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Depletion-driven assembly has been widely studied for micron-sized colloids, but questions remain at the nanoscale where the governing physics are impacted by the stabilizing surface ligands or wrapping polymers, whose length scales are on the same order as those of the colloidal core and the depletant. Here, we probe how wrapping colloidal tin-doped indium oxide nanocrystals with polymers affects their depletion-induced interactions and assembly in solutions of polyethylene glycol. Copolymers of polyacrylic acid grafted with polyethylene oxide provide nanocrystal wrappings with different effective polymer graft densities and molecular weights. (Ultra) small angle X-ray scattering, coarse-grained molecular dynamics simulation, and molecular thermodynamic theory were combined to analyze how depletant size and polymer wrapping characteristics affect depletion interactions, structure, and phase behavior. The results show how depletant molecular weight, as well as surface density and molecular weight of polymer grafts, set thresholds for assembly. These signatures are unique to depletion-driven assembly of nanoscale colloids and mirror phase behaviors of grafted nanoparticle--polymer composites. Optical and rheological responses of depletion-driven assemblies of nanocrystals with different polymer shell architectures were probed to learn how their structural differences impact properties. We discuss how these handles for depletion-driven assembly at the nanoscale may provide fresh opportunities for designing responsive depletion interactions and dynamically reconfigurable materials.

Water-walking insects can harness capillary forces by changing their body posture to climb or descend the meniscus between the surface of water and a solid object. Controlling surface tension in this manner is necessary for predation, escape and survival. Inspired by this behaviour, we demonstrate autonomous, aqueous-based synthetic systems that overcome the meniscus barrier and shuttle cargo subsurface to and from a landing site and a targeted drop-off site. We change the sign of the contact angle of a coacervate sac containing an aqueous phase or of a hydrogel droplet hanging from the surface by controlling the normal force acting on the sac or droplet. The cyclic buoyancy-induced cargo shuttling occurs continuously, as long as the supply of reactants diffusing to the sac or droplet from the surrounding aqueous phase is not exhausted. These findings may lead to potential applications in autonomously driven reaction or delivery systems and micro-/milli-robotics. Water-walking insects harness capillary forces by changing body posture to climb or descend the meniscus between water and a solid object. Now, autonomous aqueous-based synthetic systems have been shown to overcome the meniscus barrier and shuttle cargo subsurface between a landing site and targeted drop-off sites.

Rigid, solid-state components represent the current paradigm for electronic systems, but they lack post-production reconfigurability and pose ever-increasing challenges to efficient end-of-life recycling. Liquid electronics may overcome these limitations by offering flexible in-the-field redesign and separation at end-of-life via simple liquid phase chemistries. Up to now, preliminary work on liquid electronics has focused on liquid metal components, but these devices still require an encapsulating polymer and typically use alloys of rare elements like indium. Here, using the self-assembly of jammed two-dimensional titanium carbide (Ti

Fine control over the mechanical properties of thin sheets underpins transcytosis, cell shape, and morphogenesis. Applying these principles to artificial, liquid-based systems has led to reconfigurable materials for soft robotics, actuation, and chemical synthesis. However, progress is limited by a lack of synthetic two-dimensional membranes that exhibit tunable mechanical properties over a comparable range to that seen in nature. Here, we show that the bending modulus, B, of thin assemblies of nanoparticle surfactants (NPSs) at the oil-water interface can be varied continuously from sub-kBT to 106kBT, by varying the ligands and particles that comprise the NPS. We find extensive departure from continuum behavior, including enormous mechanical anisotropy and a power law relation between B and the buckling spectrum width. Our findings provide a platform for shape-changing liquid devices and motivate new theories for the description of thin-film wrinkling.

Plastics have revolutionized modern life, but have created a global waste crisis driven by our reliance and demand for low-cost, disposable materials. New approaches are vital to address challenges related to plastics waste heterogeneity, along with the property reductions induced by mechanical recycling. Chemical recycling and upcycling of polymers may enable circularity through separation strategies, chemistries that promote closed-loop recycling inherent to macromolecular design, and transformative processes that shift the life-cycle landscape. Polymer upcycling schemes may enable lower-energy pathways and minimal environmental impacts compared with traditional mechanical and chemical recycling. The emergence of industrial adoption of recycling and upcycling approaches is encouraging, solidifying the critical role for these strategies in addressing the fate of plastics and driving advances in next-generation materials design.

