Polymerized and Colloidal Ionic Liquids─Syntheses and Applications.

The breadth and importance of polymerized ionic liquids (PILs) are steadily expanding, and this review updates advances and trends in syntheses, properties, and applications over the past five to six years. We begin with an historical overview of the genesis and growth of the PIL field as a subset of materials science. The genesis of ionic liquids (ILs) over nano to meso length-scales exhibiting 0D, 1D, 2D, and 3D topologies defines colloidal ionic liquids, CILs, which compose a subclass of PILs and provide a synthetic bridge between IL monomers (ILMs) and micro to macro-scale PIL materials. The second focus of this review addresses design and syntheses of ILMs and their polymerization reactions to yield PILs and PIL-based materials. A burgeoning diversity of ILMs reflects increasing use of nonimidazolium nuclei and an expanding use of step-growth chemistries in synthesizing PIL materials. Radical chain polymerization remains a primary method of making PILs and reflects an increasing use of controlled polymerization methods. Step-growth chemistries used in creating some CILs utilize extensive cross-linking. This cross-linking is enabled by incorporating reactive functionalities in CILs and PILs, and some of these CILs and PILs may be viewed as exotic cross-linking agents. The third part of this update focuses upon some advances in key properties, including molecular weight, thermal properties, rheology, ion transport, self-healing, and stimuli-responsiveness. Glass transitions, critical solution temperatures, and liquidity are key thermal properties that tie to PIL rheology and viscoelasticity. These properties in turn modulate mechanical properties and ion transport, which are foundational in increasing applications of PILs. Cross-linking in gelation and ionogels and reversible step-growth chemistries are essential for self-healing PILs. Stimuli-responsiveness distinguishes PILs from many other classes of polymers, and it emphasizes the importance of segmentally controlling and tuning solvation in CILs and PILs. The fourth part of this review addresses development of applications, and the diverse scope of such applications supports the increasing importance of PILs in materials science. Adhesion applications are supported by ionogel properties, especially cross-linking and solvation tunable interactions with adjacent phases. Antimicrobial and antifouling applications are consequences of the cationic nature of PILs. Similarly, emulsion and dispersion applications rely on tunable solvation of functional groups and on how such groups interact with continuous phases and substrates. Catalysis is another significant application, and this is an historical tie between ILs and PILs. This component also provides a connection to diverse and porous carbon phases templated by PILs that are catalysts or serve as supports for catalysts. Devices, including sensors and actuators, also rely on solvation tuning and stimuli-responsiveness that include photo and electrochemical stimuli. We conclude our view of applications with 3D printing. The largest components of these applications are energy related and include developments for supercapacitors, batteries, fuel cells, and solar cells. We conclude with our vision of how PIL development will evolve over the next decade.

Palladium Enhanced Iron Active Site - An Efficient Dual-Atom Catalyst for Oxygen Electroreduction.

Metal-nitrogen-carbon (M-C/N) electrocatalysts have been shown to have satisfactory catalytic activity and long-term durability for the oxygen reduction reaction (ORR). Here, a strategy to prepare a new electrocatalyst (Fe&Pd-C/N) using a unique metal-containing ionic liquid (IL) is exploited, in which Fe & Pd ions are positively charged species atomically dispersed by coordination to the N of the N-doped C substrate, C/N. X-ray absorption fine structure, XPS and aberration-corrected transmission electron microscopy results verified a well-defined dual-atom configuration comprising Fe+2.x -N4 coupled Pd2+ -N4 sites and well-defined spatial distribution. Electronic control of a coupled Fe-Pd structure produces an electrocatalyst that exhibits superior performance with enhanced activity and durability for the ORR compared to that of commercial Pt/C (20%, Johnson Matthey) in both alkaline and acid media. Density functional theory calculations indicate that Pd atom can enhance the catalytic activity of the Fe active sites adjacent to Pd sites by changing the electronic orbital structure and Bader charge of the Fe centers. The excellent catalytic performance of the Fe&Pd-C/N electrocatalyst is demonstrated in zinc-air batteries and hydrogen-air fuel cells.

Frontiers in poly(ionic liquid)s: syntheses and applications.

