Low vaporization enthalpy of modified chitosan hydrogel for high performance solar evaporator.

The high vaporization enthalpy of water attributed to the strong hydrogen bonds between water molecules is limiting the performance of solar evaporators. This work demonstrates a deliberate attempt to significantly reduce the vaporization enthalpy of water through the introduction of weak water-amine hydrogen bond interactions in hydrogel evaporators. In this article, bio-based chitosan-agarose/multiwalled carbon nanotube hydrogel film evaporators (CAMFEs) exhibit larger vaporization enthalpy reduction with the presence of primary amine groups in chitosan. An interplay between vaporization enthalpy reduction and water diffusivity leads to an optimal ratio of chitosan to agarose = 7:1 (CAMFE7) showing an impressive evaporation rate of 4.13 kg m-2 h-1 under 1 sun irradiation. CAMFE7 also exhibits excellent salt resistance, with a stable water evaporation rate, using brine water of up to 10 % salinity under continuous 1 sun irradiation. The high mechanical robustness together with its scalability makes CAMFE7 a highly promising material for practical drinking water production.

Reprogrammable, Sustainable, and 3D-Printable Cellulose Hydroplastic.

Modern human societies are highly dependent on plastic materials, however, the bulk of them are non-renewable commodity plastics that cause pollution problems and consume large amounts of energy for their thermal processing activities. In this article, a sustainable cellulose hydroplastic material and its composites, that can be shaped repeatedly into various 2D/3D geometries using just water are introduced. In the wet state, their high flexibility and ductility make it conducive for the shaping to take place. In the ambient environment, the wet hydroplastic transits spontaneously into rigid materials with its intended shape in a short time of <30 min despite a thickness of hundreds of microns. They also possess humidity resistance and are structurally stable in highly humid environments. Given their excellent mechanical properties, geometry reprogrammability, bio-based, and biodegradable nature, cellulose hydroplastic poses as a sustainable alternative to traditional plastic materials and even "green" thermoplastics. This article also demonstrates the possibility of 3D-printing these hydroplastics and the potential of employing them in electronics applications. The demonstrated hydroshapable structural electronic components show capability in performing electronic functions, load-bearing ability and geometry versatility, which are attractive features for lightweight, customizable and geometry-unique electronic devices.

MIL-53(Al) assisted in upcycling plastic bottle waste into nitrogen-doped hierarchical porous carbon for high-performance supercapacitors.

Disposable aluminum cans and plastic bottles are common wastes found in modern societies. This article shows that they can be upcycled into functional materials, such as metal-organic frameworks and hierarchical porous carbon nanomaterials for high-value applications. Through a solvothermal method, used poly(ethylene terephthalate) bottles and aluminum cans are converted into MIL-53(Al). Subsequently, the as-prepared MIL-53(Al) can be further carbonized into a nitrogen-doped (4.52 at%) hierarchical porous carbon framework. With an optical amount of urea present during the carbonization process, the carbon nanomaterial of a high specific surface area of 1324 m2 g-1 with well-defined porosity can be achieved. These features allow the nitrogen-doped hierarchical porous carbon to perform impressively as the working electrode of supercapacitors, delivering a high specific capacitance of 355 F g-1 at 0.5 A g-1 in a three-electrode cell and exhibiting a high energy density of 20.1 Wh kg-1 at a power density of 225 W kg-1, while simultaneously maintaining 88.2% capacitance retention over 10,000 cycles in two-electrode system. This work demonstrates the possibility of upcycling wastes to obtain carbon-based high-performance supercapacitors.

Ionogels: recent advances in design, material properties and emerging biomedical applications.

Ionic liquid (IL)-based gels (ionogels) have received considerable attention due to their unique advantages in ionic conductivity and their biphasic liquid-solid phase property. In ionogels, the negligibly volatile ionic liquid is retained in the interconnected 3D pore structure. On the basis of these physical features as well as the chemical properties of well-chosen ILs, there is emerging interest in the anti-bacterial and biocompatibility aspects. In this review, the recent achievements of ionogels for biomedical applications are summarized and discussed. Following a brief introduction of the various types of ILs and their key physicochemical and biological properties, the design strategies and fabrication methods of ionogels are presented by means of different confining networks. These sophisticated ionogels with diverse functions, aimed at biomedical applications, are further classified into several active domains, including wearable strain sensors, therapeutic delivery systems, wound healing and biochemical detections. Finally, the challenges and possible strategies for the design of future ionogels by integrating materials science with a biological interface are proposed.