Aqueous rechargeable zinc metal batteries promise attractive advantages including safety, high volumetric energy density, and low cost; however, such benefits cannot be unlocked unless Zn reversibility meets stringent commercial viability. Herein, we report remarkable improvements on Zn reversibility in aqueous electrolytes when phosphonium-based cations are used to reshape interfacial structures and interphasial chemistries, particularly when their ligands contain an ether linkage. This novel aqueous electrolyte supports unprecedented Zn reversibility by showing dendrite-free Zn plating/stripping for over 6400 h at 0.5 mA cm-2 , or over 280 h at 2.5 mA cm-2 , with coulombic efficiency above 99 % even with 20 % Zn utilization per cycle. Excellent full cell performance is demonstrated with Na2 V6 O16 ⋅1.63 H2 O cathode, which cycles for 2000 times at 300 mA g-1 . The microscopic characterization and modeling identify the mechanism of unique interphase chemistry from phosphonium and its functionalities as the key factors responsible for dictating reversible Zn chemistry.

Microporous polymers feature shape-persistent free volume elements (FVEs), which are permeated by small molecules and ions when used as membranes for chemical separations, water purification, fuel cells and batteries1–3. Identifying FVEs that have analyte specificity remains a challenge, owing to difficulties in generating polymers with sufficient diversity to enable screening of their properties. Here we describe a diversity-oriented synthetic strategy for microporous polymer membranes to identify candidates featuring FVEs that serve as solvation cages for lithium ions (Li+). This strategy includes diversification of bis(catechol) monomers by Mannich reactions to introduce Li+-coordinating functionality within FVEs, topology-enforcing polymerizations for networking FVEs into different pore architectures, and several on-polymer reactions for diversifying pore geometries and dielectric properties. The most promising candidate membranes featuring ion solvation cages exhibited both higher ionic conductivity and higher cation transference number than control membranes, in which FVEs were aspecific, indicating that conventional bounds for membrane permeability and selectivity for ion transport can be overcome4. These advantages are associated with enhanced Li+ partitioning from the electrolyte when cages are present, higher diffusion barriers for anions within pores, and network-enforced restrictions on Li+ coordination number compared to the bulk electrolyte, which reduces the effective mass of the working ion. Such membranes show promise as anode-stabilizing interlayers in high-voltage lithium metal batteries. A diversity-oriented synthesis approach that yields a library of architecturally broad microporous polymers is used to develop structurally diverse polymer membranes with ion specificity and to screen their properties.

To understand and control the behavior of electrochemical systems, including batteries and electrocatalysts, we seek molecular-level details of the charge transfer mechanisms at electrified interfaces. Recognizing some key limitations of standard equilibrium electronic structure methods to model materials and their interfaces, we propose applying charge constraints to effectively separate electronic and nuclear degrees of freedom, which are especially beneficial to the study of conversion electrodes, where electronic charge carriers are converted to much slower polarons within a material that is nonmetallic. We demonstrate the need for such an approach within the context of sulfur cathodes and the arrival of Li ions during discharge of a Li-S cell. The requirement that electronic degrees of freedom are arrested is justified by comparison with real-time evolution of the electronic structure. Long-lived metastable configurations provide plenty of time for nuclear dynamics and relaxation in response to the electrification of the interface, a process that would be completely missed without applying charge constraints. This approach will be vital to the study of dynamics at electrified interfaces which may be created deliberately, adding charge to the electrode, or spontaneously, due to finite temperature dynamics in the electrolyte.

Plasmonic metal oxide nanocrystals are interesting electrochromic materials because they display high modulation of infrared light, fast switching kinetics, and durability. Nanocrystals facilitate ...

The efficiency by which monomers may be recovered during the chemical recycling of plastic waste has thus far dominated the discussion over which future polymer chemistries might be more sustainable than those in use today. However, at scale, other factors emerge as equally important, such as the costs of primary versus secondary resin production as well as the energy and carbon intensity of circular manufacturing processes. We apply systems analysis to identify problematic chemical processes used for the primary production of plastics designed for infinite recyclability: polydiketoenamine (PDK) resins from novel triketone and amine monomers. Leveraging this knowledge, we advance a less intensive process for triketone production, which lowers the cost of primary PDK production by 57% and results in 66% less life-cycle greenhouse gas (GHG) emissions. Using the automotive sector as a case study, we discuss the impact of replacing nonrecyclable polyurethane with circular PDK over the next 60 years. We find that the cumulative GHG emissions associated with introducing PDK are half those of staying the course with polyurethane. However, the extent to which circularity is realized through targeted collection and sorting plays the dominant role in determining how much of those savings is practically achievable.