We review recent works on the synthesis and application of poly(ionic liquid)s (PILs). Novel chemical structures, different synthetic strategies and controllable morphologies are introduced as a supplement to PIL systems already reported. The primary properties determining applications, such as ionic conductivity, aqueous solubility, thermodynamic stability and electrochemical/chemical durability, are discussed. Furthermore, the near-term applications of PILs in multiple fields, such as their use in electrochemical energy materials, stimuli-responsive materials, carbon materials, and antimicrobial materials, in catalysis, in sensors, in absorption and in separation materials, as well as several special-interest applications, are described in detail. We also discuss the limitations of PIL applications, efforts to improve PIL physics, and likely future developments.

Catalysis of Carbon Dioxide Photoreduction on Nanosheets: Fundamentals and Challenges.

The transformation of CO2 into fuels and chemicals by photocatalysis is a promising strategy to provide a long-term solution to mitigating global warming and energy-supply problems. Achievements in photocatalysis during the last decade have sparked increased interest in using sunlight to reduce CO2 . Traditional semiconductors used in photocatalysis (e.g. TiO2 ) are not suitable for use in natural sunlight and their performance is not sufficient even under UV irradiation. Some two-dimensional (2D) materials have recently been designed for the catalytic reduction of CO2 . These materials still require significant modification, which is a challenge when designing a photocatalytic process. An overarching aim of this Review is to summarize the literature on the photocatalytic conversion of CO2 by various 2D materials in the liquid phase, with special attention given to the development of novel 2D photocatalyst materials to provide a basis for improved materials.

Scalable exfoliation and dispersion of two-dimensional materials - an update.

The preparation of dispersions of single- and few-sheet 2D materials in various solvents, as well as the characterization methods applied to such dispersions, is critically reviewed. Motivating factors for producing single- and few-sheet dispersions of 2D materials in liquids are briefly discussed. Many practical applications are expected for such materials that do not require high purity formulations and tight control of donor and acceptor concentrations, as required in conventional Fab processing of semiconductor chips. Approaches and challenges encountered in exfoliating 2D materials in liquids are reviewed. Ultrasonication, mechanical shearing, and electrochemical processing approaches are discussed, and their respective limitations and promising features are critiqued. Supercritical and more conventional liquid and solvent processing are then discussed in detail. The effects of various types of stabilizers, including surfactants and other amphiphiles, as well as polymers, including homopolymeric electrolytes, nonionic polymers, and nanolatexes, are discussed. Consideration of apparent successes of stabilizer-free dispersions indicates that extensive exfoliation in the absence of dispersing aids results from processing-induced surface modifications that promote stabilization of 2D material/solvent interactions. Also apparent paradoxes in "pristineness" and optical extinctions in dispersions suggest that there is much we do not yet quantitatively understand about the surface chemistry of these materials. Another paradox, emanating from modeling dilute solvent-only exfoliation by sonication using polar components of solubility parameters and surface tension for pristine graphene with no polar structural component, is addressed. This apparent paradox appears to be resolved by realizing that the reactivity of graphene to addition reactions of solvent radicals produced by sonolysis is accompanied by unintended polar surface modifications that promote attractive interactions with solvent. This hypothesis serves to define important theoretical and experimental studies that are needed. We conclude that the greatest promise for high volume and high concentration processing lies in applying methods that have not yet been extensively reported, particularly wet comminution processing using small grinding media of various types.

Polymerized Paired Ions as Polymeric Ionic Liquid-Proton Conductivity.

A new polymerized ionic liquid has been derived by photopolymerization of a stimuli-responsive ionic liquid surfactant, ILAMPS, which is composed of polymerizable, paired ions. The cation is 1-methyl-3-[11-(acryloyloxy)undecyl] imidazolium (IL), and the anion is 2-acrylamido-2-methyl-1-propanesulfonate (AMPS). This ion combination is a new ionic liquid. The resulting hygroscopic resins are highly polarizable, suitable for sensor design and for ultracapacitor fabrication and proton conducting. Interactions of imidazolium with anions provide basis for stimuli-responsiveness, and are used to promote proton transport. Doping with one equivalent of HPF6 at 0% relative humidity produces a 100-fold increase in proton conductivity at 100-125 °C and activation energies for proton transport lower than those of Nafion at water loadings less than 5 per sulfonate.

Comprehensive assessment of radiation dose estimates for the CORE320 study.

