Dual-Channel-Ion Conductor Membrane for Low-Energy Lithium Extraction.

The development of energy-efficient and environmentally friendly lithium extraction techniques is essential to meet the growing global demand for lithium-ion batteries. In this work, a dual-channel ion conductor membrane was designed for a concentration-driven lithium-selective ion diffusion process. The membrane was based on a porous lithium-ion conductor, and its pores were modified with an anion-exchange polymer. Thus, the sintered lithium-ion conductors provided highly selective cation transport channels, and the functionalized nanopores with positive charges enabled the complementary permeation of anions to balance the transmembrane charges. As a result, the dual-channel membrane realized an ultrahigh Li+/Na+ selectivity of ∼1389 with a competitive Li+ flux of 21.6 mmol·m-2·h-1 in a diffusion process of the LiCl/NaCl binary solution, which was capable of further maintaining the high selectivity over 7 days of testing. Therefore, this work demonstrates the great potential of the dual-channel membrane design for high-performing lithium extraction from aqueous resources with low energy consumption and minimal environmental impact.

Thermoresponsive Poly(N-isopropylacrylamide) Grafted from Cellulose Nanofibers via Silver-Promoted Decarboxylative Radical Polymerization.

A family of thermoresponsive poly(N-isopropylacrylamide) [PNIPAM]-grafted cellulose nanofibers (CNFs) was synthesized via a novel silver-promoted decarboxylative polymerization approach. This method relies on the oxidative decarboxylation of carboxylic acid groups to initiate free radicals on the surface of CNFs. The polymerization reaction employs relatively mild reaction conditions and can be performed in a one-step, one-pot fashion. This rapid reaction forms a C─C bond between CNF and PNIPAM, along with the formation of free polymer in solution. The degree of functionalization (DF) and the amount of PNIPAM grafted can be controlled by the Ag concentration in the reaction. Similar to native bulk PNIPAM, PNIPAM-grafted CNFs (PNIPAM-g-CNFs) show remarkable thermoresponsive properties, albeit exhibiting a slight hysteresis between the heating and cooling stages. Grafting PNIPAM from CNFs changes its cloud point from about 32 to 36 °C, influenced by the hydrophilic nature of CNFs. Unlike physical blending, covalently tethering PNIPAM transforms the originally inert CNFs into thermosensitive biomaterials. The Ag concentration used does not significantly change the cloud point of PNIPAM-g-CNFs, while the cloud point slightly decreases with fiber concentration. Rheological studies demonstrated the sol-gel transition of PNIPAM-g-CNFs and revealed that the storage modulus (G') above cloud point increases with the amount of PNIPAM grafted. The novel chemistry developed paves the way for the polymerization of any vinyl monomer from the surface of CNFs and carbohydrates. This study validates a novel approach to graft PNIPAM from CNFs for the synthesis of new thermoresponsive and transparent hydrogels for a wide range of applications.

Development of a Paper-Based Microfluidic System for a Continuous High-Flow-Rate Fluid Manipulation.

The current study describes the development of a disposable paper-based microfluidic system, which unlike its predecessors that are only capable of processing a small amount of fluid, can continuously process the fluid at a high flow rate of up to 1.5 mL/min. The fabrication procedure was clean-room-free and robust, involving the use of a CO2 laser to engrave the microchannels on a paper substrate, followed by alkenyl ketene dimer treatment to hydrophobize the paper and lamination. The microchannel down to a minimum depth of ∼80 µm with an average roughness of ∼8 µm was engraved on the substrate. As a proof of concept, the applicability of this system to enrich the microparticles based on the inertial focusing mechanism was tested. This new generation of paper-based microfluidic system can be potentially used for the diagnostic applications where the analyte is low in quantity and processing a large volume of fluid sample is required.

Vertically Aligned Gold Nanowires as Stretchable and Wearable Epidermal Ion-Selective Electrode for Noninvasive Multiplexed Sweat Analysis.