Chemical systems may be maintained far from equilibrium by sequestering otherwise reactive species into different microenvironments. It remains a significant challenge to control the amount of chemical energy stored in such systems and to utilize it on demand to perform useful work. Here, we show that redox-active molecules compartmentalized in multiphasic structured-liquid devices can be charged and discharged to power a load on an external circuit. The two liquid phases of these devices feature charge-complementary polyelectrolytes that serve a dual purpose: they generate an ionically conductive coacervate membrane at the liquid-liquid interface, providing structural support; they also mitigate active-material crossover between phases via ion pairing with the oppositely charged anolyte and catholyte active materials. Structured-liquid batteries enabled by this design were rechargeable over hundreds of hours. We envision that these devices may be integrated with soft electronics to enable functional circuits for smart textiles, medical implants, and wearables.

The ongoing development of redox-active charge carriers for nonaqueous redox-flow batteries has led to energy-dense storage concepts and chemistries with high cell voltages. However, rarely are these candidates for flowable energy storage evaluated in tandem with cell separators compatible with organic solvent, limiting progress in the identification of suitable charge carrier-separator pairings. This is important, as the efficiency of a redox-flow battery is dictated by extent of active species crossover through a separator, dividing the two cells, and the contribution of the separator to cell resistance. Here, we report the size-dependent crossover behavior of a series of redox-active vanadium(III) acetoacetonate, and two polyoxovanadate-alkoxide clusters, [V6O7(OR)12] (R = CH3, C5H11) through separators derived from polymers of intrinsic microporosity (PIMs). We find that highly efficacious active-material blocking requires both increasing the size of the vanadium species and restricting pore swelling of the PIMs in nonaqueous electrolyte. Notably, increasing the size of the vanadium species does not significantly affect its redox reversibility, and reducing swelling decreases the conductivity of the separator by only 50%. By pairing polyoxometalate clusters with PIM membranes in nonaqueous redox-flow batteries, more efficient systems may well be within reach.

The self-assembly of nanoscale materials at the liquid-liquid interface allows for fabrication of three-dimensionally structured liquids with nearly arbitrary geometries and tailored electronic, optical, and magnetic properties. Two-dimensional (2D) materials are highly anisotropic, with thicknesses on the order of a nanometer and lateral dimensions upward of hundreds of nanometers to micrometers. Controlling the assembly of these materials has direct implications for their properties and performance. We here describe the interfacial assembly and jamming of Ti3C2Tx MXene nanosheets at the oil-water interface. Planar, as well as complex, programmed three-dimensional all-liquid objects are realized. Our approach presents potential for the creation of all-liquid 3D-printed devices for possible applications in all-liquid electrochemical and energy storage devices and electrically active, all-liquid fluidics that exploits the versatile structure, functionality, and reconfigurability of liquids.

Summary A hallmark of biological systems is the ability to compartmentalize and coordinate system functions, which has been a challenge even in the most sophisticated synthetic mimics. Here, we demonstrate a strategy to fabricate compartmentalized systems in 3D water-in-water constructs stabilized by an elastic polyanion-polycation coacervate membrane. Using a 3D printer, the length, shape, and diameter of all-aqueous tubules are broadly controlled. We demonstrate directional diffusion of ionic species across the membrane dictated by the preferential affinity of the polyelectrolyte in the oppositely charged phase. In conjunction with microfluidic techniques, continuous selective diffusion and compartmentalized reactions are demonstrated in such all-aqueous systems. A layer-by-layer strategy is also used to tune the membrane’s mechanical properties and to functionalize them. Such a new platform is demonstrated for developing and manipulating continuous separations media or compartmentalized reactive systems that function independently or can be coupled with selective diffusion across the membrane.

