Voltammetry at Hexamethyl-P-Terphenyl Poly(Benzimidazolium) (HMT-PMBI)-Coated Glassy Carbon Electrodes: Charge Transport Properties and Detection of Uric and Ascorbic Acid.

We describe the voltammetric behavior of an anion-exchange membrane, hexamethyl-p-terphenyl poly(benzimidazolium) (HMT-PMBI). The anion-exchange properties of HMT-PMBI chemically modified electrodes were investigated using K4Fe(CN)6 and K2IrCl6 as redox probes. The permselectivity properties of HMT-PMBI chemically modified electrodes were ascertained using tris(2-2')bipyridyl-ruthenium(II) chloride Ru(bpy)32+. Cyclic voltammetry and chronoamperometry were utilized to extract parameters such as the concentration of the redox mediators inside the films and the apparent diffusion coefficients. We found the concentration of K4Fe(CN)6 and K2IrCl6 redox species within HMT-PMBI-coated films to be on the order of 0.04-0.1 mol·dm-3, and values of Dapp ca. 10-10-10-9 cm2·s-1. To evaluate the possibility of using such a polymer coating in electroanalysis, HMT-PMBI-modified electrodes were utilized for the voltammetric detection of uric acid in artificial urine, Surine® and ascorbic acid in Vitamin C samples. The results showed that HMT-PMBI-coated electrodes can detect uric acid in Surine® with a limit of detection (LoD) of 7.7 µM, sensitivity of 0.14 µA·µM-1·cm-2, and linear range between 5 µM and 200 µM, whereas for Vitamin C tablets, the LoD is 41.4 µM, the sensitivity is 0.08 µA·µM-1·cm-2, and the linear range is between 25 µM and 450 µM.

Poly(phenylene) and m-Terphenyl as Powerful Protecting Groups for the Preparation of Stable Organic Hydroxides.

Four benzimidazolium hydroxide compounds, in which the C2-position is attached to a phenyl group possessing hydrogen, bromine, methyl groups, or phenyl groups at the ortho positions, are prepared and investigated for stability in a quantitative alkaline stability test. The differences between the stability of the various protecting groups in caustic solutions are rationalized on the basis of their crystal structures and DFT calculations. The highest stability was observed for the m-terphenyl-protected benzimidazolium, showing a half-life in 3 M NaOD/CD3OD/D2O at 80 °C of 3240 h. A high-molecular-weight polymer analogue of this model compound is prepared that exhibits excellent mechanical properties, high ionic conductivity and ion-exchange capacity, as well as remarkable hydroxide stability in alkaline solutions: only 5% degradation after 168 h in 2 M KOH at 80 °C. This is the most stable hydroxide-conducting benzimidazolium polymer to date.

Morphology of Anion-Conducting Ionenes Investigated by X-ray Scattering and Simulation.

We have studied the morphology of a novel series of benzimidazole-based ionenes, methylated poly(hexamethyl-p-terphenylbenzimidazolium) (HMT-PMBI), in halide form. Materials with anion-exchange capacities ranging from 0 to 2.5 mequiv/g were studied. X-ray scattering reveals three length scales in the materials: ion-polymer spacing (4 Å), polymer-polymer interchain spacing (6 Å), and an intrachain repeat distance (20 Å). No long-range structure is apparent above the monomer length, which is rare in ion-conducting polymer membranes. In preliminary molecular dynamics simulations, water molecules were observed forming chains between ions, even at a modest level of hydration, providing an interpenetrating network where conductivity can occur.

Transparent Bipolar Membrane for Water Splitting Applications.

This study describes the use of a benzimidazolium-based anion exchange membrane for creating bipolar membranes and the assessment of their suitability for solar-driven water splitting. Bipolar membranes were prepared by laminating anion exchange membrane with Nafion NR-211 membrane without modification of the interface. Under acidic and basic conditions, proton and hydroxide ion conductivities of 103 and 102 mS cm-1 were obtained for Nafion and benzimidazolium-based membranes, respectively. The fabricated bipolar membranes have an average thickness of 90 µm and show high transmittance, up to 75% of the visible light. The findings suggest that the two membranes create a sharp hydrophilic interface with a space charge region of only a few nanometers, thereby generating a large electric field at the interface that enhances water dissociation.

Cationic Polyelectrolytes, Stable in 10 M KOHaq at 100 °C.

We report on poly(arylene-imidazoliums), which were synthesized by microwave polycondensation of dialdehyde with bisbenzil and quantitatively functionalized by alkylation. This cationic polyelectrolyte is sterically protected around the C2-position and is stable in 10 M KOHaq at 100 °C (t1/2 of >5000 h). Alkaline stability is rationalized through analyses of model compounds, single crystal X-ray diffraction, and density functional theory. The polyelectrolytes form tough, pliable, transparent, ionically conductive films.

Hydroxide-Stable Ionenes.

In the pursuit of stable, hydroxide ion-exchange ionomers and solid polymer electrolytes for fuel cells and electrolyzers, we present a novel, sterically C2-protected poly(benzimidazole) derivative incorporating a hexamethyl-p-terphenylene group. Using a new, scalable, and air-insensitive methylation procedure, N-methylation of the polymer is controlled to yield an unprecedented hydroxide-stable, methanol-soluble, and water-insoluble poly(benzimidazolium) ionene. This original polymer is also soluble in aqueous ethanol, which makes it suitable for use as a processable ionomer for catalyst layers. The water uptake and ionic conductivity is correlated to the degree of methylation. The anionic conductivity reached 9.7 ± 0.6 mS cm-1 for polymers with a 92% degree of methylation. Additionally, the hexamethyl-p-terphenylene unit shows interesting atropisomerism, which may influence their physical properties.