Study of Anion Exchange Membrane Properties Incorporating N-spirocyclic Quaternary Ammonium Cations and Aqueous Organic Redox Flow Battery Performance

Flexible cross-linked anion exchange membranes (AEMs) based on poly (p-phenylene oxide) grafted with N-spirocyclic quaternary ammonium cations were synthesized via UV-induced free-radical polymerization by using diallylpiperidinium chloride as an ionic monomer. Five membranes with ion exchange capacity (IEC) varying between 1.5 to 2.8 mmol Cl−·g−1 polymer were obtained and the correlation between IEC, water uptake, state of water in the membrane and ionic conductivity was studied. In the second part of this study, the influence of properties of four of these membranes on cell cycling stability and performance was investigated in an aqueous organic redox flow battery (AORFB) employing dimethyl viologen (MV) and N,N,N-2,2,6,6-heptamethylpiperidinyl oxy-4-ammonium chloride (TMA-TEMPO). The influence of membrane properties on cell cycling stability and performance was studied. At low-current density (20 mA·cm−2), the best capacity retention was obtained with lower IEC membranes for which the water uptake, freezable water and TMA-TEMPO and MV crossover are low. However, at a high current density (80 mA·cm−2), membrane resistance plays an important role and a membrane with moderate IEC, more precisely, moderate ion conductivity and water uptake was found to maintain the best overall cell performance. The results in this work contribute to the basic understanding of the relationship between membrane properties and cell performance, providing insights guiding the development of advanced membranes to improve the efficiency and power capability for AORFB systems.

Rational Design of Molecularly Imprinted Polymers Using Quaternary Ammonium Cations for Glyphosate Detection

Molecularly imprinted polymers have emerged as cost-effective and rugged artificial selective sorbents for combination with different sensors. In this study, quaternary ammonium cations, as functional monomers, were systematically evaluated to design imprinted polymers for glyphosate as an important model compound for electrically charged and highly water-soluble chemical compounds. To this aim, a small pool of monomers were used including (3-acrylamidopropyl)trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium chloride, and diallyldimethylammonium chloride. The simultaneous interactions between three positively charged monomers and glyphosate were preliminary evaluated using statistical design of the experiment method. Afterwards, different polymers were synthesized at the gold surface of the quartz crystal microbalance sensor using optimized and not optimized glyphosate-monomers ratios. All synthesized polymers were characterized using atomic force microscopy, contact angle, Fourier-transform infrared, and X-ray photoelectron spectroscopy. Evaluated functional monomers showed promise as highly efficient functional monomers, when they are used together and at the optimized ratio, as predicted by the statistical method. Obtained results from the modified sensors were used to develop a simple model describing the binding characteristics at the surface of the different synthesized polymers. This model helps to develop new synthesis strategies for rational design of the highly selective imprinted polymers and to use as a sensing platform for water soluble and polar targets.

Variation of counter quaternary ammonium cations of anionic cage germanoxanes as building blocks of nanoporous materials

Double-four ring (D4R)-type cage germanoxanes, having fluoride anion in the cage, contain organic ammonium cations as counter cations outside the cage, and they are attractive as unique nano-building blocks of...

Acid Properties of Hierarchical Zeolites Y

The article reviews different strategies towards obtaining mesoporous zeolites Y: desilication; surfactant templating and assembly of zeolite crystals. The impact of those methods on physicochemical properties is covered, with a special focus on the acidity of the samples measured with infrared (IR) spectroscopy. The methods of characterization of acidity are presented. Quaternary ammonium cations used for desilication lead to obtaining crystalline; mesoporous and highly acidic zeolites. Si-OH-Al groups of extremely high acidity can be produced by calcination in a humid atmosphere. When the conditions are optimized, post-synthetic surfactant templating allows crystalline mesoporous zeolite to be obtained with no loss of material. All mesoporous zeolites Y proved to be active catalysts in liquid phase isomerization, catalytic cracking, and other reactions.

Rational molecular design of anion exchange membranes functionalized with alicyclic quaternary ammonium cations

Piperidine-based cations tethered to ether-free polymer membranes via the 4-position instead of the conventional 1(N)-position show significantly improved thermal and alkaline stability while retaining high hydroxide conductivity.