OBJECTIVE. The purpose of this study was to comprehensively study estimated radiation doses for subjects included in the main analysis of the Combined Non-invasive Coronary Angiography and Myocardial Perfusion Imaging Using 320 Detector Computed Tomography (CORE320) study ( ClinicalTrials.gov identifier NCT00934037), a clinical trial comparing combined CT angiography (CTA) and perfusion CT with the reference standard catheter angiography plus myocardial perfusion SPECT. SUBJECTS AND METHODS. Prospectively acquired data on 381 CORE320 subjects were analyzed in four groups of testing related to radiation exposure. Radiation dose estimates were compared between modalities for combined CTA and perfusion CT with respect to covariates known to influence radiation exposure and for the main clinical outcomes defined by the trial. The final analysis assessed variations in radiation dose with respect to several factors inherent to the trial. RESULTS. The mean radiation dose estimate for the combined CTA and perfusion CT protocol (8.63 mSv) was significantly (p < 0.0001 for both) less than the average dose delivered from SPECT (10.48 mSv) and the average dose from diagnostic catheter angiography (11.63 mSv). There was no significant difference in estimated CTA-perfusion CT radiation dose for subjects who had false-positive or false-negative results in the CORE320 main analyses in a comparison with subjects for whom the CTA-perfusion CT findings were in accordance with the reference standard SPECT plus catheter angiographic findings. CONCLUSION. Radiation dose estimates from CORE320 support clinical implementation of a combined CT protocol for assessing coronary anatomy and myocardial perfusion.

A Kinetic Model for Exfoliation Kinetics of Layered Materials.

Exfoliation of two-dimensional materials is key to obtaining high-performance properties. We present a simple kinetic model for exfoliation that is readily solved analytically. Random and irreversible sheet separation is postulated in the presence of highly effective stabilizers. This model appears to quantitatively fit graphene exfoliation data, and it illuminates mechanistic aspects of exfoliation. Thicker sheets exfoliate much faster than trilayer and bilayer sheets. Exfoliation follows highly activated diffusion-controlled intercalation of stabilizer into inter-sheet galleries. Application to the most concentrated graphene exfoliation data available supports these assumptions and provides insight for practical treatment regimens.

Leaflet-heterostructures by MWCNT self-assembly following electrospinning.

Electrospinning of nanocarbons such as graphene and carbon nanotubes typically produces mats composed of one-dimensional fibers where the carrier polymer encapsulates the nanocarbons. Recently it was found that decreasing the amount of carrier polymer in approaching the electrospinning-electrospray boundary for graphene suspensions resulted in retention of the graphene two-dimensional anisotropy with one-dimensional carrier polymer fibers connecting flakes. We explored a similar decrease in carrier polymer in MWCNT suspensions to investigate the network topology that might ensue. Unexpectedly, two-dimensional leaflet meso-networks were obtained wherein the leaflets comprise laterally aligned MWCNTs one to several nanotubes thick. A mechanism based on capillary force-driven MWCNT self-assembly activated by menisci formed during drying of electrospun fibers is presented. Such materials offer new approaches to producing high surface-area coatings for catalytic and energy applications and suggest ways of formulating two-dimensional MWCNT assemblies in metal foams and other open-cell porous materials.

Porating anion-responsive copolymeric gels.

A polymerizable ionic liquid surfactant, 1-(11-acryloyloxyundecyl)-3-methylimidiazolium bromide (ILBr), was copolymerized with methyl methacrylate (MMA) in aqueous microemulsions at 30% (ILBr w/w) and various water to MMA ratios. The ternary phase diagram of the ILBr/MMA/water system was constructed at 25 and 60 °C. Homopolymers and copolymers of ILBr and MMA were produced by thermally initiated chain radical microemulsion polymerization at various compositions in bicontinuous and reverse microemulsion subdomains. Microemulsion polymerization reaction products varied from being gel-like to solid, and these materials were analyzed by thermal and scanning electron microscopy methods. Microemulsion polymerized materials were insoluble in all solvents tested, consistent with light cross-linking. Ion exchange between Br(-) and PF6(-) in these copolymeric materials resulted in the formation of open-cell porous structures in some of these materials, as was confirmed by scanning electron microscopy (SEM). Several compositions illustrate the capture of prepolymerization nanoscale structure by thermally initiated polymerization, expanding the domain of compositions exhibiting this feat and yet to be demonstrated in any other system. Regular cylindrical pores in interpenetrating ILBr-co-MMA and PMMA networks are produced by anion exchange in the absence of templates. A percolating cluster/bicontinuous transition is "captured" by SEM after using anion exchange to visualize the mixed cluster/pore morphology. Some design principles for achieving this capture and for obtaining stimuli responsive solvogels are articulated, and the importance of producing solvogels in capturing the nanoscale is highlighted.

