Exfoliation of 2D Materials for Energy and Environmental Applications.

The fascinating properties of single-layer graphene isolated by mechanical exfoliation have inspired extensive research efforts toward two-dimensional (2D) materials. Layered compounds serve as precursors for atomically thin 2D materials (briefly, 2D nanomaterials) owing to their strong intraplane chemical bonding but weak interplane van der Waals interactions. There are newly emerging 2D materials beyond graphene, and it is becoming increasingly important to develop cost-effective, scalable methods for producing 2D nanomaterials with controlled microstructures and properties. The variety of developed synthetic techniques can be categorized into two classes: bottom-up and top-down approaches. Of top-down approaches, the exfoliation of bulk 2D materials into single or few layers is the most common. This review highlights chemical and physical exfoliation methods that allow for the production of 2D nanomaterials in large quantities. In addition, remarkable examples of utilizing exfoliated 2D nanomaterials in energy and environmental applications are introduced.

Multifunctional Role of MoS2 in Preparation of Composite Hydrogels: Radical Initiation and Cross-Linking.

This paper describes the multifunctional effect of molybdenum disulfide (MoS2) that enables the rapid and accessible preparation of nanocomposite hydrogels via a bottom-up design. The MoS2 nanoplatelet forms radical species through a redox reaction with persulfate under aqueous conditions while initiating the polymerization of acrylic monomers and providing noncovalent cross-linking points without requiring external stimuli or extra cross-linkers, leading to the formation of hydrogels that are in situ embedded with inorganic flakes. Furthermore, the addition of MoS2 could induce more rigid and elastic networks compared to those in control hydrogels using a typical cross-linker at the same level; for example, 0.08 wt % MoS2 resulted in a composite hydrogel of which the elastic modulus was 2.5 times greater than that from a hydrogel using N,N'-methylenebis(acrylamide) as the showing phase transition during polymerization. The composite hydrogels are self-healable, taking advantage of reversible physical cross-links. Thus, two cut hydrogel strips could be readily rejoined by heating at 70 °C, and the resulting whole strip showed mechanical strength similar to that of the pristine sample before it was cut. This synthetic approach would give way to the modular design of MoS2-containing composite hydrogels.

Sustainable, Naringenin-Based Thermosets Show Reversible Macroscopic Shape Changes and Enable Modular Recycling.

A sustainable biobased thermoset exhibiting shape-memory behavior and modular recycling capabilities has been developed herein. The prepared thermoset consists of naringenin and biocompatible polymer components. Naringenin, which has three phenolic moieties, has been converted to a multifunctional monomer containing glycidyl groups and readily formed a thermosetting network via epoxide ring opening reaction with a poly(ethylene glycol) diacid under solvent-free conditions. The resulting material is malleable yet as strong as articular cartilage and selectively absorbs water when compared with n-dodecane oil. Moreover, the thermoset can be physically reused. After being crumpled, stretched, or coiled, the initial shape of the material is restored in response to heat or water. Furthermore, the material is amenable to chemical recycling in a bulk state via transesterification, and its components can be recovered on a molecular level after degradation under benign conditions, as was confirmed using a model compound.

Facile fluorescent labeling of a polyacrylamide-based hydrogel film via radical initiation enables selective and reversible detection of Al3.

Stimuli-responsive hydrogels have attracted significant attention for their promising characteristics and have been used in diverse platforms developed for practical applications. When processed as films, these hydrogels show enhanced properties, including faster responses and higher loading capacities, and enhanced interfacial interactions. In this study, we prepared a functional polyacrylamide hydrogel film containing a rhodamine-based probe. The probe plays two fundamental roles: in the fabrication of the film via redox-initiated radical polymerization and in providing a fluorescence response to Al3+. The amine-containing probe initiated the polymerization reaction at room temperature; the resulting film synthesized through the one-step reaction was transparent and stretchable, elongating by more than five times under tensile tension. The fluorogenic probe in the film showed a sensitive, selective response to Al3+ with a detection limit of 1.5 µM. Furthermore, after detection, the addition of ethylenediaminetetraacetic acid (EDTA) to the film turned off the fluorescence from the probe; this facilitated reversible fluorescence sensing when the film was repeatedly exposed to Al3+, as expected. The facile preparation method can be expanded to incorporate other multi-functional amine probes that can impart hydrogel films with autonomous, responsive systems.

Rapid Accessible Fabrication and Engineering of Bilayered Hydrogels: Revisiting the Cross-Linking Effect on Superabsorbent Poly(acrylic acid).

Superabsorbent hydrogels are significant not only in materials science but also in industries and daily life, being used in diapers or soil conditioners as typical examples. The main feature of these materials is their capacity to hold considerable amount of water, which is strongly dependent on the cross-linking density. This study focuses on the preparation of hydrogels by reweighing the effect of cross-linking density on physical properties, which provides green fabrication of bilayered hydrogels that consist of homogeneous structural motifs but show programmed responses via sequential radical polymerization. In particular, when two hydrogel layers containing different cross-linking densities are joined together, an integrated linear bilayer shows heterogeneous deformation triggered by water. We monitor the linear hydrogel bilayer bending into a circle and engineer it by incorporating disperse dyes, changing colors as well as physical properties. In addition, we demonstrate an electric circuit switch using a patterned hydrogel. Anisotropic shape change of the polyelectrolyte switch closes an open circuit and lights a light-emitting diode in red. This proposed fabrication and engineering can be expanded to other superabsorbent systems and create smart responses in cross-linked systems for biomedical or environmental applications.