Tailoring intermolecular interactions to develop a low-temperature electrolyte system consisting of 1-butyl-3-methylimidazolium iodide and organic solvents.

Ionic liquids (ILs) exhibit remarkable properties and great tunability, which make them an attractive class of electrolyte materials for a variety of electrochemical applications. However, despite the promising progress for operating conditions at high temperatures, the development of their low-temperature viability as electrolytes is still limited due to the constrains from thermal and ion transport issues with a drastic decrease in temperature. In this study, we present a liquid electrolyte system based on a mixture of 1-butyl-3-methylimidazolium iodide ([BMIM][I]), γ-butyrolactone (GBL), propylene carbonate (PC), and lithium iodide (LiI) and utilize its molecular interactions to tailor its properties for extremely low-temperature sensing applications. In particular, the carbonyl group on both PC and GBL can form hydrogen bonds with the imidazolium cation, as indicated by Fourier transform infrared spectroscopy (FTIR), and the extent of these interactions between ions and molecules was also characterized and quantified via proton nuclear magnetic resonance (1H NMR) spectroscopy. More importantly, at the optimal ratio, the organic solvents do not have excess content to form aggregates, which may cause undesired crystallization before the glass transition. The microscopic evolutions of the systems are correlated with their bulk behaviors, leading to improvements in their thermal and transport properties. The optimized formulation of [BMIM][I]/PC/GBL/LiI showed a low glass transition temperature (T g) of -120 °C and an effectively reduced viscosity of 0.31 Pa s at -75 °C. The electrochemical stability of the electrolyte was also validated to support the targeted iodide/triiodide redox reactions without interference.

A Dual Ionic Liquid-Based Low-Temperature Electrolyte System.

Ionic liquids (ILs) show a promising future as electrolytes in electrochemical devices. In particular, IL-based electrolytes bring operations at extreme temperatures to realization that conventional electrolytes fail to accomplish. Although IL electrolytes demonstrate considerable progress in high-temperature applications, their breakthroughs in devices operating at low temperatures are still very limited due to undesirable phase transitions and unsatisfying transport properties. In this study, we present an approach where, by tuning molecular interactions in the system, the designed electrolyte of an IL-based mixture can reach a lower operating temperature with improved transport properties. We have discovered that the incorporation of the IL, ethylammonium nitrate ([EA][N]), can contribute to reforming the molecular interactions within the system, which effectively resolve the crystallization accompanied with the excess of water and retain a low glass transition temperature. The reported liquid electrolyte systems based on a mixture of 1-butyl-3-methylimidazolium iodide ([BMIM][I]), [EA][N], water, and lithium iodide exhibit a glass transition temperature below -105 °C. Furthermore, the optimized electrolyte system shows significant viscosity reduction and ionic conductivity enhancement from 25 to -75 °C. The influence is also noticeable on the increased ionicity, which made the developed electrolyte comparable with other good ILs under the Walden rule. The electrochemical stability of the electrolyte system is revealed by a steady and reproducible profile of iodide/triiodide redox reactions at room temperature over a proper potential window via cyclic voltammetry. The results from this work not only provide a potential solution to applications of the iodide/triiodide redox couple-based electrochemical devices at low temperatures but also show a practical approach to obtain tailored properties of a mixture system via modifying molecular interactions.

Development of visible-light responsive and mechanically enhanced "smart" UCST interpenetrating network hydrogels.