Liquid reconfigurable ferromagnetic materials Ferromagnetic materials show a permanent magnetic dipole, whereas superparamagnetic ones only show magnetic properties under an applied field. Some materials, like ferrofluids, show liquid-like behavior but do not retain their magnetization in the absence of an applied field. Liu et al. show remnant magnetization of otherwise superparamagnetic magnetite nanoparticles at an oil-water interface of emulsion droplets (see the Perspective by Dreyfus). The permanent magnetization could be controlled by coupling and uncoupling the magnetization of individual nanoparticles, making it possible to “write and erase” shapes of the droplets or to elongate them into cylinders. Science , this issue p. 264 ; see also p. 219

While many synthetic nanotubes with a hydrophobic lumen and fast molecular transport have been developed, decorating the interior of these channels with polar and/or responsive functional groups remains challenging. In transmembrane proteins like the aquaporin and M2 channels, the presence of histidine residues in a mostly hydrophobic channel has led to enhanced selectivity and pH-based activation. Herein, we report the synthesis of Bzim-CP, a cyclic octapeptide that contains a benzimidazole functionality as a chemical and structural mimic of histidine. Bzim-CP undergoes different protonation states, forms subnanometer nanotubes, and projects two different ionizable functionalities into the lumen. Present studies open up synthetic possibilities to functionalize subnanometer porous channels as a basis toward understanding new transport phenomena.

Recycled plastics are low-value commodities due to residual impurities and the degradation of polymer properties with each cycle of re-use. Plastics that undergo reversible polymerization allow high-value monomers to be recovered and re-manufactured into pristine materials, which should incentivize recycling in closed-loop life cycles. However, monomer recovery is often costly, incompatible with complex mixtures and energy-intensive. Here, we show that next-generation plastics-polymerized using dynamic covalent diketoenamine bonds-allow the recovery of monomers from common additives, even in mixed waste streams. Poly(diketoenamine)s 'click' together from a wide variety of triketones and aromatic or aliphatic amines, yielding only water as a by-product. Recovered monomers can be re-manufactured into the same polymer formulation, without loss of performance, as well as other polymer formulations with differentiated properties. The ease with which poly(diketoenamine)s can be manufactured, used, recycled and re-used-without losing value-points to new directions in designing sustainable polymers with minimal environmental impact.

Here we describe structured liquid batteries, whose membranes self-form via coacervation of polyelectrolytes. The membrane serves as an ion conductor, a physical barrier, and a structural support. Complexation of redox-active small molecules with their complementary polyelectrolyte also mitigates the crossover. The reconfigurability of liquids allows the cell to conform to prescribed patterns and the cells are rechargeable for hundreds of hours.

While not yet competitive with commodity polymers, PDKs are recycled to monomer at lower cost and emissions than virgin resins., Mechanical recycling of polymers downgrades them such that they are unusable after a few cycles. Alternatively, chemical recycling to monomer offers a means to recover the embodied chemical feedstocks for remanufacturing. However, only a limited number of commodity polymers may be chemically recycled, and the processes remain resource intensive. We use systems analysis to quantify the costs and life-cycle carbon footprints of virgin and chemically recycled polydiketoenamines (PDKs), next-generation polymers that depolymerize under ambient conditions in strong acid. The cost of producing virgin PDK resin using unoptimized processes is ~30-fold higher than recycling them, and the cost of recycled PDK resin ($1.5 kg−1) is on par with PET and HDPE, and below that of polyurethanes. Virgin resin production is carbon intensive (86 kg CO2e kg−1), while chemical recycling emits only 2 kg CO2e kg−1. This cost and emissions disparity provides a strong incentive to recover and recycle future polymer waste.

Footwear, carpet, soft furnishings, automotive interiors, and multi-layer packaging are examples of products manufactured from several types of polymers whose inextricability poses significant challenges for recycling at end-of-life. Here, we show that chemical circularity in mixed-polymer recycling becomes possible by controlling the rates of depolymerization of polydiketoenamines (PDKs) over several orders of magnitude through molecular engineering. Stepwise deconstruction of mixed-PDK composites, laminates, and assemblies is chemospecific, allowing a prescribed subset of monomers, fillers, and additives to be recovered in pristine condition at each stage of the recycling process. We provide a theoretical framework to understand PDK depolymerization via acid-catalyzed hydrolysis and experimentally validate trends predicted for the rate-limiting step. The control achieved by PDKs in managing thermal and materials entropy points to new opportunities for pairing circular design with sustainable manufacturing.