The noninvasive continuous analysis of human sweat is of great significance for improved healthcare diagnostics and treatment in the future, for which a wearable potentiometry-based ion-selective electrode (ISE) has attracted increasing attention, particularly involving ion detection. Note that traditional solid-state ISE electrodes are rigid ion-to-electron transducers that are not conformal to soft human skin and cannot function under stretched states. Here, we demonstrated that vertically aligned mushroom-like gold nanowires (v-AuNW) could serve as stretchable and wearable ion-to-electron transducers for multiplexed, in situ potentiometric analysis of pH, Na+, and K+ in sweat. By modifying v-AuNW electrodes with polyaniline, Na ionophore X, and a valinomycin-based selective membrane, we could specifically detect pH, Na+, and K+, respectively, with high selectivity, reproducibility, and stability. Importantly, the electrochemical performance could be maintained even under 30% strain and during stretch-release cycles without the need of extrinsic structural design. Furthermore, our stretchable v-AuNW ISEs could be seamlessly integrated with a flexible printed circuit board, enabling wireless on-body detection of pH, Na+, and K+ with fast response and negligible cross-talk, indicating considerable promise for noninvasive wearable sweat analysis.

Vertical Gold Nanowires Stretchable Electrochemical Electrodes.

Conventional electrodes produced from gold or glassy carbon are outstanding electrochemical platforms for biosensing applications due to their chemical inertness and wide electrochemical window, but are intrinsically rigid and planar in nature. Hence, it is challenging to seamlessly integrate them with soft and curvilinear biological tissues for real-time wearable or implantable electronics. In this work, we demonstrate that vertically gold nanowires (v-AuNWs) possess an enokitake-like structure, with the nanoparticle (head) on one side and nanowires (tail) on the opposite side of the structure, and can serve as intrinsically stretchable, electrochemical electrodes due to the stronger nanowire-elastomer bonding forces preventing from interfacial delamination under strains. The exposed head side of the electrode comprising v-AuNWs can achieve a detection limit for H2O2 of 80 µM, with a linear range of 0.2-10.4 mM at 20% strain, with a reasonably high sensitivity using chronoamperometry. This excellent electrochemical performance in the elongated state, in conjunction with low-cost wet-chemistry fabrication, demonstrates that v-AuNWs electrodes may become a next-generation sensing platform for conformally integrated, in vivo biodiagnostics.

Atomistic insights into the adsorption and stimuli-responsive behavior of poly(N-isopropylacrylamide)-graphene hybrid systems.

Non-covalent functionalization of graphene materials with responsive polymers is a promising approach for synthesizing new, hybrid composites with improved dispersibility and functional properties. However, the interplay between various components of the hybrid systems, their structural configurations, and stimuli-responsive behavior are not yet well understood at the atomic level. Here, we investigate the temperature-responsive behavior of physisorbed poly(N-isopropylacrylamide) (PNIPAM) on to graphene (G) and graphene oxide (GO) sheets in aqueous solution using large scale molecular dynamics simulations. It was observed that PNIPAM can be spontaneously anchored to the surfaces of both G and GO at 290 K with a macromolecular coil shape. However, the configuration of PNIPAM on G is markedly different in comparison with that on GO, leading to its distinct thermoresponsive behavior. Specifically, the adsorption on G gives rise to an increase in the temperature of the coil-to-globule transition when compared to the native polymer, the origin of which can be interpreted in terms of the interactions and the solvation behavior. The results obtained here are of significance to the design and manipulation of graphene-based stimuli-responsive hybrid systems with optimal functional properties.

Functionalized Boron Nitride Nanosheets: A Thermally Rearranged Polymer Nanocomposite Membrane for Hydrogen Separation.

Amino functionalized boron nitride nanosheets (FBN) were incorporated into a crosslinked, thermally rearranged polyimide (XTR) to fabricate FBN-XTR nanocomposite membrane. The FBN-XTR membrane exhibited a small decrease in H2 permeability but demonstrated a remarkably increased H2 gas selectivity over other gases, compared with XTR. The XTR membrane heat-treated at 425 °C had a H2 permeability of 210 Barrers and a H2 /CH4 separation factor of 24.1, whereas the nanocomposite membrane with 1 wt % FBN exhibited a H2 permeability of 110 Barrers and H2 /CH4 separation factor of 275, an order of magnitude greater. At 1 wt % FBN loading, the FBN-XTR membrane showed three times higher tensile strength and 60 % higher elongation than pristine XTR membrane. In addition, FBN-XTR was found to be able to be readily processed into thin-film membranes for practical H2 separation applications.

Renewable Green Platform Chemicals for Polymers.

n/a.

Robust Thermoresponsive Polymer Composite Membrane with Switchable Superhydrophilicity and Superhydrophobicity for Efficient Oil-Water Separation.

