Molecular design of ambipolar redox-active molecules II: closed-shell systems

This mini-review highlights key structural features that should be taken into account when creating ambipolar redox-active closed-shell metal-free molecules. This type of compound is strongly required for the fabrication of all-organic ‘poleless’ batteries and semiconductors. The suggested strategies aimed at stabilization of both oxidized (cationic) and reduced (anionic) redox-states are based on the comprehensive analysis of the most successful structures taken from the recent publications.     

Negatively Charged Metallacarborane Redox Couples with Both Members Stable to Air

The metallacarborane [3,3′‐Co(1,2‐closo‐C₂B₉H₁₁)₂]^? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E_1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C₂B₉H₇I₄)₂]^? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed.     

Quinones for redox flow batteries

Quinones are electroactive species that have shown great promise for redox flow batteries due to the ability to tune their properties and to act as both negative and positive electrolytes. The following review outlines highlights of work in the last couple of years working to provide materials with higher stability, solubility, and performance. Developments toward stable negolytes have provided opportunities for potential commercial opportunities when paired with alternate chemistries. However, the stability of quinones in high potential electrolytes is still not sufficient and the number of potential quinones limited.     

Methyl orange degradation enhanced by hydrogen spillover onto platinum nanocatalyst surface

Following a thermal reduction method, platinum nanoparticles were synthesized and stabilized by polyvinylpyrrolidone. The colloidal platinum nanoparticles were stable for more than 3 months. The micrograph analysis unveiled that the colloidal platinum nanoparticles were well dispersed with an average size of 2.53 nm. The sol–gel‐based inverse micelle strategy was applied to synthesize mesoporous iron oxide material. The colloidal platinum nanoparticles were deposited on mesoporous iron oxide through the capillary inclusion method. The small‐angle X‐ray scattering analysis indicated that the dimension of platinum nanoparticles deposited on mesoporous iron oxide (Pt‐Fe₂O₃) was 2.64 nm. X‐ray photoelectron spectroscopy (XPS) data showed that the binding energy on Pt‐Fe₂O₃ surface decreased owing to mesoporous support–nanoparticle interaction. Both colloidal and deposited platinum nanocatalysts improved the degradation of methyl orange under reduction conditions. The activation energy on the deposited platinum nanocatalyst interface (2.66 kJ mol^?1) was significantly lowered compared with the one on the colloidal platinum nanocatalyst interface (40.63 ± 0.53 kJ mol^?1).     

New protonic solid electrolyte with tetragonal tungsten bronze structure obtained through ionic exchange

Proton exchange reactions have been performed on tetragonal tungsten bronze-like NaNbWO₆ by using nitric acid as an exchanging agent. The characterization of the exchange reaction products has been made by means of chemical analysis, X-ray diffraction, thermal analysis, and IR spectroscopy. The exchange reaction takes place topotactically and the following formula is proposed for the obtained phase of variable composition: Na_1−xH_xNbWO₆·yH₂O (0<x?0.46 and 0?y?0.12). Impedance spectroscopy on the present proton exchanged samples indicated that these samples behaved as solid electrolytes under high humidity. As an example, the compound with the composition Na_0.68H_0.32NbWO₆·0.1 H₂O exhibits ionic conductivity of 8×10⁻³ and 1×10⁻² S cm⁻¹ at 70°C and 90°C, respectively.     

Ionic conductivity of multiarm star polymer/LiClO4 electrolytes

A series of polymer electrolytes based on multiarm polymers and lithium salt complexes were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and impedance measurement. The relationships of conductivity with salt concentration, temperature, and arm numbers are discussed. It is suggested that the star polymer has a higher solvency and ion transfer ability on lithium salts than on linear polymers. The conductivity maximum appeared at a higher salt concentration ([EO]/[Li] = 4). Impedance measurement suggested that the optimum conductivity was 2 × 10^?4 s · cm^?1. The conductivity increased with temperature and the dependence of ionic conductivity on temperature fits the Arrhenius equation. Among the studied systems, the star polymer with a five arm number performs better than other structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4195–4198, 2004     

Two-Layered Poly-o-phenylenediamine/Polyaniline Composite: Electrosynthesis and Spectroelectrochemical Properties

Spectroelectrochemical properties of poly-o-phenylenediamine (PPD) and the synthesized composite of PPD and polyaniline—two chemically related polymers containing an amino-substituted benzene ring but having different conduction nature—are studied. The polyaniline synthesis on PPD-modified electrodes involves stages of the reaction initiation, the copolymer formation, and the formation of a polyaniline layer at the copolymer/solution interface.     

Optimization of Mass Transfer Processes in the Zone of the Air Electrode of a Fuel Cell with a Solid Polymer Electrolyte

A two-dimensional mathematical model for the transport of reactants in a fuel cell with a solid polymer electrolyte is developed. The model is used for analyzing spatial distributions of the concentration of reactants and current density over the cell. The effect of the catalytic-layer activity, reactant speed, bipolar-plate geometry, thickness and porosity of current collector and/or gas-diffusion sublayer, and the reaction mixture composition on the fuel cell efficiency is estimated theoretically and experimentally.     

Effect of core-shell micelle formation on the redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide)

Redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide) (PT-EGE_n-b-EO_m) are reversibly changed by core-shell micelle formation. In the temperature range higher than the critical micellization temperature (cmt), the anodic potential of PT group positively shifts and concomitantly its anodic current decrease, or levels off compared to those of the reference polymer PT-EO_m without the thermo-responsive EGE_n segment. The former alteration is caused by incorporation of hydrophobic PT groups into a core of the micelle and the latter by the decrease in the diffusion coefficient of PT groups due to formation of the core-shell micelles. The cmt value and the temperature-dependent alteration in the redox properties strongly depend on the polymer structure, especially the length of thermo-responsive EGE_n segment. The electrochemically determined hydrodynamic radii of the polymer aggregates seem to be overestimated, compared to the values reported for the aggregates of other thermo-responsive polymers with similar molecular weights, implying the presence of electrochemically inactive PT groups in the copolymers having longer thermo-responsive segments.