Organosiloxane supramolecular liquids--surface-energy-driven phase transitions.

Autocondensation of organoalkoxysilanes and subsequent anion exchange produces organosiloxane supramolecular liquids which are core-free and solvent-free nanoparticle nanofluids. This hybrid supramolecular liquid, [C(81)H(156)NO(3)S(SiO([2>x>3/2]))](y), exhibits (see TEM image; 200 nm width) interparticle menisci and softness (from imputed deformations) of interparticle potential.

Anion responsive imidazolium-based polymers.

Stimuli responsiveness in polymer design is providing basis for diversely new and advanced materials that exhibit switchable porosity in membranes and coatings, switchable particle formation and thermodynamically stable nanoparticle dispersions, polymers that provide directed mechanical stress in response to intensive fields, and switchable compatibility of nanomaterials in changing environments. The incorporation of ionic liquid monomers has resulted in many new polymers based on the imidazolium group. These polymers exhibit all of the above-articulated material properties. Some insight into how these anion responsive polymers function has become empirically available. Much opportunity remains for extending our understanding as well as for designing more refined stimuli-responsive materials.

Triblock copolymer based on poly(propylene oxide) and poly(1-[11-acryloylundecyl]-3-methyl-imidazolium bromide).

The controlled atom transfer radical polymerization of an ionic liquid, 1-(11-acryloylundecyl)-3-methyl imidazolium bromide (ILBr), from both ends of a telechelic poly(propylene oxide) (PPO) macroinitiator, end-functionalized with bromoisobutyryloyl is reported. The resulting highly water-soluble triblock, poly(ILBr-b-PO-b-ILBr) is multistimuli responsive. This new class of triblocks exhibits classical surface activity in lowering surface tension at the air-water interface and in modifying wetting in waterborne coatings. It also immunizes model colloids against coagulation induced by Debye-Hückel (indifferent electrolyte) electrostatic screening. Further, sol-gel thermoreversibility is unexpectedly found as an additional form of stimuli responsiveness.

Stimuli responsive poly(1-[11-acryloylundecyl]-3-methyl-imidazolium bromide): dewetting and nanoparticle condensation phenomena.

A stimuli-responsive homopolymer poly(ILBr) is fabricated via a "two-phase" atom transfer radical polymerization (ATRP) process, where ILBr stands for the reactive ionic liquid surfactant, 1-[11-acryloylundecyl]-3-methyl-imidazolium bromide. An extraordinarily wide molecular weight distribution (PDI = 6.0) was obtained by introducing the initiator (4-bromomethyl methyl benzoate) in a heterogeneous two-phase process. The molecular weight distribution of poly(ILBr) was characterized by size-exclusion chromatography (SEC). The resulting homopolymer was found to be surface active and stimuli responsive. Poly(ILBr) films coated on quartz exhibit stimuli-responsive dewetting after ion exchange of Br(-) by PF(6)(-). This dewetting phenomenon can be understood in chain segmental terms as a stimuli-induced structural relaxation and appears to be the first such reported stimuli-responsive polymeric dewetting. Titrating aqueous poly(ILBr) with aqueous bis(2-ethylhexyl)sulfosuccinate induces nanophase separation and results in the condensation of nanoparticles 30-60 nm in diameter.

Sustainable polymerizations in recoverable microemulsions.

Free radical and atom-transfer radical polymerizations were conducted in monomer/ionic liquid microemulsions. After the polymerization and isolation of the resultant polymers, the mixture of the catalyst and ionic liquids (surfactant and continuous phase) can be recovered and reused, thereby dramatically improving the environmental sustainability of such chemical processing. The addition of monomer to recovered ionic liquid mixtures regenerates transparent, stable microemulsions that are ready for the next polymerization cycle upon addition of initiator. The method combines the advantages of IL recycling and microemulsion polymerization and minimizes environmental disposable effects from surfactants and heavy metal ions.

