No abstract

Conventional metal-organic framework (MOF) powders have periodic micro/mesoporous crystalline architectures tuned by their three-dimensional coordination of metal nodes and organic linkers. To add practical macroscopic shapeability and extrinsic hierarchical porosity, fibrous MOF aerogels were produced by synthesizing MOF crystals on the template of TEMPO-cellulose nanofibrils. Cellulose nanofibrils not only offered extrinsic porosities and mechanical flexibility for the resultant MOF aerogels, but also shifted the balance of nucleation and growth for synthesizing smaller MOF crystals, and further decreased their aggregation possibilities. Thanks to their excellent shapeability, hierarchical porosity up to 99%, and low density below 0.1 g/cm, these MOF aerogels could make the most of their pores and accessible surface areas for higher adsorption capacity and rapid adsorption kinetics of different molecules, in sharp contrast to conventional MOF powders. Thus, this scalable and low-cost production pathway is able to convert MOF powders into a shapeable and flexible form and thereby extend their applications in more broad fields, for example, adapting a conventional filtration setup.

Nanometerization of liquid metal in organic systems can facilitate deposition of liquid metals onto substrates and then recover its conductivity through sintering. Although having broader potential applications, producing stable aqueous inks of liquid metals keeps challenging because of rapid oxidation of liquid metal when exposing to water and oxygen. Here, a biocompatible aqueous ink is produced by encapsulating alloy nanodroplets of gallium and indium (EGaIn) into microgels of marine polysaccharides. During sonicating bulk EGaIn in aqueous alginate solution, alginate not only facilitates the downsizing process via coordination of their carboxyl groups with Ga ions but also forms microgel shells around EGaIn droplets. Due to the deceasing oxygen-permeability of microgel shells, aqueous ink of EGaIn nanodroplets can maintain colloidal and chemical stability for a period of >7 d. Crosslinked alginate-gel with tunable thickness can retard the generation and release of toxic cations, thereby affording high biocompatibility. The soft alginate shells also enable to recover electric conductivity of EGaIn layers by "mechanical sintering" for applications in microcircuits, electric-thermal actuators, and wearable sensors, offering huge potential for electronic tattoos, artificial limbs, electric skins, etc.

Electricity harvest from ubiquitous water has been endeavored, using nanogenerators based on carbon nanomaterials, to acquire renewable and clean energy and cope with fossil depletion and pollution as well. Meanwhile, though many biological organisms can harness water for bioelectricity, it is still challenging to produce biological nanogenerators based on biological nanomaterials with billions of tons of annual production in nature. Herein biological nanofibrils, including cellulose, chitin, silk fibroin, and amyloid, are produced either by liquid-exfoliation of biomasses or by supramolecular assembly of bio-macromolecules. With the intrinsic hydrophilicity and charged states, they can capture moisture from air and form hydrated nanochannels, in analogue to ionic channels of cytomembranes. When exposing their aerogels to moist air flow, there is a balance of water absorption and evaporation, thus producing a streaming potential and an open-circuit voltage across the aerogel. With flexibility, sustainability, biocompatibility, and biodegradability, these biological nanogenerators can harvest electricity from moist air flow in nature (e.g., wind, respiration and perspiration) and in industry, and serve for environmentally-friendly, low-cost, high-efficiency, wearable, and miniaturized power devices.

A 2D membrane-based separation technique has been increasingly applied to solve the problem of fresh water shortage via ion rejection. However, these 2D membranes often suffer from a notorious swelling problem when immersed in solution, resulting in poor rejection for the monovalent metal ion. The design of the antiswelling 2D lamellar membranes has been proved to be a big challenge for highly efficient desalination. Here a kind of self-crosslinked MXene membrane is proposed for ion rejection with an obviously suppressed swelling property, which takes advantage of the hydroxyl terminal groups on the MXene nanosheets by forming Ti–O–Ti bonds between the neighboring nanosheets via the self-crosslinking reaction (−OH + −OH = −O– + H2O) through a facile thermal treatment. The permeation rates of the monovalent metal ions through the self-crosslinked MXene membrane are about two orders of magnitude lower than those through the pristine MXene membrane, which indicates the obviously improved performance of the ion exclusion by self-crosslinking between the MXene lamellae. Moreover, the excellent stability of the self-crosslinked MXene membrane during the 70 h long-term ion separation also demonstrates its promising antiswelling property. Such a facile and efficient self-crosslinking strategy gives the MXene membrane a good antiswelling property for metal ion rejection, which is also suitable for many other 2D materials with tunable surface functional groups during membrane assembly.

Membrane‐based reverse electrodialysis (RED) is considered as the most promising technique to harvest osmotic energy. However, the traditional membranes are limited by high internal resistance and low efficiency, resulting in undesirable power densities. Herein, we report the combination of oppositely charged Ti3C2Tx MXene membranes (MXMs) with confined 2D nanofluidic channels as high‐performance osmotic power generators. The negatively or positively charged 2D MXene nanochannels exhibit typical surface‐charge‐governed ion transport and show excellent cation or anion selectivity. By mixing the artificial sea water (0.5 m NaCl) and river water (0.01 m NaCl), we obtain a maximum power density of ca. 4.6 Wm−2, higher than most of the state‐of‐the‐art membrane‐based osmotic power generators, and very close to the commercialization benchmark (5 Wm−2). Through connecting ten tandem MXM‐RED stacks, the output voltage can reach up 1.66 V, which can directly power the electronic devices.

Silk, one of the strongest natural biopolymers, was hybridized with Kevlar, one of the strongest synthetic polymers, through a biomimetic nanofibrous strategy. Regenerated silk materials have outstanding properties in transparency, biocompatibility, biodegradability and sustainability, and promising applications as diverse as in pharmaceutics, electronics, photonic devices and membranes. To compete with super mechanic properties of their natural counterpart, regenerated silk materials have been hybridized with inorganic fillers such as graphene and carbon nanotubes, but frequently lose essential mechanic flexibility. Inspired by the nanofibrous strategy of natural biomaterials (e.g., silk fibers, hemp and byssal threads of mussels) for fantastic mechanic properties, Kevlar was integrated in regenerated silk materials by combining nanometric fibrillation with proper hydrothermal treatments. The resultant hybrid films showed an ultimate stress and Young's modulus two times as high as those of pure regenerated SF films. This is not only because of the reinforcing effect of Kevlar nanofibrils, but also because of the increasing content of silk β-sheets. When introducing Kevlar nanofibrils into the membranes of silk nanofibrils assembled by regenerated silk fibroin, the improved mechanic properties further enabled potential applications as pressure-driven nanofiltration membranes and flexible substrates of electronic devices.

No abstract