Investigation of Nafion series membranes on the performance of iron‐chromium redox flow battery

To boost the performance of the iron‐chromium redox flow battery (ICRFB), opting an appropriate proton exchange membrane (PEM) as the core component of ICRFB is of great importance. For the purpose, in this paper, various widely adopted commercial Nafion membranes with a different thickness of 50 μm (Nafion 212, N212), 126 μm (N115), and 178 μm (N117) are chosen for the sake of evaluating the influence of membrane thickness on the ICRFB single‐cell performance. Physicochemical properties, electrolyte utilization, cell efficiency, long‐term cycling stability, and the self‐discharge process of ICRFBs based on a series of Nafion membranes are contrasted comprehensively. The cycling test of ICRFBs is carried out under the current density range of 40 to 120 mA/cm² for the charge‐discharge process. As a result of the good equilibrium of membrane resistance and electro‐active species permeability, Nafion 212 membrane exhibits the highest electrolyte utilization and energy efficiency during the operation, accompanied by the lowest overpotential. In the final part, the selection of Nafion membrane thickness was optimized on the basis of single‐cell performance and the overall cost of the system.     

Microfluidic Tumor-on-a-Chip Model to Study Tumor Metabolic Vulnerability

Tumor-specific metabolic adaptations offer an interesting therapeutic opportunity to selectively destroy cancer cells. However, solid tumors also present gradients of nutrients and waste products across the tumor mass, forcing tumor cells to adapt their metabolism depending on nutrient availability in the surrounding microenvironment. Thus, solid tumors display a heterogenous metabolic phenotype across the tumor mass, which complicates the design of effective therapies that target all the tumor populations present. In this work, we used a microfluidic device to study tumor metabolic vulnerability to several metabolic inhibitors. The microdevice included a central chamber to culture tumor cells in a three-dimensional (3D) matrix, and a lumen in one of the chamber flanks. This design created an asymmetric nutrient distribution across the central chamber, generating gradients of cell viability. The results revealed that tumor cells located in a nutrient-enriched environment showed low to no sensitivity to metabolic inhibitors targeting glycolysis, fatty acid oxidation, or oxidative phosphorylation. Conversely, when cell density inside of the model was increased, compromising nutrient supply, the addition of these metabolic inhibitors disrupted cellular redox balance and led to tumor cell death.     

Electrochemical Characterization of Isolated Nitrogenase Cofactors from Azotobacter vinelandii

The nitrogenase cofactors are structurally and functionally unique in biological chemistry. Despite a substantial amount of spectroscopic characterization of protein-bound and isolated nitrogenase cofactors, electrochemical characterization of these cofactors and their related species is far from complete. Herein we present voltammetric studies of three isolated nitrogenase cofactor species: the iron–molybdenum cofactor (M-cluster), iron–vanadium cofactor (V-cluster), and a homologue to the iron–iron cofactor (L-cluster). We observe two reductive events in the redox profiles of all three cofactors. Of the three, the V-cluster is the most reducing. The reduction potentials of the isolated cofactors are significantly more negative than previously measured values within the molybdenum–iron and vanadium–iron proteins. The outcome of this study provides insight into the importance of the heterometal identity, the overall ligation of the cluster, and the impact of the protein scaffolds on the overall electronic structures of the cofactors.     

The influence of pyrite content on the flotation of chalcopyrite/pyrite mixtures

In the flotation of copper ores, several processing plants report that copper recovery is affected by the proportion and reactivity of pyrite in the ore, with the effect becoming more intense when the feed particles are finer as a result of regrinding. In this work, a mixed model mineral system consisting of chalcopyrite (CuFeS₂) and pyrite (FeS₂) with varying pyrite content (20–80 wt.%) was used to investigate the effect of pyrite on the pulp chemistry and chalcopyrite recovery. Flotation tests showed that chalcopyrite flotation rate, recovery and grade, as well as the pulp oxidation potential, decreased with increasing pyrite content whilst pyrite recovery increased. Surface analysis (XPS, ToF-SIMS and EDTA) indicated that copper activation of pyrite increased with increasing pyrite content, facilitating pyrite recovery. The decrease in chalcopyrite recovery can be attributed to increased surface oxidation.     

Solution‐processable and electroactive aromatic polyamides with 3,5‐bis(trifluoromethyl)triphenylamine moiety

New fluorine‐containing, triphenylamine‐based diamine and dicarboxylic acid monomers, namely 3,5‐bis(trifluoromethyl)‐4′,4″‐diaminotriphenylamine and 3,5‐bis(trifluoromethyl)‐4′,4″‐dicarboxytriphenylamine, were synthesized and polymerized with commercially available aromatic dicarboxylic acids and diamines, respectively, leading to two series of aromatic polyamides, 5a–h and 7a–e . Most of the polyamides were amorphous and readily soluble in many common organic solvents and could be solution‐cast into transparent, flexible and strong films with good mechanical properties. The polyamides had useful levels of thermal stability associated with high glass transition temperatures of 273–305 °C and 10% weight‐loss temperatures in excess of 500 °C. Cyclic voltammograms of films of polymers 5a–h on indium–tin oxide‐coated glass substrates exhibited reversible oxidation redox couples with E_1/2 around 1.15 V versus Ag/AgCl in tetrabutylammonium perchlorate/acetonitrile solution, accompanied by a color change from colorless neutral state to reddish brown oxidized state. The 7 series polymers displayed a higher oxidation potential and less electrochemical stability as compared to the 5 series analogues. © 2017 Society of Chemical Industry     