Herein, we report for the first time on the fabrication of a robust, thermoresponsive polymer membrane produced by the combination of an elastic polyurethane (TPU) microfiber web and poly(N-isopropylacrylamide) (PNIPAM). PNIPAM hydrogel is evenly coated on the surface of TPU microfibers, and thus, the wettability of TPU-PNIPAM membrane is amplified by taking advantage of the hierarchical structure and increased surface roughness. The TPU-PNIPAM membrane possesses switchable superhydrophilicity and superhydrophobicity as the temperature of membrane changes from 25 to 45 °C. The composite membrane is shown successfully able to separate a 1 wt % oil-in-water emulsion and 1 wt % water-in-oil emulsion at 25 and 45 °C, respectively, with a high separation efficiency of ≥99.26%. Furthermore, the composite membranes show excellent mechanical properties, and they are highly flexible and mechanically tough. The smart composite membranes reported here have shown great potential for further development for practical high-efficiency oil-water separations.

A Versatile Iron-Tannin-Framework Ink Coating Strategy to Fabricate Biomass-Derived Iron Carbide/Fe-N-Carbon Catalysts for Efficient Oxygen Reduction.

The conversion of biomass into valuable carbon composites as efficient non-precious metal oxygen-reduction electrocatalysts is attractive for the development of commercially viable polymer electrolyte membrane fuel-cell technology. Herein, a versatile iron-tannin-framework ink coating strategy is developed to fabricate cellulose-derived Fe3 C/Fe-N-C catalysts using commercial filter paper, tissue, or cotton as a carbon source, an iron-tannin framework as an iron source, and dicyandiamide as a nitrogen source. The oxygen reduction performance of the resultant Fe3C/Fe-N-C catalysts shows a high onset potential (i.e. 0.98 V vs the reversible hydrogen electrode (RHE)), and large kinetic current density normalized to both geometric electrode area and mass of catalysts (6.4 mA cm(-2) and 32 mA mg(-1) at 0.80 V vs RHE) in alkaline condition. This method can even be used to prepare efficient catalysts using waste carbon sources, such as used polyurethane foam.

Photodegradable Gelatin-Based Hydrogels Prepared by Bioorthogonal Click Chemistry for Cell Encapsulation and Release.

In this study, we present a method for the fabrication of in situ forming gelatin and poly(ethylene glycol)-based hydrogels utilizing bioorthogonal, strain-promoted alkyne-azide cycloaddition as the cross-linking reaction. By incorporating nitrobenzyl moieties within the network structure, these hydrogels can be designed to be degradable upon irradiation with low intensity UV light, allowing precise photopatterning. Fibroblast cells encapsulated within these hydrogels were viable at 14 days and could be readily harvested using a light trigger. Potential applications of this new class of injectable hydrogel include its use as a 3D culturing platform that allows the capture and release of cells, as well as light-triggered cell delivery in regenerative medicine.

Biodegradability of Poly-3-hydroxybutyrate/Bacterial Cellulose Composites under Aerobic Conditions, Measured via Evolution of Carbon Dioxide and Spectroscopic and Diffraction Methods.

Poly-3-hydroxybutyrate (PHB) and bacterial cellulose (BC) are both natural polymeric materials that have the potential to replace traditional, nonrenewable polymers. In particular, the nanofibrillar form of bacterial cellulose makes it an effective reinforcement for PHB. Neat PHB, bacterial cellulose, and a composite of PHB/BC produced with 10 wt % cellulose were composted under accelerated aerobic test conditions, with biodegradability measured by the carbon dioxide evolution method, in conjunction with spectroscopic and diffraction methods to assess crystallinity changes during the biodegradation process. The PHB/BC composite biodegraded at a greater rate and extent than that of PHB alone, reaching 80% degradation after 30 days, whereas PHB did not reach this level of degradation until close to 50 days of composting. The relative crystallinity of PHB and PHB in the PHB/BC composite was found to increase in the initial weeks of degradation, with degradation occurring primarily in the amorphous region of the material and some recrystallization of the amorphous PHB. Small angle X-ray scattering indicates that the change in PHB crystallinity is accompanied by a change in morphology of semicrystalline lamellae. The increased rate of biodegradability suggests that these materials could be applicable to single-use applications and could rapidly biodegrade in compost on disposal.

Nitrile Oxide-Norbornene Cycloaddition as a Bioorthogonal Crosslinking Reaction for the Preparation of Hydrogels.

This communication describes the first application of cycloaddition between an in situ generated nitrile oxide with norbornene leading to a polymer crosslinking reaction for the preparation of poly(ethylene glycol) hydrogels under physiological conditions. Hydrogels with high water content and robust physical strength are readily formed within 2-5 min by a simple two-solution mixing method which allows 3D encapsulation of neuronal cells. This bioorthogonal crosslinking reaction provides a simple yet highly effective method for preparation of hydrogels to be used in bioengineering.