Water-walking insects can harness capillary forces by changing their body posture to climb or descend the meniscus between the surface of water and a solid object. Controlling surface tension in this manner is necessary for predation, escape and survival. Inspired by this behaviour, we demonstrate autonomous, aqueous-based synthetic systems that overcome the meniscus barrier and shuttle cargo subsurface to and from a landing site and a targeted drop-off site. We change the sign of the contact angle of a coacervate sac containing an aqueous phase or of a hydrogel droplet hanging from the surface by controlling the normal force acting on the sac or droplet. The cyclic buoyancy-induced cargo shuttling occurs continuously, as long as the supply of reactants diffusing to the sac or droplet from the surrounding aqueous phase is not exhausted. These findings may lead to potential applications in autonomously driven reaction or delivery systems and micro-/milli-robotics.

Super-concentrated "water-in-salt" electrolytes recently spurred resurgent interest for high energy density aqueous lithium-ion batteries. Thermodynamic stabilization at high concentrations and kinetic barriers towards interfacial water electrolysis significantly expand the electrochemical stability window, facilitating high voltage aqueous cells. Herein we investigated LiTFSI/H2O electrolyte interfacial decomposition pathways in the "water-in-salt" and "salt-in-water" regimes using synchrotron X-rays, which produce electrons at the solid/electrolyte interface to mimic reductive environments, and simultaneously probe the structure of surface films using X-ray diffraction. We observed the surface-reduction of TFSI(-)at super-concentration, leading to lithium fluoride interphase formation, while precipitation of the lithium hydroxide was not observed. The mechanism behind this photoelectron-induced reduction was revealed to be concentration-dependent interfacial chemistry that only occurs among closely contact ion-pairs, which constitutes the rationale behind the "water-in-salt" concept., Angewandte Chemie. International Edition, 59 (51), ISSN:1433-7851, ISSN:1521-3773, ISSN:0570-0833

Microemulsions, mixtures of oil, water, and surfactant, are thermodynamically stable. Unlike conventional emulsions, microemulsions form spontaneously, have a monodisperse droplet size that can be controlled by adjusting the surfactant concentration, and do not degrade with time. To make microemulsions, a judicious choice of surfactant molecules must be made, which significantly limits their potential use. Nanoparticle surfactants, on the other hand, are a promising alternative because the surface chemistry needed to make them bind to a liquid–liquid interface is both well flexible and understood. Here, we derive a thermodynamic model predicting the conditions in which nanoparticle surfactants drive spontaneous emulsification that agrees quantitatively with experiments using Noria nanoparticles. This new class of microemulsions inherits the mechanical, chemical, and optical properties of the nanoparticles used to form them, leading to novel applications.

Direct observation of nanoparticle adsorption to the water-oil interface captures early attachment and jamming., Electrostatic interactions between nanoparticles (NPs) and functionalized ligands lead to the formation of NP surfactants (NPSs) that assemble at the water-oil interface and form jammed structures. To understand the interfacial behavior of NPSs, it is necessary to understand the mechanism by which the NPSs attach to the interface and how this attachment depends on the areal coverage of the interface. Through direct observation with high spatial and temporal resolution, using laser scanning confocal microscopy and in situ atomic force microscopy (AFM), we observe that early-stage attachment of NPs to the interface is diffusion limited and with increasing areal density of the NPSs, further attachment requires cooperative displacement of the previously assembled NPSs both laterally and vertically. The unprecedented detail provided by in situ AFM reveals the complex mechanism of attachment and the deeply nonequilibrium nature of the assembly.

Dendrite formation during electrodeposition while charging lithium metal batteries compromises their safety. Although high-shear-modulus (Gs) solid-ion conductors (SICs) have been prioritized to resolve the pressure-driven instabilities that lead to dendrite propagation and cell shorting, it is unclear whether these or alternatives are needed to guide uniform lithium electrodeposition, which is intrinsically density-driven. Here, we show that SICs can be designed within a universal chemomechanical paradigm to access either pressure-driven dendrite-blocking or density-driven dendrite-suppressing properties, but not both. This dichotomy reflects the competing influence of the SIC's mechanical properties and the partial molar volume of Li+ ([Formula: see text]) relative to those of the lithium anode (GLi and VLi) on plating outcomes. Within this paradigm, we explore SICs in a previously unrecognized dendrite-suppressing regime that are concomitantly 'soft', as is typical of polymer electrolytes, but feature an atypically low [Formula: see text] that is more reminiscent of 'hard' ceramics. Li plating (1 mA cm-2; T = 20 °C) mediated by these SICs is uniform, as revealed using synchrotron hard X-ray microtomography. As a result, cell cycle life is extended, even when assembled with thin Li anodes (~30 µm) and either high-voltage NMC-622 cathodes (1.44 mAh cm-2) or high-capacity sulfur cathodes (3.02 mAh cm-2).