Coronary CT angiography using 64 detector rows: methods and design of the multi-centre trial CORE-64.

Multislice computed tomography (MSCT) for the noninvasive detection of coronary artery stenoses is a promising candidate for widespread clinical application because of its non-invasive nature and high sensitivity and negative predictive value as found in several previous studies using 16 to 64 simultaneous detector rows. A multi-centre study of CT coronary angiography using 16 simultaneous detector rows has shown that 16-slice CT is limited by a high number of nondiagnostic cases and a high false-positive rate. A recent meta-analysis indicated a significant interaction between the size of the study sample and the diagnostic odds ratios suggestive of small study bias, highlighting the importance of evaluating MSCT using 64 simultaneous detector rows in a multi-centre approach with a larger sample size. In this manuscript we detail the objectives and methods of the prospective "CORE-64" trial ("Coronary Evaluation Using Multidetector Spiral Computed Tomography Angiography using 64 Detectors"). This multi-centre trial was unique in that it assessed the diagnostic performance of 64-slice CT coronary angiography in nine centres worldwide in comparison to conventional coronary angiography. In conclusion, the multi-centre, multi-institutional and multi-continental trial CORE-64 has great potential to ultimately assess the per-patient diagnostic performance of coronary CT angiography using 64 simultaneous detector rows.

Supercritical Fluid-Facilitated Exfoliation and Processing of 2D Materials.

Since the first intercalation of layered silicates by using supercritical CO2 as a processing medium, considerable efforts have been dedicated to intercalating and exfoliating layered two-dimensional (2D) materials in various supercritical fluids (SCFs) to yield single- and few-layer nanosheets. Here, recent work in this area is highlighted. Motivating factors for enhancing exfoliation efficiency and product quality in SCFs, mechanisms for exfoliation and dispersion in SCFs, as well as general metrics applied to assess quality and processability of exfoliated 2D materials are critically discussed. Further, advances in formation and application of 2D material-based composites with assistance from SCFs are presented. These discussions address chemical transformations accompanying SCF processing such as doping, covalent surface modification, and heterostructure formation. Promising features, challenges, and routes to expanding SCF processing techniques are described.

Stimuli-responsively porating gels by condensation.

A polyurethane (PU) resin derived from glycerol and hexamethylene diisocyanate and an imidazolium bromide ionic liquid chain terminator yield a stimuli-responsive resin that reversibly porates as a solvation response.

Reactive CeO2 nanofluids for UV protective films.

We investigate surface modification by organo-trimethoxysilanes of nano-ceria and if such surface-modified nano-ceria can be transformed into solvent-free nanofluids. We also examine whether simultaneous modification with ionic liquid salts and with acrylate groups yields nanofluids suitable for forming UV-protective films and clear coatings by UV-initiated polymerization. Nominally 3nm diameter CeO2 was successfully synthesized and surface decorated with an ionic liquid salt and with acrylate groups to produce a core/shell structured solvent-free nanofluid after ion exchange of chloride for a soft polyoxyethylene sulfonate anion. This room temperature nanofluid melts at about -10°C and exhibits a glass transition at about -71°C. The melting enthalpy, about 19J/g, corresponds approximately to the gain in surface free energy of such nanofluid particles upon transforming from the solid state to liquid state. Robust films were made by UV photoinitiation of this nanofluid in combination with ethylene glycol dimethacrylate and with a polyoxyethylene diacrylate to yield cross-linked films with absorption coefficients α350nm=6.6±0.8cm2/mg and α300nm=24.5±3.5cm2/mg. Average near UV protection over 300-350nm of 1-3 optical density units can be obtained with 0.065-0.19mg/cm2 of CeO2. These materials appear almost three-fold more effective, per unit ceria, than previously reported clearcoats of nanoceria.

Surfactant ionic liquid-based microemulsions for polymerization.

Surfactants based on imidazolium ionic liquids (ILs), including polymerizable surfactant ILs, have been synthesized and used to stabilize polymerizable microemulsions useful for producing polymer nanoparticles, gels, and open-cell porous materials.