Self-Healing Approach toward Catalytic Soft Robots.

Soft robotics is a rapidly evolving research field that focuses on developing robots with bioinspired actuation/sensing mechanisms and highly flexible soft materials, some of which are similar to those found in living organisms. The hydrogel has the characteristics of excellent biocompatibility, softness, and elasticity, which makes it an ideal candidate material for the preparation of soft robots. Here we utilized a self-healing approach to develop a catalytically driven soft robot, which was constructed by dynamic imine bonds between modular hydrogels. One of the modules was a hydrogel formed by dynamic aldimine cross-linking of chitosan and glutaraldehyde, and the other module was a hydrogel embedded with catalase. The soft hydrogel robot moved because of catalytic reactions between the robot and environment [hydrogen peroxide (H2O2) fuel], giving rise to a fluidic release that supports propulsion, as inspired by the jet-propulsive mechanism in swimming dragonfly larvae. The speed of the soft robot can be mediated by adjusting the concentration of H2O2 and enable/disable movement based on the folding and unfolding of enzymes. In addition, the hydrogel formed by replacing glutaraldehyde with dialdehyde-functionalized PEG2000 had excellent elastic properties, and the soft robot based on PEG2000 had a higher movement speed than that based on glutaraldehyde under the same H2O2 concentration. Moreover, the addition of iron oxide nanoparticles can realize the magnetic guidance of the soft robot and the combination of different modules can realize different motion modes. The highly configurable self-healing catalytic soft robot holds great potential for a variety of interesting applications, including swimming robots, robot-assisted water treatment, and drug release.

An Asymmetric Hygroscopic Structure for Moisture-Driven Hygro-Ionic Electricity Generation and Storage.

The interactions between moisture and materials give rise to the possibility of moisture-driven energy generation (MEG). Current MEG materials and devices only establish this interaction during water sorption in specific configurations, and conversion is eventually ceased by saturated water uptake. This paper reports an asymmetric hygroscopic structure (AHS) that simultaneously achieves energy harvesting and storage from moisture absorption. The AHS is constructed by the asymmetric deposition of a hygroscopic ionic hydrogel over a layer of functionalized carbon. Water absorbed from the air creates wet-dry asymmetry across the AHS and hence an in-plane electric field. The asymmetry can be perpetually maintained even after saturated water absorption. The absorbed water triggers the spontaneous development of an electrical double layer (EDL) over the carbon surface, which is termed a hygro-ionic process, accounting for the capacitive properties of the AHS. A peak power density of 70 µW cm-3  was realized after geometry optimization. The AHS shows the ability to be recharged either by itself owing to a self-regeneration effect or via external electrical means, which allows it to serve as an energy storage device. In addition to insights into moisture-material interaction, AHSs further shows potential for electronics powering in assembled devices.

Fatty Acid-Based Coacervates as a Membrane-free Protocell Model.

Membrane-less scenarios that involve liquid-liquid phase separation (coacervation) provide clues for how protocells might emerge. Here, we report a versatile approach to construct coacervates by mixing fatty acid with biomolecule dopamine as the protocell model. The coacervate droplets are easily formed over a wide range of concentrations. The solutes with different interaction characteristics, including cationic, anionic, and hydrophobic dyes, can be well concentrated within the coacervates. In addition, reversible self-assemblies of the coacervates can be controlled by concentration, pH, temperature, salinity, and bioreaction realizing cycles between compartmentalization and noncompartmentalization. Through in situ dopamine polymerization, the stability of coacervate droplets is significantly improved, leading to higher resistance toward external factors. Therefore, the coacervates based on fatty acid and dopamine could serve as a bottom-up membrane-less protocell model that provides the links between the simple (small molecule) and complex (macromolecule) systems in the process of cell evolution.

Reversible Hydration Composite Films for Evaporative Perspiration Control and Heat Stress Management.

