Quinone Reduction in Ionic Liquids for Electrochemical CO₂ Separation

We report the redox activity of quinone materials, in the presence of ionic liquids, with the ability to bind reversibly to CO₂. The reduction potential at which 1,4-naphthoquinone transforms to the quinone dianion depends on the strength of the hydrogen-bonding characteristics of the ionic liquid solvent; under CO₂, this transformation occurs at much lower potentials than in a CO₂-inert environment. In the absence of CO₂, two consecutive reduction steps are required to form first the radical anion and then the dianion, but with the quinones considered here, a single two-electron wave reduction with simultaneous binding of CO₂ occurs. In particular, the 1,4-napthoquinone and 1-ethyl-3-methylimidazolium tricyanomethanide, [emim]­[tcm], system reported here shows a higher quinone solubility (0.6 and 1.9 mol·L^–1 at 22 and 60 °C, respectively) compared to other ionic liquids and most common solvents. The high polarity determined through the Kamlet–Taft parameters for [emim]­[tcm] explains the measured solubility of quinone. The achieved high quinone solubility enables effective CO₂ separation from the dilute gas mixture that is contact with the cathode by overcoming back-diffusive transport of CO₂ from the anodic side

Capture and Electrochemical Reduction of CO₂ Using Molten Alkali Metal Borates

Molten alkali metal borates are a class of molten salts that have recently shown promise as high-temperature sorbents for capture of CO2 and other acid gases. Thermal swing systems based on molten borates have demonstrated CO2 capture capacities greater than those of amines, enabling efficient recovery of high-temperature heat in flue gas without practical concerns commonly associated with solid sorbents at these temperatures. In this work, we exploited generation of carbonates upon CO2 capture by borates to enable their use as electrolytic media for carbon nanotube (CNT) synthesis by CO2 splitting. Here, we report the conditions necessary to synthesize valuable multiwalled CNTs by CO2 capture and conversion as a sustainable alternative to conventional carbon-intensive CNT synthesis techniques. Effects of cathode materials and operating conditions are quantified in sodium lithium borate, achieving significantly higher CO2 uptake capacities than alkali metal carbonate salts for conversion of CO2 into CNTs in the 550–650 °C range

Light-Regulated Supramolecular Engineering of Polymeric Nanocapsules

This article describes the light-driven supramolecular engineering of water-dispersible nanocapsules (NCPs). The novelty of the method lies in the utilization of an appropriate phototrigger to stimulate spherical polymer brushes, consisting of dual-responsive 2-(dimethylamino)­ethyl methacrylate (DMAEMA) and light-sensitive spiropyran (SP) moieties, for the development or disruption of the NCPs in a controlled manner. The fabrication of the nanocarriers is based on the formation of H-type π–π interactions between merocyanine (MC) isomers within the sterically crowded environment of the polymer brushes upon UV irradiation, which enables the SP-to-MC isomerization of the photosensitive species. After HF etching of the inorganic core, dual-responsive polymeric vesicles whose walls’ robustness is provided by the MC–MC cross-link points are formed. Disruption of the vesicles can be achieved remotely by applying a harmless trigger such as visible-light irradiation. The hydrophilic nature of the DMAEMA comonomer facilitates the engineering of the vesicles in environmentally benign aqueous media and enables the controlled alteration of the NCPs size upon variation of the solution pH. The inherent ability of the NCPs to fluoresce in water opens new possibilities for the development of addressable nanoscale capsules for biomedical applications

Kinetics of the Change in Droplet Size during Nanoemulsion Formation

The evolution of droplet size during nanoemulsion formation is critical for the rational design of nanoemulsions in areas such as drug delivery and materials synthesis. In this article, we discuss the relative importance of various time scales involved in nanoemulsion formation and propose a population balance model for droplet breakup that takes into account the droplet’s internal viscosity. The proposed model gives a qualitative agreement between average droplet size and polydispersity data for nanoemulsions prepared by high-pressure homogenization and ultrasonication. On the basis of these modeling results, we propose a correlation to obtain a parity plot for the droplet size data. We show that our model and correlation also work well with data from the existing literature. The proposed model and correlation can be used to guide future population balance studies and experimental preparation of nanoemulsions

Ultra-Wide-Range Electrochemical Sensing Using Continuous Electrospun Carbon Nanofibers with High Densities of States

Carbon-based sensors for wide-range electrochemical detection of redox-active chemical and biological molecules were fabricated by the electrospinning of polyacrylonitrile fibers directly onto a polyacrylonitrile-coated substrate followed by carbonization at 1200 °C. The resulting electrospun carbon nanofibers (ECNFs) were firmly attached to the substrate with good mesh integrity and had high densities of electronic states (DOS), which was achieved without need for further modifications or the use of any additives. The mass of ECNFs deposited, and thus the electroactive surface area (ESA) of the sensor, was adjusted by varying the electrospinning deposition time, thereby enabling the systematic manipulation of the dynamic range of the sensor. A standard redox probe (Fe­(CN)₆^3–/4–) was used to demonstrate that the ECNF sensor exhibits strong electrocatalytic activity without current saturation at high analyte concentrations. Dopamine was used as a model analyte to evaluate the sensor performance; we find that the ECNF device exhibits a dynamic range ∼10⁵ greater than that of many existing carbon-based sensors. The ECNF sensors exhibited excellent sensitivity, selectivity, stability, and reproducibility for dopamine detection