Impact of Shell Composition on Dye Uptake by Capsules of Ionic Liquid.

Encapsulation of ionic liquids (ILs) has been shown to be an effective technique to overcome slow mass transfer rates and handling difficulties that stem from the high viscosity of bulk ILs. These systems commonly rely on diffusion of small molecules through the encapsulating material (shell), into the IL core, and thus the composition of the shell impacts uptake performance. Herein, we report the impact of polymer shell composition on the uptake of the small molecule dye methyl red from water by encapsulated IL. Capsules with core of 1-hexyl-3-methylimidazolium bis(trifluorosulfonyl)imide ([Hmim][TFSI]) were prepared by interfacial polymerization in emulsions stabilized by graphene oxide (GO) nanosheets; the use of different diamines and diisocyanates gave capsule shells with polyureas that were all aliphatic, aliphatic/aromatic, and aliphatic/polar aprotic. These capsules were then added to aqueous solutions of methyl red at different pH values, and migration of the dye into the capsules was monitored by UV-vis spectroscopy, compared to the capsule shell alone. Regardless of the polymer identity, similar extents of dye uptake were observed (>90% at pH = 2), yet capsules with shells containing polyureas with polar aprotic linkages took longer to reach completion. These studies indicate that small changes in capsule shell composition can lead to different performance in small molecule uptake, giving insight into how to tailor shell composition for specific applications, such as solvent remediation and gas uptake.

Capsules of Reactive Ionic Liquids for Selective Capture of Carbon Dioxide at Low Concentrations.

The task-specific ionic liquid (IL), 1-ethyl-3-methylimidazolium 2-cyanopyrolide ([EMIM][2-CNpyr]), was encapsulated with polyurea (PU) and graphene oxide (GO) sheets via a one-pot Pickering emulsion, and these capsules were used to scrub CO2 (0-5000 ppm) from moist air. Up to 60 wt % of IL was achieved in the synthesized capsules, and we demonstrated comparable gravimetric CO2 capacities to zeolites and enhanced absorption rates compared to those of bulk IL due to the increased gas/liquid surface-to-volume area. The reactive IL capsules show recyclability upon mild temperature increase compared to zeolites that are the conventional absorber materials for CO2 scrubbing. The measured breakthrough curves in a fixed bed under 100% relative humidity establish the utility of reactive IL capsules as moisture-stable scrubber materials to separate CO2 from air, outperforming zeolites owing to their higher selectivity. It is shown that thermal stability, CO2 absorption capacity, and rate of uptake by IL capsules can be further modulated by incorporating low-viscosity and nonreactive ILs to the capsule core. This study demonstrates an alternative and facile approach for CO2 scrubbing, where separation from gas mixtures with extremely low partial pressures of CO2 is required.

Stabilization of oil-in-water emulsions with graphene oxide and cobalt oxide nanosheets and preparation of armored polymer particles.

Pickering emulsions are emulsions stabilized by particles instead of small molecules or polymers, and commonly consist of oil droplets dispersed into a continuous water phase with particles lying at the fluid-fluid interface. New particle surfactants are important for tuning the composition and properties of assemblies and enabling advanced applications, such as energy harvesting and management. Although most particle surfactants are spherical, graphene oxide (GO) nanosheets and clay platelets have garnered recent attention as 2D (i.e., planar) particle surfactants. Herein, we report the preparation of Pickering emulsions stabilized by a composite of GO nanosheets and cobalt oxide (CoOx) nanosheets, and illustrate the impact of GO:CoOx ratio, oil identity, and flocculating agent (i.e., salts) on emulsion formation and stability. Distinct effects were noted for salt concentration and identity, as well as GO: CoOx ratio. We further illustrate the applicability of these GO-CoOx-stabilized emulsions in dispersion polymerization, preparing polystyrene particles armored with both nanosheets. This work provides a method for facilitating oil-in-water emulsions with composite particle surfactants that are stable for at least a week and offers the foundation for using the fluid-fluid interface to architect structures of dissimilar materials.

Nitro derivatives of triazetidine: potential high energy density materials.

In a continuing effort to evaluate the properties of new possible high energy density materials, we have calculated the optimized geometries and thermodynamic properties of a series of nitro derivatives of triazetidine, c-CH2(NH)3. After evaluating approximately 50 different levels of NO2 substitution and conformations, we predict that several nitrotriazetidine compounds show some significantly desirable HEDM properties. Graphical abstract The triazetidine molecule, the parent structure for a series of new hypothetical high energy densitymaterials with various NO2 content.

2D Particles at Fluid-Fluid Interfaces: Assembly and Templating of Hybrid Structures for Advanced Applications.

Fluid-fluid interfaces have widespread applications in personal care products, the food industry, oil recovery, mineral processes, etc. and are also important and versatile platforms for generating advanced materials. In Pickering emulsions, particles stabilize the fluid-fluid interface, and their presence reduces the interfacial energy between the two fluids. To date, most Pickering emulsions stabilized by 2D particles make use of clay platelets or GO nanosheets. These systems have been used to template higher order hybrid, functional materials, most commonly, armored polymer particles, capsules, and Janus nanosheets. This review discusses the experimental and computational study of the assembly of sheet-like 2D particles at fluid-fluid interfaces, with an emphasis on the impact of chemical composition, and the use of these assemblies to prepare composite structures of dissimilar materials. The review culminates in a perspective on the future of Pickering emulsions using 2D particle surfactants, including new chemical modification and types of particles as well as the realization of properties and applications not possible with currently accessible systems, such as lubricants, porous structures, delivery, coatings, etc.

Organic Carbon Amendments for Enhanced Biological Attenuation of Trace Organic Contaminants in Biochar-Amended Stormwater Biofilters.

This study sought to evaluate how dissolved organic carbon (DOC) affects attenuation of trace organic contaminants (TOrCs) in biochar-amended stormwater biofilters. It was hypothesized that (1) DOC-augmented runoff would demonstrate enhanced TOrC biodegradation and (2) biochar-amended sand bearing DOC-cultivated biofilms would achieve enhanced TOrC attenuation due to sorptive retention and biodegradation. Microcosm and column experiments were conducted utilizing actual runoff, DOC from straw and compost, and a suite of TOrCs. Biodegradation of TOrCs in runoff was more enhanced by compost DOC than straw DOC (particularly for atrazine, prometon, benzotriazole, and fipronil). 16S rRNA gene quantification and sequencing revealed that growth-induced microbial community changes were, among replicates, most consistent for compost-augmented microcosms and least consistent for raw runoff microcosms. Compost DOC most robustly enhanced utilization of TOrCs as carbon substrates, possibly due to higher residual nutrient levels upon TOrC exposure. Sand columns containing just 0.5 wt % biochar maintained sorptive TOrC retention in the presence of compost-DOC-cultivated biofilms, and TOrC removal was further enhanced by biological activity. Overall, these results suggest that coamendment with biochar and compost may robustly enhance TOrC attenuation in stormwater biofilters, a finding of significance for efforts to mitigate the impacts of runoff on water quality.