Transition and stability of copolymer adsorption morphologies on the surface of carbon nanotubes and implications on their dispersion.

In this study, the adsorption morphologies as well as stability and transitions of a commercial dispersant copolymer (BYK 9076) on the surface of multiwalled carbon nanotubes (MWCNTs) were studied using Fourier transform infrared and UV-vis spectroscopy, dynamic light scattering, and electron microscopy techniques. The results show that the dispersion of carbon nanotubes in ethanol does not increase continuously with increasing copolymer/CNT ratio, which is correlated with the adsorption morphologies of the copolymer on the CNT surface. At a ratio of copolymer/CNT below 0.5, the morphology is random, shifting to a hemimicelle structure at a ratio from 0.5 to 1.0 while at ratios above 1.0, a cylindrical pattern is seen. The hemimicelle morphology is able to prevent the agglomeration of CNTs when the CNT concentration increases to 8.7 mg/mL, while cylindrical morphology is more efficient and stable to provide dispersion of CNTs at higher concentrations of CNTs.

A Homochiral Porous Organic Cage-Polymer Membrane for Enantioselective Resolution.

Membrane-based enantioselective separation is a promising method for chiral resolution due to its low cost and high efficiency. However, scalable fabrication of chiral separation membranes displaying both high enantioselectivity and high flux of enantiomers is still a challenge. Here, the authors report the preparation of homochiral porous organic cage (Covalent cage 3 (CC3)-R)-based enantioselective thin-film-composite membranes using polyamide (PA) as the matrix, where fully organic and solvent-processable cage crystals have good compatibility with the polymer scaffold. The hierarchical CC3-R channels consist of chiral selective windows and inner cavities, leading to favorable chiral resolution and permeation of enantiomers; the CC3-R/PA composite membranes display an enantiomeric excess of 95.2% for R-(+)-limonene over S-(-)-limonene and a high flux of 99.9 mg h-1 m-2. This work sheds light on the use of homochiral porous organic cages for preparing enantioselective membranes and demonstrates a new route for the development of next-generation chiral separation membranes.

Accurate prediction of solvent flux in sub-1-nm slit-pore nanosheet membranes.

Nanosheet-based membranes have shown enormous potential for energy-efficient molecular transport and separation applications, but designing these membranes for specific separations remains a great challenge due to the lack of good understanding of fluid transport mechanisms in complex nanochannels. We synthesized reduced MXene/graphene hetero-channel membranes with sub-1-nm pores for experimental measurements and theoretical modeling of their structures and fluid transport rates. Our experiments showed that upon complete rejection of salt and organic dyes, these membranes with subnanometer channels exhibit remarkably high solvent fluxes, and their solvent transport behavior is very different from their homo-structured counterparts. We proposed a subcontinuum flow model that enables accurate prediction of solvent flux in sub-1-nm slit-pore membranes by building a direct relationship between the solvent molecule-channel wall interaction and flux from the confined physical properties of a liquid and the structural parameters of the membranes. This work provides a basis for the rational design of nanosheet-based membranes for advanced separation and emerging nanofluidics.

Bifunctional polymer hydrogel layers as forward osmosis draw agents for continuous production of fresh water using solar energy.

The feasibility of bilayer polymer hydrogels as draw agent in forward osmosis process has been investigated. The dual-functionality hydrogels consist of a water-absorptive layer (particles of a copolymer of sodium acrylate and N-isopropylacrylamide) to provide osmotic pressure, and a dewatering layer (particles of N-isopropylacrylamide) to allow the ready release of the water absorbed during the FO drawing process at lower critical solution temperature (32 °C). The use of solar concentrated energy as the source of heat resulted in a significant increase in the dewatering rate as the temperature of dewatering layer increased to its LSCT more rapidly. Dewatering flux rose from 10 to 25 LMH when the solar concentrator increased the input energy from 0.5 to 2 kW/m(2). Thermodynamic analysis was also performed to find out the minimum energy requirement of such a bilayer hydrogel-driven FO process. This study represents a significant step forward toward the commercial implementation of hydrogel-driven FO system for continuous production of fresh water from saline water or wastewaters.

Fast deswelling of nanocomposite polymer hydrogels via magnetic field-induced heating for emerging FO desalination.