An interpenetrating polymer network (IPN), chlorophyllin-incorporated environmentally responsive hydrogel was synthesized and exhibited the following features: enhanced mechanical properties, upper critical solution temperature (UCST) swelling behavior, and promising visible-light responsiveness. Poor mechanical properties are known challenges for hydrogel-based materials. By forming an interpenetrating network between polyacrylamide (PAAm) and poly(acrylic acid) (PAAc) polymer networks, the mechanical properties of the synthesized IPN hydrogels were significantly improved compared to hydrogels made of a single network of each polymer. The formation of the interpenetrating network was confirmed by Fourier Transform Infrared Spectroscopy (FTIR), the analysis of glass transition temperature, and a unique UCST responsive swelling behavior, which is in contrast to the more prevalent lower critical solution temperature (LCST) behaviour of environmentally responsive hydrogels. The visible-light responsiveness of the synthesized hydrogel also demonstrated a positive swelling behavior, and the effect of incorporating chlorophyllin as the chromophore unit was observed to reduce the average pore size and further enhance the mechanical properties of the hydrogel. This interpenetrating network system shows potential to serve as a new route in developing "smart" hydrogels using visible-light as a simple, inexpensive, and remotely controllable stimulus.

Colloidal lattices of environmentally responsive microgel particles at ionic liquid-water interfaces.

This work reports new evidence of the versatility of soft and environmentally responsive micron-sized colloidal gel particles as stabilizers at ionic liquid-water droplet interfaces. These particles display a duality with properties ascribed typically to both polymeric and colloidal systems. The utilization of fluorescently labeled composite microgel particles allows in-situ and facile visualization without the necessity of invasive sample preparation. When the prepared particles form monolayers equilibrated at the ionic liquid-water interface on fully covered droplets, the colloidal lattice re-orders itself depending on the surface charge of these particles. Finally, we demonstrate that the spontaneously formed and densely packed layer of microgel particles can be employed for extraction applications, as the interface remains permeable to small active species.

Pyrrole-based poly(ionic liquids) as efficient stabilizers for formation of hollow multi-walled carbon nanotubes particles.

Poly(ionic liquid) (PIL) derivatives with pyrrole intrinsically conducting polymer (ICP) backbones were synthesized and utilized as novel dispersants of multi-walled carbon nanotubes (MWCNTs) in various aqueous and non-aqueous systems, including polar and nonpolar solvents. This is due to the highly tunable nature of the PIL, in which the PILs of varying polarity with the same pyrrole-based polycation can be synthesized. The dispersions are exceedingly stable over many months, and with the addition of hexane, Pickering (solid-stabilized) emulsions with the PIL-stabilized MWCNTs at the droplet interfaces were formed. Depending on the hydrophobicity of the PIL, hexane-in-water and hexane-in-acetonitrile emulsions were formed, the latter marking the first non-aqueous CNT-stabilized emulsions, further advancing the processability of CNTs. The PIL-stabilized CNT Pickering emulsion droplets generated hollow conductive particles by subsequent drying of the emulsions. With emulsion templating, the hollow shells could be used as a payload carrier, depending on the solubility of the payload in the droplet phase of the emulsion. This was demonstrated with silicon nanoparticles, which have limited dispersibility in aqueous environments, but great scientific interest due to their potential electrochemical applications. Overall, this work explored a new class of efficient PIL-ICP hybrid stabilizers with tunable hydrophobicity, with hollow particle formation capability.

Multipetal-Structured and Dumbbell-Structured Gold-Polymer Composite Particles with Self-Modulated Catalytic Activity.

A simple synthesis route for gold-polymer composite particles with controlled structure (multipetal structure and dumbbell structure) is developed. It is intriguing to observe that by controlling the reaction time and size of gold nanoparticles (AuNPs), tetrapetal-, tripetal-, and dumbbell-structured gold-polystyrene composite are obtained via seeded polymerization. The average number of petals on a single AuNP increases with the AuNP diameter. These particles show potential applications as building blocks for advanced ordered and hierarchical supracolloidal materials. Further, with the incorporation of poly(N-isopropylacrylamide) (PNIPAm), "smart" thermoresponsive dumbbell-structured gold-PNIPAm/polystyrene composite particles are formed. Significant size variation is validated for particles with 83 and 91 wt % PNIPAm content around lower critical solution temperature (LCST), which results in self-modulated catalytic activity.

A Combined Experimental and Molecular Dynamics Study of Iodide-Based Ionic Liquid and Water Mixtures.

