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Electrochemically mediated amine regeneration (EMAR) was recently developed to avoid the use of thermal means to release CO 2 captured from postcombustion flue gas in the benchmark amine process. To address concerns related to the high vapor pressure of ethylenediamine (EDA) as the primary amine used in EMAR, a mixture of EDA and aminoethylethanolamine (AEEA) was investigated. The properties of the mixed amine systems, including the absorption rates, electrolyte pH and conductivity, and CO 2 capacity, were evaluated in comparison with those of solely EDA. The mixed amine system had similar properties to that of EDA, indicating no significant changes would be necessary for the future implementation of the EMAR process with mixed amines as opposed to that with just EDA. The electrochemical performance of the mixed amines in terms of the cell voltage, gas desorption rate, electron utilization, and energetics was also investigated. A 50/50 mixture of EDA and AEEA displayed the lowest energetics: ∼10% lower than that of 100% EDA. With this mixture, a continuous EMAR process, in which the absorption column was connected to the electrochemical cell as the desorption stage, was tested over 100 h. The cell voltage was very stable and there was a steady gas output close to theoretical values. The desorbed gas was further analyzed and found to be 100% CO 2 , confirming no evaporation of the amine. The mixed absorbent composition was also characterized using titration and nuclear magnetic resonance (NMR) spectroscopy, and the results showed no amine degradation. These findings that demonstrate a stable, low vapor pressure absorbent with improved energetics are promising and could be a guideline for the future development of EMAR for CO 2 capture from flue gas and other sources.

Global water security is jeopardized by the presence of anthropogenic contaminants, which can persist resiliently in the environment and adversely affect human health. Surface adsorption of polluting species is an effective technique for water purification. In this work, redox-active magnetic compounds were designed for the targeted removal of inorganic and organic anions in water via polymeric redox-active vinylferrocene (VFc) and pyrrole (Py) moieties. An Fe3O4@SiO2@PPy@P­(VFc-co-HEMA) composite was prepared in a four-step process, with the outermost layer possessing heightened hydrophilicity as a result of the optimized incorporation of 2-hydroxyethylmethacrylate (HEMA) monomers into the backbone of the ferrocene macromolecule. The synthesized materials are able to separate carcinogenic hexavalent chromium oxyanions and other charged micropollutants, and exhibit a 2-fold or greater enhancement in adsorption uptake once the redox-active ferrocene groups are oxidized to ferrocenium cations, with capacities of 23, 49, 66, and 95 mg/g VFc for maleic acid, 2-(6-methoxy-2-naphthyl)­propionic acid (Naproxen), (2,4-dichlorophenoxy)­acetic acid (2,4-D), and (2-dodecylbenzene)­sulfonic acid (DBS), respectively, and a > 99% extractability of chromium in the 1 ppm range. The application of redox-active components to a magnetic particulate scaffold improves maneuverability and phase contact, giving rise to new potential aqueous separation process frameworks for water or product purification.

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The determination of sulfur in food samples via the rotational molecular absorption of carbon monosulfide (CS) was performed using a solid sampling high-resolution continuum source electrothermal atomic absorption spectrophotometer (SS-HR-CS-ETAAS). In the presence of plenty of carbon in the graphite furnace as well as in food samples, CS was formed in the gas phase without the addition of any molecule forming element externally. The effects of the wavelength selected to detect CS, graphite furnace program, amount of sample, coating of the graphite tube and platform with Ir, and the use of a Pd modifier on the accuracy, precision, and sensitivity were investigated and optimized. Sulfur was determined in an iridium-coated graphite tube/platform at 258.056 nm by applying a pyrolysis temperature of 1000 °C and a molecule forming temperature of 2400 °C. The calibration curve prepared from Na2S was linear between 0.01 μg (LOQ) and 10 μg of S. The accuracy of the method was tested by analyzing certified reference spinach and milk powder samples by applying a linear calibration technique prepared from aqueous standard. The results were in good agreement with certified values. The limit of detection and characteristic mass of the method were 3.5 and 8.1 ng of S, respectively. By applying the optimized parameters, the concentrations of S in onion and garlic samples were determined.

A framework of ferrocene-containing polymers bearing adjustable pH-and redox-active properties in aqueous electrolyte environments was developed. The electroactive metallopolymers were designed to possess enhanced hydrophilicity compared to the vinylferrocene (VFc) homopolymer, poly-(vinylferrocene) (PVFc), by virtue of the comonomer incorporated into the macromolecule, and could also be prepared as conductive nanoporous carbon nanotube (CNT) composites that offered a variety of different redox potentials spanning a ca. 300 mV range. The presence of charged non-redox-active moieties such as methacrylate (MA) in the polymeric structure endowed it with acid dissociation properties that interacted synergistically with the redox activity of the ferrocene moieties to impart pH-dependent electrochemical behavior to the overall polymer, which was subsequently studied and compared to several Nernstian relationships in both homogeneous and heterogeneous configurations. This zwitterionic characteristic was leveraged for the enhanced electrochemical separation of several transition metal oxyanions using a P(VFc 0.63 -co-MA 0.37 )-CNT polyelectrolyte electrode, which yielded an almost twofold preference for chromium as hydrogen chromate versus its chromate form, and also exemplified the electrochemically mediated and innately reversible nature of the separation process through the capture and release of vanadium oxyanions. These investigations into pH-sensitive redox-active materials provide insight for future developments in stimuliresponsive molecular recognition, with extendibility to areas such as electrochemical sensing and selective separation for water purification.