Author(s): Nugent, P; Prendergast, D | Abstract: We employed ab-initio simulations and quantum chemical calculations to develop a computational framework for simulating the microscopic structure and mechanical properties of novel polymer membranes used in lithium sulfur batteries. To meet industry targets, next generation batteries with high specific energy (Wh/kg) are essential. Efforts to commercialize light-weight, energy-dense lithium-sulfur secondary batteries (2510 Wh/kg) have been stalled by ongoing problems with the battery’s separator membrane, which should prevent cross-over of active material from cathode to anode that, if unchecked, limits cycle-life. However, Sepion Technologies’ polymer membranes yield long-lasting lithium-sulfur cells. Advancing to 10 Ah battery prototypes, Sepion faces challenges in membrane manufacturing related to polymer processing and the molecular basis for membrane performance and durability. High performance computing offers critical new insight into these phenomena, which in turn will accelerate product entry into the market.

To suppress dendrite formation in lithium metal batteries, high cation transference number electrolytes that reduce electrode polarization are highly desirable, but rarely available using conventional liquid electrolytes. Here, we show that liquid electrolytes increase their cation transference numbers (e.g., ∼0.2 to >0.70) when confined to a structurally rigid polymer host whose pores are on a similar length scale (0.5-2 nm) as the Debye screening length in the electrolyte, which results in a diffuse electrolyte double layer at the polymer-electrolyte interface that retains counterions and reject co-ions from the electrolyte due to their larger size. Lithium anodes coated with ∼1 μm thick overlayers of the polymer host exhibit both a low area-specific resistance and clear dendrite-suppressing character, as evident from their performance in Li-Li and Li-Cu cells as well as in post-mortem analysis of the anode's morphology after cycling. High areal capacity Li-S cells (4.9 mg cm-2; 8.2 mAh cm-2) implementing these high transference number polymer-hosted liquid electrolytes were remarkably stable, considering ∼24 μm of lithium was electroreversibly deposited in each cycle at a C-rate of 0.2. We further identified a scalable manufacturing path for these polymer-coated lithium electrodes, which are drop-in components for lithium metal battery manufacturing.

Natural and man-made robotic systems use the interfacial tension between two fluids to support dense objects on liquid surfaces. Here, we show that coacervate-encased droplets of an aqueous polymer solution can be hung from the surface of a less dense aqueous polymer solution using surface tension. The forces acting on and the shapes of the hanging droplets can be controlled. Sacs with homogeneous and heterogeneous surfaces are hung from the surface and, by capillary forces, form well-ordered arrays. Locomotion and rotation can be achieved by embedding magnetic microparticles within the assemblies. Direct contact of the droplet with air enables in situ manipulation and compartmentalized cascading chemical reactions with selective transport. Applications including functional microreactors, motors, and biomimetic robots are evident.

Batteries assembled with lithium metal anodes and high-capacity cathodes—including air, sulfur, and lithium-rich transition metal oxides—have higher energy density than conventional Li-ion counterparts. Unfortunately, the lifetime of lithium metal cells is typically short, owing to the formation of dendrites on charging, which eventually shorts the cells. Short cycle life is also observed when lithium deposits with a “mossy” morphology; the high surface area of mossy deposits increases the rate of electrolyte degradation, eventually drying out the cells. Here we show that a lithium-ion-conducting, architected macroporous polyelectrolyte (AMP-1) serves as a long-lasting host for uniform and dense lithium–metal electrodeposits. High Coulombic efficiencies indicate the low occurrence of parasitic reactions with the electrolyte. Galvanostatic discharge experiments indicate that AMP-1 suppresses dendrite formation, extending over 2-fold the short-circuit time at high current density. Our success opens new dire...