Iodide-based ionic liquids have been widely employed as iodide sources in electrolytes for applications utilizing the triiodide/iodide redox couple. While adding a low-viscosity solvent such as water to ionic liquids can greatly enhance their usefulness, mixtures of highly viscous iodide-containing ILs with water have never been studied. This paper investigates, for the first time, mixtures of water and the ionic liquid 1-butyl-3-methylimidazolium iodide ([BMIM][I]) through a combined experimental and molecular dynamics study. The density, melting point, viscosity, and conductivity of these mixtures were measured by experiment. The composition region below 50% water by mole was found to differ dramatically from the region above 50% water, with trends in density and melting point differing before and after that point. Water was found to have a profound effect on viscosity and conductivity of the IL, and the effect of hydrogen bonding was discussed. Molecular dynamics simulations representing the same mixture compositions were performed. Molecular ordering was observed, as were changes in this ordering corresponding to water content. Molecular ordering was related to the experimentally measured mixture properties, providing a possible explanation for the two distinct composition regions identified by experiment.

Adsorption and release of surfactant into and from multifunctional zwitterionic poly(NIPAm-co-DMAPMA-co-AAc) microgel particles.

We synthesize monodispersed zwitterionic microgel (ZI-MG) particles that undergo an extensive, reversible change in volume in response to environmental stimuli such as pH and temperature. These aqueous ZI-MG dispersions exhibit a minimum hydrodynamic diameter value at an adjustable isoelectric point (IEP). In addition, the study elucidates the controlled uptake and release of ionic and nonionic surfactants from these particle systems. The extent of surfactant loading and the ensuing relative swelling/deswelling behaviors within the colloidal polymer networks are explained in terms of their binding interactions.

Thermo-responsiveness and tunable optical properties of asymmetric polystyrene/PNIPAM-gold composite particles.

Environmentally responsive polystyrene/poly (N-isopropylacrylamide)-gold composite particles are successfully synthesized via a Pickering emulsion polymerization method. It is found that the core-shell and asymmetric structured particles are simultaneously formed during the polymerization. Compared with the core-shell structured composite particles, the asymmetric particles have a higher thermo-responsiveness as a result of differences in morphology and formation mechanism. For asymmetric composite particles, an increase in N-isopropylacrylamide (NIPAAM) content leads to more significant size variation upon temperature changes. From rheology measurements, the viscosity of asymmetric particles suspension greatly decreases as temperature is increased above the lower critical solution temperature (LCST). The large size decrease in asymmetric composite particles gives rise to a significant scattering intensity increase, as a result of increased refractive index contrast between the PNIPAM content and surrounding water. The resulting size decrease also leads to tunable surface plasmon resonance properties.

Core-shell and asymmetric polystyrene-gold composite particles via one-step Pickering emulsion polymerization.

Core-shell structured polystyrene-gold composite particles are synthesized from one-step Pickering emulsion polymerization. The surface coverage of the core-shell composite particles is improved with increasing gold nanoparticle (AuNP) hydrophobicity and concentration. At high surface coverage, the AuNPs exhibit an ordered hexagonal pattern, likely due to electrostatic repulsion during the emulsion polymerization process. In addition to core-shell structured polystyrene-gold composite particles, an intriguing observation is that at low AuNP concentrations, asymmetric polystyrene-gold nanocomposite particles are simultaneously formed, where a single gold nanoparticle is attached onto each polystyrene particle. It is found that these asymmetric particles are formed via a "seeded-growth" mechanism. The core-shell and asymmetric polystyrene-gold composite particles prove to be efficient catalysts as they successfully catalyze the Rhodamine B reduction reaction with stable performance and show high recyclability as catalysts.

Particle self-assembly at ionic liquid-based interfaces.

This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid-water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid-water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water-ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil or water is incorporated.

Comparison of the capillary wave method and pressure tensor route for calculation of interfacial tension in molecular dynamics simulations.

