier transform infrared (FTIR) analysis, x-ray diffraction (XRD), and electron microscopy.