Freshwater shortage is one of the most pressing global issues. Forward osmosis (FO) desalination technology is emerging for freshwater production from saline water, which is potentially more energy-efficient than the current reverse osmosis process. However, the lack of a suitable draw solute is the major hurdle for commercial implementation of the FO desalination technology. We have previously reported that thermoresponsive hydrogels can be used as the draw agent for a FO process, and this new hydrogel-driven FO process holds promise for further development for practical application. In the present work, magnetic field-induced heating is explored for the purpose of developing a more effective way to recover water from swollen hydrogel draw agents. The composite hydrogel particles are prepared by copolymerization of sodium acrylate and N-isopropylacrylamide in the presence of magnetic nanoparticles (γ-Fe2O3, <50 nm). The results indicate that the magnetic heating is an effective and rapid method for dewatering of hydrogels by generating the heat more uniformly throughout the draw agent particles, and thus, a dense skin layer commonly formed via conventional heating from the outside of the particle is minimized. The FO dewatering performance is affected by the loading of magnetic nanoparticles and magnetic field intensity. Significantly enhanced liquid water recovery (53%) is achieved under magnetic heating, as opposed to only around 7% liquid water recovery obtained via convection heating. Our study shows that the magnetic heating is an attractive alternative stimulus for the extraction of highly desirable liquid water from the draw agent in the polymer hydrogel-driven forward osmosis process.

Tailoring the humidity response of cellulose nanocrystal-based films by specific ion effects.

HYPOTHESIS: The optical properties and humidity response of iridescent films made of cellulose nanocrystal (CNC) and polyethylene glycol (PEG) can be tailored by the incorporation of electrolytes chosen based on specific ion effects (SIE). EXPERIMENTS: A series of inorganic salts comprising five different cations and five anions based on the Hofmeister series were mixed with CNC/PEG suspensions, followed by an air-dried process into iridescent solid films. These films were tested in changing relative humidity (RH) environments from 30% to 90% and their photonic properties and mass change monitored. The underlying structures and the mechanism of their formation were quantified in terms of interparticle distance derived from small angle X-ray scattering experiment and pitch size quantified by scanning electron microscope (SEM). FINDINGS: The specific color and color range of CNC/PEG based films are controlled by a specific anion effect achieved by selection of the salt while the specific cation effect is negligible. The salting-in type anions with the same valency result in a red-shift color when films are in the dried state. The salting-in type leads to a greater color changing range during RH changes than the salting-out type. The resultant mass gain/loss trend is consistent with the color change. In contrast, cations do not show any relationships between salting-in effect and the measured properties as observed for anions. The observed SIE can be used to engineer CNC/polymer-based humidity and bio-diagnostic colorimetric indicator devices.

Effect of temperature on the conformation and functionality of poly(N-isopropylacrylamide) (PNIPAM)-grafted nanocellulose hydrogels.

HYPOTHESIS: Poly(N-isopropylacrylamide) [PNIPAM]-grafted cellulose nanofibers (CNFs) are new thermo-responsive hydrogels which can be used for a wide range of applications. Currently, there is no clear understanding of the precise mechanism by which CNFs and PNIPAM interact together. Here, we hypothesize that the physical crosslinking of grafted PNIPAM on CNF inhibits the free movement of individual CNF, which increases the gel strength while sustaining its thermo-responsive properties. EXPERIMENTS: The thermo-responsive behaviour of PNIPAM-grafted CNFs (PNIPAM-g-CNFs), synthesized via silver-catalyzed decarboxylative radical polymerization, and PNIPAM-blended CNFs (PNIPAM-b-CNFs) was studied. Small angle neutron scattering (SANS) combined with Ultra-SANS (USANS) revealed the nano to microscale conformation changes of these polymer hybrids as a function of temperature. The effect of temperature on the optical and viscoelastic properties of hydrogels was also investigated. FINDINGS: Grafting PNIPAM from CNFs shifted the lower critical solution temperature (LCST) from 32 °C to 36 °C. Below LCST, the PNIPAM chains in PNIPAM-g-CNF sustain an open conformation and poor interaction with CNF, and exhibit water-like behaviour. At and above LCST, the PNIPAM chains change conformation to entangle and aggregate nearby CNFs. Large voids are formed in solution between the aggregated PNIPAM-CNF walls. In comparison, PNIPAM-b-CNF sustains liquid-like behaviour below LCST. At and above LCST, the blended PNIPAM phase separates from CNF to form large aggregates which do not affect CNF network and thus PNIPAM-b-CNF demonstrates low viscosity. Understanding of temperature-dependent conformation of PNIPAM-g-CNFs engineer thermo-responsive hydrogels for biomedical and functional applications.