Donning of personal protective equipment (PPE) in the healthcare sector has been intensified by the on-going COVID-19 pandemic around the globe. While extensive PPE provides protection, it typically limits moisture permeability and severely hinders the sweat evaporation process, resulting in greater heat stress on the personnel. Herein, a zinc-poly(vinyl alcohol) (Zn-PVA) composite film is fabricated by embedding a super-hygroscopic zinc-ethanolamine complex (Zn-complex) in the PVA matrix. By attaching the Zn-PVA composite film, the relative humidity (RH) inside the protective suit decreases from 91.0% to 48.2%. The reduced RH level, in turn, enhances evaporative cooling, hence bringing down the heat index from 64.6 to 40.0 °C at an air temperature of 35 °C, remarkably lowering the likelihood of heat stroke. The American Society for Testing and Materials tests conducted on a sweating manikin have also proven that the Zn-PVA composite films can significantly reduce the evaporative resistance of the protective suit by 90%. The low material cost, facile fabrication process, and reusability allow the Zn-PVA composition films to be readily available for healthcare workers worldwide. This application can be further extended to other occupations that are facing severe thermal discomfort and heat stress.

Diverse-shaped tin dioxide nanoparticles within a plastic waste-derived three-dimensional porous carbon framework for super stable lithium-ion storage.

Tin dioxides (SnO2) inserted into carbons to serve as anodes for rechargeable lithium-ion batteries are known to improve their cycling stability. However, studies on diverse-shaped SnO2 nanoparticles within a porous carbon matrix for super stable lithium-ion storage are rare. Herein, a hollow carbon sphere/porous carbon flake (HCS/PCF) framework is fabricated through template carbonization of plastic waste. By changing the doping mechanism and tuning the loading content, nano SnO2 spheres and cubes as well as bulk SnO2 flakes and blocks are in-situ grown within the HCS/PCF. Then, the as-prepared hybrids with built-in various morphological SnO2 nanoparticles serve as anodes towards advanced lithium-ion batteries. Notably, HCS/PCF embedded with nano SnO2 spheres and cubes anodes possess superb long-term cycling stability (~0.048% and ~0.05% average capacitance decay per cycle at 1 A/g over 400 cycles) with high reversible specific capacities of 0.45 and 0.498 Ah/g after 1000 cycles at 5 A/g. The ultra-stabilized Li+ storage is attributed to the effective mitigation of nano SnO2 spheres/cubes volume expansion, originating from the compact SnO2 yolk-HCS/PCF shell construction. This study paves a general strategy for disposing of polymeric waste to produce SnO2 core-carbon shell anodes for super stable lithium-ion storage.

Entropy-Driven Ultratough Blends from Brittle Polymers.

Polymer blends with synergetic performance play an integral part in modern society. The discovery of compatible polymer systems often relies on strong chemical interactions. By contrast, the role of entropy in polymers is often neglected. In this work, we show that entropy effect could control the phase structure and mechanical behaviors of polymer blends. For weakly interacting polymer pairs, the seemingly small mixing entropy favors the formation of nanoscale cocontinuous structures. The abundant nanointerfaces could initiate large plastic deformations by crazing or shear, thus, transforming brittle polymers (elongation < 9%) into superductile materials (elongation ∼ 146%). The resultant polymer blends display high transparency, strength (∼70 MPa), and toughness (∼60 MJ/m3) beyond most engineering plastics. The principle of entropy-driven blends may also be applied in other polymer systems, offering a strategy to develop mechanically robust bulk polymeric materials for emerging applications such as biomedicine and electronics.

Super Tough and Self-Healable Poly(dimethylsiloxane) Elastomer via Hydrogen Bonding Association and Its Applications as Triboelectric Nanogenerators.

Poly(dimethylsiloxane) (PDMS) as one of the electron-drawing materials has been widely used in triboelectric nanogenerators (TENG), which is expected to generate electron through friction and required to endure dynamic loads. However, the nature of the siloxane bond and the low interchain interaction between the methyl side groups result in low fracture energy in PDMS elastomers. Here, a strategy that combined the advantages of the dynamic of hierarchical hydrogen bonding and phase-separation-like structure was adopted to improve the toughness of PDMS elastomers. By varying both stronger and weaker hydrogen bonding within the PDMS network, a series of super tough (up to 24,000 J/m2), notch-insensitive, transparent, and autonomous self-healable elastomers were achieved. In addition, a hydrophilic polymeric material (PDMAS-U10) was synthesized as the conductive layer. A transparent TENG was fabricated by sandwiching the PDMAS-U10 between two pieces of the PDMS elastomer. Despite its hydrophilic nature, PDMAS-U10 exhibit strong adhesion interaction with hydrophobic PDMS elastomers. As such, a tough (16,500 J/m2), self-healable (efficiency ∼97%), and transparent triboelectric nanogenerator was constructed. A self-powered system employing the TENG is also demonstrated in this work.