Experimental quantification and modelling of reaction zones in a cyclic watergas shift reactor

The cyclic watergas shift reactor (CWGSR) is a cyclically operated fixed bed reactor for the production of hydrogen. It is based on the alternating reduction of an iron oxide fixed bed with synthesis gas and its subsequent oxidation with steam. We show experimental data of moving reaction zones in a tubular CWGSR. Based on this data and to help further design of these reactors, we propose a dynamic, one-dimensional model of the reactor. The formulated process model was fitted to experimental data by adjusting only two parameters describing the catalytic activity and the oxygen capacity of the fixed bed. Exemplary simulation results are shown.     

Chain Dechlorination of Organic Chlorinated Compounds in Alcohol Solutions by 60Co γ-Rays, (III)

Chlorinated benzenes dissolved in deoxygenated alkaline 2-propanol were dechlorinated by irradiating with ⁶⁰Co γ-rays to produce the lower chlorinated benzenes and chloride ion. The yield of dechlorination was found to depend on the number of chlorine atoms on the benzene ring, the G (CI^?)-values being, for instance, 6,500, 480 and 2.0 for 0.07 M penta-chlorobenzene, 1, 2, 4-trichlorobenzene, and monochlorobenzene, respectively, in 0.2 M KOH-2-propanol solution. In contrast, the values of G(C1^?) differed little between the isomers of trichlorobenzene. The large difference in G (CI^?) according to the number of chlorine atoms can be explained by considering the redox potential of the chlorinated benzenes and the ketyl radical ion.

Trichlorobenzene is dechlorinated to dichlorobenzene and then to monochlorobenzene while producing potassium chloride and acetone, and consuming hydroxide ion. In the experiment, some chlorinated benzene derivatives were observed to be generated in the course of this process—probably dichlorophenyl-2-propanol and monochlorophenyl-2-propanol, judging from observation by gaschromatograph-mass spectrometer and from the path-way of formation. The observation also indicated the presence of dichlorophenyl-2-propanol in predominant amounts in 1, 3, 5-trichlorobenzene solution, but only in a small fraction in 1, 2, 3-trichlorobenzene.     

Rapid and direct determination of fructose in food: A new osmium-polymer mediated biosensor

This paper describes the development and performance of a new rapid amperometric biosensor for fructose monitoring in food analysis. The biosensor is based on the activity of fructose dehydrogenase (FDH) immobilised into a carbon nanotube paste electrode according to two different procedures. The direct wiring of the FDH in a highly original osmium-polymer hydrogel was found to offer a better enzyme entrapment compared to the immobilisation of the enzyme in an albumin hydrogel. The optimised biosensor required only 5 U of FDH and kept the 80% of its initial sensitivity after 4 months. During this time, the biosensor showed a detection limit for fructose of 1 μM, a large linear range between 0.1 and 5 mM, a high sensitivity (1.95 μA cm⁻² mM), good reproducibility (RSD = 2.1%) and a fast response time (4 s).     

Electro‐induced polymerization of acrylamide initiated by the potassium permanganate–titriplex VI redox system

The polymerization of acrylamide (AAm) was carried out with a potassium permanganate–Titriplex VI redox initiator system with and without electrolysis. Because of the high metal‐ion concentration in general, low‐molecular‐weight polymers were obtained (weight‐average molecular weight = 2600–4000). The effect of potassium permanganate and AAm concentrations and temperature on the polymerization yield was studied and compared with results obtained under the same experimental conditions used for electrolysis. The results of Fourier transform infrared spectroscopy, atomic absorption spectrometry, and scanning electron microscopy (SEM) results are given. SEM micrographs of the polymer obtained by electrochemical methods exhibited smoother surfaces than those obtained by nonelectrolytic methods. In the absence of potassium permanganate, there was no polymerization under experimental conditions. A possible reaction mechanism is suggested. The electro‐induced system resulted in about a 50% increase in the yield. Manganese content in the electro‐induced and chemical polymerization systems were 2.7 and 8.2%, respectively, supporting the yield increase in the electro‐induced system. A graphite electrode was used and resulted in a high yield and a fibrous polymeric structure. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1526–1534, 2001     

Redox behavior of indium in molten chlorides

An electrochemical study on the redox behavior of indium in the eutectic LiCl-KCl system at 450 °C was carried out with the transient techniques of cyclic voltammetry and chronopotentiometry on an inert molybdenum electrode. The reduction of In(III) was found to be a two-step process involving In(III)/In(I) and In(I)/In couples at the potentials of about ?0.4 and ?0.8 V versus Ag/AgCl, respectively. The redox mechanism was further confirmed by the theoretical evaluation of the number of transferred electrons based on cyclic voltammetry and characterizations of the precipitates generated by the potentiostatic electrolysis. The diffusion coefficients of indium ions in the eutectic LiCl-KCl melt at 450 °C were estimated by cyclic voltammetry and chronopotentiometry. The results obtained through the two methods are in fair agreement, delivering an average diffusion coefficient of approximately 1.8×10^?5 cm²/s for In(III), and 1.4×10^?4 cm²/s for In(I).