Here we show how to design organic redox-active solutions for use in redox-flow batteries, with an emphasis on attaining high volumetric capacity electrodes that minimize active-material crossover through the flow cell’s membrane. Specifically, we advance oligoethylene oxides as versatile core motifs that grant access to liquid redox-active oligomers having infinite miscibility with organic electrolytes. The resulting solutions exhibit order-of-magnitude increases in volumetric capacity and obviate deleterious effects on redox stability. The design is broadly applicable, allowing both low potential and high potential redox centers to be appended to these core motifs, as demonstrated by benzofurazan, nitrobenzene, 2,2,6,6-tetramethylpiperidin-1-yl)oxyl, and 2,5-di-tert-butyl-1-methoxy-4-(2′-methoxy)benzene pendants, whose reduction potentials range from −1.87 to 0.76 V vs Ag/Ag+ in acetonitrile. Notably, the oligoethylene oxide scaffold minimizes membrane crossover relative to redox-active small molecules,...

Few reports to date have focused on the chemical and electrochemical reversibility of redox pendants assembled into soluble redox-active polymers (RAPs). Here we report a series of soluble RAPs for flow battery applications designed with cyclopropenium (CP) pendants. The tether length between CP and a polystyrene backbone was varied and found to influence electrochemical activity and stability. Different tether lengths of x methylene groups (x = 1–7) were simulated, and x = 1, 5, and 7 were synthesized to evaluate experimentally. This study illustrates that polymers with extended tether groups display an improved reversibility in cyclic voltammetry. The behavior is mirrored in the stability of the charged state tested in galvanostatic half-cells. When paired with a viologen polymer, these CP-based polymers produce a 1.55 V nonaqueous flow battery. The capacity decays for the polymers were structure-dependent, which provides empirical insight into materials design for high potential catholyte polymers.

Interfacial assemblies of nanoparticles can stabilize liquid-liquid interfaces. Due to the interactions between functional groups on nanoparticles dispersed in one liquid and polymers having complementary end-functionality dissolved in a second immiscible fluid, the anchoring of a well-defined number of polymer chains onto the nanoparticles leads to the formation of NP-surfactants that assemble at the interface and reduce the interfacial energy. We have developed droplet interfaces covered with elastic, responsive monolayers of NP-surfactants. Due to the presence of an elastic layer at the interface, the droplets offer a greater resistance to coalescence and can prevent the exchange of materials across interfaces. Our results show the successful encapsulation of nanoparticles, dyes, and proteins with diameters in the 2.4-30 nm range. Further, we show that stable water-in-oil droplets can be generated for various combinations of polymer ligands and nanoparticles bearing complementary functionalities. These NP-surfactant-stabilized microfluidic emulsions would enable applications requiring liquid-liquid interfaces that can adapt and respond to external stimuli and whose mechanical properties can be easily tailored.

Despite the availability of chemistries to tailor the pore architectures of microporous polymer membranes for chemical separations, trade-offs in permeability and selectivity with functional group manipulations nevertheless persist, which ultimately places an upper bound on membrane performance. Here we introduce a new design strategy to uncouple these attributes of the membrane. Key to our success is the incorporation of phase-change metal-organic frameworks (MOFs) into the polymer matrix, which can be used to increase the solubility of a specific gas in the membrane, and thereby its permeability. We further show that it is necessary to scale the size of the phase-change MOF to nanoscopic dimensions, in order to take advantage of this effect in a gas separation. Our observation of an increase in solubility and permeability of only one of the gases during steady-state permeability measurements suggests fast exchange between free and chemisorbed gas molecules within the MOF pores. While the kinetics of this exchange in phase-change MOFs are not yet fully understood, their role in enhancing the efficacy and efficiency of the separation is clearly a compelling new direction for membrane technology.

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved. Bicontinuous jammed emulsions (or bijels) are tortuous, interconnected structures of two immiscible liquids, kinetically trapped by colloidal particles that are irreversibly bound to the oil-water interface. A wealth of applications has been proposed for bijels in catalysis, energy storage and molecular encapsulation, but large domain sizes (on the order of 5 μm or larger) and difficulty in fabrication pose major barriers to their use. Here, we show that bijels with sub-micrometre domains can be formed via homogenization, rather than spinodal decomposition. We achieve this by using nanoparticle surfactants: polymers and nanoparticles of complementary functionality (for example, ion-pairing) that bind to one another at the oil-water interface. This allows the stabilization of the bijel far from the demixing point of the liquids, with interfacial tensions on the order of 20 mN m-1. Furthermore, our strategy is extremely versatile, as solvent, nanoparticle and ligand can all be varied.

