Transparent Ion-Exchange Membrane Exhibiting Intense Emission under a Specific pH Condition Based on Polypyridyl Ruthenium(II) Complex with Two Imidazophenanthroline Groups

The development and the photophysical behavior of a transparent ion-exchange membrane based on a pH-sensitive polypyridyl ruthenium(II) complex, [(bpy)2RuII(H2bpib)RuII(bpy)2](ClO4)4 (bpy = 2,2′-bipyridine, H2bpib = 1,4-bis([1,10]phenanthroline[5,6-d]-imidazol-2-yl)benzene), are experimentally and theoretically reported. The emission spectra of [(bpy)2RuII(H2bpib)RuII(bpy)2]@Nafion film were observed between pH 2 and pH 11 and showed the highest relative emission intensity at pH 5 (λmaxem = 594.4 nm). The relative emission intensity of the film significantly decreased down to 75% at pH 2 and 11 compared to that of pH 5. The quantum yields (Φ) and lifetimes (τ) showed similar correlations with respect to pH, Φ = 0.13 and τ = 1237 ns at pH 5, and Φ = 0.087 and τ = 1014 ns and Φ = 0.069 and τ = 954 ns at pH 2 and pH 11, respectively. These photophysical data are overall considerably superior to those of the solution, with the radiative- (kr) and non-radiative rate constants (knr) at pH 5 estimated to be kr = 1.06 × 105 s−1 and knr = 7.03 × 105 s−1. Density functional theory calculations suggested the contribution of ligand-to-ligand- and intraligand charge transfer to the imidazolium moiety in Ru-H3bpib species, implying that the positive charge on the H3bpib ligand works as a quencher. The Ru-Hbpib species seems to enhance non-radiative deactivation by reducing the energy of the upper-lying metal-centered excited state. These would be responsible for the pH-dependent “off-on-off” emission behavior.

Correction: Nafion film transport properties in a low-Pt PEM fuel cell: impedance spectroscopy study

Correction for ‘Nafion film transport properties in a low-Pt PEM fuel cell: impedance spectroscopy study’ by Tatyana Reshetenko et al., RSC Adv., 2019, 9, 38797–38806, DOI: 10.1039/C9RA07794D.

Electric Migration of Hydrogen Ion in Pore-Voltammetry Suppressed by Nafion Film

Micro-hole voltammetry exhibiting rectified current-voltage curves was performed in hydrochloric acid by varying the lengths and the diameters of the micro-holes on one end of which a Nafion film was mounted. Some voltammetric properties were compared with those in NaCl solution. The voltammograms were composed of two line-segments, the slope of one segment being larger than the other. They were controlled by electric migration partly because of the linearity of the voltammograms and partly the independence of the scan rates. Since the low conductance which appeared in the current from the hole to the Nafion film was proportional to the cross section area of the hole and the inverse of the length of the hole, it should be controlled by the geometry of the hole. The conductance of the hydrogen ion in the Nafion film was observed to be smaller than that in the bulk, because the transport rate of hydrogen ion by the Grotthuss mechanism was hindered by the destruction of hydrogen bonds in the film. In contrast, the conductance for the current from the Nafion to the hole, enhancing by up to 30 times in magnitude from the opposite current, was controlled by the cell geometry rather than the hole geometry except for very small holes. A reason for the enhancement is a supply of hydrogen ions from the Nafion to increase the concentration in the hole. The concentration of the hydrogen ion was five times smaller than that of sodium ion because of the blocking of transport of the hydrogen ion in the Nafion film. However, the rectification ratio of H+ was twice as large as that of Na+.

Energy Harvesting of Ionic Polymer-Metal Composites Based on Microcellular Foamed Nafion in Aqueous Environment

The purpose of this study was to determine how to improve the energy-harvesting properties of polymer electrolyte membranes by varying their porosity. We achieved this by applying microcellular foaming process (MCP) to Nafion-based ionic polymer–metal composites (IPMCs). We manufactured an IPMC by forming a Pt electrode through an electroless plating method on the Nafion film, to which porosity was imparted by varying the foaming ratio and inducing deformation by vibrating the specimen using a prototype device that we developed ourselves. We attempted to harvest energy via fluid flow that occurred owing to displacement movement. When the Nafion film was foamed at a temperature of 140 °C or higher, it was observed that cells with size of approximately 1 µm or more were formed, and when the saturation temperature was lowered, a denser and larger number of cells were formed. Moreover, the cells formed on the electrolyte membrane allowed the retention of more water. Water retention generated charges contributed to the operational stability of IPMC. This was attributed to the difference in the amount of charge generated by changing only the internal morphology of the electrolyte membrane, without changing the substrate or the electrode material.