3D-Printed Anti-Fouling Cellulose Mesh for Highly Efficient Oil/Water Separation Applications.

The ability of additive manufacturing to print mesh structure was exploited to fabricate highly efficient filtration meshes for oil/water separation applications. Through Direct Ink Writing (DIW) technique, pure cellulose acetate with a mesh architecture can be created easily, using cellulose acetate/ethyl acetate solution as the ink and simply drying off the solvent in ambient conditions. Besides conventional mesh structures, more complex structures can be fabricated in order to manipulate the pore size and hence tune the separation properties of the mesh. The superhydrophilic 3D-printed cellulose meshes are able to achieve a high separation efficiency of >95% as long as the average pore size is smaller than 280 µm. More importantly, the mesh that possesses an unconventional complex structure boasts a separation efficiency of ∼99% while maintaining a high water flux of ∼160 000 Lm2-h-1. The 3D-printed cellulose meshes are also able to separate oil substances of a wide range of viscosity, from highly viscous PDMS (∼97 cP) to nonviscous cyclohexane (∼1 cP) and are chemically resistant to extreme acidic and alkaline conditions. Moreover, the 3D-printed cellulose meshes also possess antioil-fouling/self-cleaning ability, which makes its surfaces resilient to contamination. In addition, the 3D-printed meshes do not suffer from surface inhomogeneity and interfacial adhesion issues as compared to the usual coated meshes. Such a robust yet practical system is highly applicable for highly efficient oil-water separation applications.

Robust Oil-Fouling Resistance of Amorphous Cellulose Surface Underwater: A Wetting Study and Application.

The antioil-fouling characteristic of an amorphous cellulose (a-cellulose) surface was elucidated using the sessile droplet method (static) and a modified Wilhelmy plate technique (dynamic). As compared to other hydrophilic surfaces (cellulose acetate, poly(vinyl alcohol), and glass), the oil (poly(dimethylsiloxane)) contact angle on the a-cellulose surface underwater shows the largest value (170.5 ± 5.0°), having the smallest deviation from its theoretical value (180.0°) as estimated by Young's equation. Also, the a-cellulose surface demonstrates the strongest affinity with water in an oil medium (stable hydrophilicity). Moreover, the work of adhesion between the receding oil phase and a-cellulose underwater is quantified to be 10.3 mN/m, approximately one-fourth of that in air (42.0 mN/m). The overall wetting study suggests a rather low oil/solid/water three-phase contact line (TPL) friction in the direction that water displaces oil. A proposed mechanism attributes these phenomena to the water-accessible rigid cellulose chains and supramolecular structure of a-cellulose. The former hinders molecular rearrangement during processing or upon exposure to oil, such that its polar hydroxyl groups are readily accessible to water, thereby retaining its hydrophilicity. The latter allows water to diffuse across the TPL, forming the hydration shells that weaken the van der Waals interactions between oil and cellulose chains. Such findings of the a-cellulose surface can be exploited to fabricate mesh membranes with high water permeation flux (375.4 ± 13.5 L m-2 h-1 Pa-1), high oil/water separation efficiency (93-98%), and long-lasting stability, which is suitable for offshore oil spill remediation.

Fully biodegradable Poly(lactic acid)/Starch blends: A review of toughening strategies.

Polylactic acid (PLA) and Starch are both bio-based biodegradable polymers that have properties that are complementary to each other. PLA/starch blend exploits the good mechanical property of PLA and the low cost of Starch. However, PLA/Starch blend is intrinsically brittle. This paper reviews the current state of arts in toughening of PLA/Starch blend, which are categorized as: Additive Plasticization, Mixture Softening, Elastomer Toughening and Interphase Compatibilization. These strategies are not mutually exclusive and can be applied jointly in a single blend, opening up a wide range of toughening techniques that can be employed in PLA/Starch blend. Even though significant progress has been made in this area, there is still much room for research, in order to achieve easy to process, fully bio-based and completely biodegradable PLA/Starch blends that have mechanical properties suitable for a wide range of applications.