We have studied the calculation of surface and interfacial tension for a variety of liquid-vapor and liquid-liquid interfaces using molecular dynamics (MD) simulations. Because of the inherently small scale of MD systems, large pressure fluctuations can cause imprecise calculations of surface tension using the pressure tensor route. The capillary wave method exhibited improved precision and stability throughout all of the simulated systems in this study. In order to implement this method, the interface was defined by fitting an error function to the density profile. However, full mapping of the interface from coordinate files produced enhanced accuracy. Upon increasing the system size, both methods exhibited higher precision, although the capillary wave method was still more reliable.

Adsorption and release of active species into and from multifunctional ionic microgel particles.

We synthesize monodisperse ionic microgel particles which undergo a large change in volume in response to environmental stimuli such as pH and temperature. In addition, the study elucidates the effective uptake and release of rheology modifiers from these microgel particles to alter the bulk viscosity of a surrounding fluid. Moreover, we found that the prepared ionic microgel particles can demonstrate abilities to adsorb and repel iron oxide nanoparticles (Fe3O4-NPs) upon pH variation. The extent of the loading of Fe3O4-NPs within the colloidal particles and morphology can be manipulated by tunable interactions between the Fe3O4-NPs and ionic microgel particles.

Nonconvective mixing of miscible ionic liquids.

Ionic liquids (ILs) are ionic compounds that are liquid at room temperature. We studied the spontaneous mixing behavior between two ILs, ethylammonium nitrate (EAN) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), and observed notable phenomena. Experimental studies showed that the interface between the two ILs was unusually long-lived, despite the ILs being miscible with one another. Molecular dynamics (MD) simulations supported these findings and provided insight into the micromixing behavior of the ILs. We found that not only did the ions experience slow diffusion as they mix but also exhibited significant ordering into distinct regions. We suspect that this ordering disrupted concentration gradients in the direction normal to the interface, thus hindering diffusion in this direction and allowing the macroscopic interface to remain for long periods of time. Intermolecular interactions responsible for this behavior included the O-NH interaction between the EAN ions and the carbon chain-carbon chain interactions between the [BMIM](+) cations, which associate more strongly in the mixed state than in the pure IL state.

Spontaneous transport of microparticles across liquid-liquid interfaces.

Transporting micrometer-sized particles through the liquid-liquid interface generally requires high shear force and sometimes surfactant functionalization. Without these aids, particles adhere to the interface due to strong capillary forces (can be on the order of 10(6) kT). Thus, spontaneous transport of microparticles through the liquid-liquid interface has not yet been reported. However, we present a new phenomenon here: some ionic liquids (ILs) possess powerful extraction capabilities and can cause microparticles to migrate across the interface without the aid of any shear forces. Both single particles and clusters of particles were observed to adsorb to, then "jump" across the interface and finally detach. In the absence of external mixing, particles as large as 4 µm (in diameter) could completely penetrate the IL/water interface, despite the significant adhesive forces. We have presented a hypothesis that these forces were overcome by ions dissolved in the non-IL phase, which helped by covering the particle surfaces, allowing for more favorable interactions with the IL.

Controlled morphology of thin film silicon integrated with environmentally responsive hydrogels.

Environmentally responsive hydrogels hold multiple important applications. However, the functionality of these materials alone is often limited in comparison to other materials like silicon; thus, there is a need to integrate soft and hard materials for the advancement of environmentally sensitive materials. Here we demonstrate the capability of integrating a thermoresponsive hydrogel, poly(N-isopropylacrylamide), with thin film silicon ribbons, enabling the stiff silicon ribbons to become adaptive and drivable by the soft environmentally sensitive substrate. This integration provides a means of mechanical buckling of the thin silicon film due to changes in environmental stimuli (e.g., temperature, pH). We also investigate how advanced lithographic techniques can be used to generate patterned deformation on the aforementioned integrated structures. Furthermore, we explore multilayer hybrid hydrogel structures formed by the integration of different types of hydrogels that have tunable curvatures under the influence of different stimuli. Silicon thin film integration on such tunable curvature substrates reveal characteristic reversible buckling of the thin film in the presence of multiple stimuli. These results open new opportunities for developing stretchable and intelligent devices for multiple applications.