The controlled structuring of liquids into arbitrary shapes can be achieved in biphasic liquid media using the interfacial assemblies of nanoparticle surfactants (NP-surfactants), that consist of a polar nanoparticle "head group" bound to one or more hydrophobic polymer "tails". The nonequilibrium shapes of the suspended liquid phase can be rendered permanent by the jamming of the NP-surfactants formed and assembled at the interface between the liquids as the system attempts to minimize the interfacial area between the liquids. While critical to the structuring process, little is known of the dynamic mechanical properties of the NP-surfactant monolayer at the interface as it is dictated by the characteristics of the component, including NP size and concentration and the molecular weight and concentration of polymers bound to the NPs. Here we provide the first comprehensive understanding of the dynamic mechanical character of two-dimensional NP-surfactant assemblies at liquid/liquid interfaces. Our results indicate that the dynamics of NP-polymer interactions are self-regulated across multiple time scales and are associated with specific mesoscale interactions between self-similar and cross-complementary components. Furthermore, the mechanical properties of the NP-surfactant monolayer are tunable over a broad range and deterministic on the basis of those component inputs. This control is key to tailoring the functional attributes of the reconfigurable structured liquids to suit specific applications.

Structured liquids, whose 3-D morphology can adapt and respond to external stimuli, represent a revolutionary materials platform for next-generation energy technologies, such as batteries, photovoltaics, and thermoelectrics. Structured liquids can be crafted by the jamming of interfacial assemblies of nanoparticle (NP) surfactants. Due to the interactions between functional groups on nanoparticles dispersed in one liquid and polymers having complementary end-functionality dissolved in a second immiscible fluid, the anchoring of a well-defined number of polymer chains onto the NPs leads to the formation of NP surfactants that assemble at the interface and reduce the interfacial energy. Microfluidic techniques provide a simple and versatile route to produce one liquid phase in a second where the shape of the dispersed liquid phase can range from droplets to tubules depending on the flow conditions and the interfacial energies. In this study, the effect of NP surfactants on Plateau-Rayleigh (PR) instabilities of a free-falling jet of an aqueous dispersion of carboxylic acid functionalized silica NPs into a toluene phase containing amine-terminated polydimethylsiloxane (PDMS-NH

Spinodal decomposition is not the only way to make a bijel. Indeed, while spinodal decomposition produces structures with a potentially useful morphology, it can be challenging to make bijels using this method and the resulting systems can be hard to process and manipulate. Furthermore, exploiting the functional properties of the assembled particle monolayer is extremely challenging. In this chapter, we show how the assembly of nanoparticle surfactants at the liquid–liquid interface can be used to kinetically trap liquids into a wealth of complex structures without using spinodal decomposition. We apply liquid three-dimensional printing and moulding methods, along with patterned substrates with controllable wetting properties, to build all-liquid devices with applications in chemical synthesis, separation, and purification. The functional properties of the assembled nanomaterials can be exploited to produce interfacially structured liquids that are plasmonically and magnetically responsive. Finally, we conclude by arguing that, while the field shows great promise, efforts need to be made to translate liquid bicontinuous systems out of the laboratory and into meaningful, real-world applications, as well applications in more ‘exotic’ disciplines, such as synthetic biology.

Control of equilibrium and non-equilibrium thermomechanical behavior of poly(diketoenamine) vitrimers is shown by incorporating linear polymer segments varying in molecular weight (MW) and conformational degrees of freedom into the dynamic covalent network. While increasing MW of linear segments yields a lower storage modulus at the rubbery plateau after softening above the glass transition (Tg ), both Tg and the characteristic time of stress relaxation are independently governed by the conformational entropy of the embodied linear segments. Activation energies for bond exchange in the solid state are lower for networks incorporating flexible chains; the network topology freezing temperature decreases with increasing MW of flexible linear segments but increases with increasing MW of stiff segments. Vitrimer reconfigurability is therefore influenced not only by the energetics of bond exchange for a given network density, but also the entropy of polymer chains within the network.