Electronically programmable, reversible shape change in two- and three-dimensional hydrogel structures.

Combining compliant electrode arrays in open-mesh constructs with hydrogels yields a class of soft actuator, capable of complex, programmable changes in shape. The results include materials strategies, integration approaches, and mechanical/thermal analysis of heater meshes embedded in thermoresponsive poly(N-isopropylacrylamide) (pNIPAM) hydrogels with forms ranging from 2D sheets to 3D hemispherical shells.

Molecular dynamics studies on the adaptability of an ionic liquid in the extraction of solid nanoparticles.

Recently, a number of publications have suggested that ionic liquids (ILs) can absorb solid particles. This development may have implications in fields like oil sand processing, oil spill beach cleanup, and water treatment. In this Article, we provide a computational investigation of this phenomenon via molecular dynamics simulations. Two particle surface chemistries were investigated: (1) hydrocarbon-saturated and (2) silanol-saturated, representing hydrophobic and hydrophilic particles, respectively. Employing 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]) as a model IL, these nanoparticles were allowed to equilibrate at the IL/water and IL/hexane interfaces to observe the interfacial self-assembled structures. At the IL/water interface, the hydrocarbon-based nanoparticles were nearly completely absorbed by the IL, while the silica nanoparticles maintained equal volume in both phases. At the IL/hexane interface, the hydrocarbon nanoparticles maintained minimal interactions with the IL, whereas the silica nanoparticles were nearly completely absorbed by it. Studies of these two types of nanoparticles immersed in the bulk IL indicate that the surface chemistry has a great effect on the corresponding IL liquid structure. These effects include layering of the ions, hydrogen bonding, and irreversible absorption of some ions to the silica nanoparticle surface. We quantify these effects with respect to each nanoparticle. The results suggest that ILs likely exhibit this absorption capability because they can form solvation layers with reduced dynamics around the nanoparticles.

Understanding droplet bridging in ionic liquid-based Pickering emulsions.

We have studied the unique bridging behavior of solid-stabilized oil-in-ionic liquid (IL) and water-in-ionic liquid emulsions with respect to particle concentration, particle size, and droplet phase using a confocal laser scanning microscope. The emulsions exhibited three morphology regimes: (1) single, sparingly covered droplets, (2) bridged clusters of droplets, and (3) fully covered droplets. The degree of bridging was directly proportional to the total potential bridging area which can be determined from the particle size and concentration. This type of emulsion diverges from much of the conventional wisdom of oil-water Pickering emulsions regarding the particle self-assembly onto droplet interfaces and liquid film stability. While the focus here is the bridging regime, we also report interesting observations, specifically, the deformed oil droplets and the transport of excess solid particles into the water droplets, in the fully covered droplet regime. The work identified new self-assembled particle structure and morphology in solid-stabilized emulsions.

Molecular dynamics simulations of charged nanoparticle self-assembly at ionic liquid-water and ionic liquid-oil interfaces.

Nanoparticle self-assembly at liquid-liquid interfaces can be significantly affected by the individual nanoparticle charges. This is particularly true at ionic liquid (IL) based interfaces, where Coulombic forces play a major role. Employing 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]) as a model IL, we have studied the self-assembly of hydrophobic nanoparticles with different surface charges at the IL/water and IL/oil (hexane) interfaces using molecular dynamics simulations. In the IL/water system, the nanoparticles were initially dispersed in the water phase but quickly equilibrated at the interface, somewhat in favor of the IL phase. This preference was lessened with increased nanoparticle charge. In the IL/hexane system, all charged nanoparticles interacted with the IL to some extent, whereas the uncharged nanoparticles remained primarily in the hexane phase. Potential of mean force calculations supported the observations from the equilibrium studies and provided new insights into the interactions of the nanoparticles and ionic liquid based interfaces.