Light Enables the Cathodic Interface Reaction Reversibility in Solid-State Lithium-Oxygen Batteries.

Limited triple-phase boundaries arising from the accumulation of solid discharge product(s) in solid-state cathodes (SSCs) pose a challenge to high-property solid-state lithium-oxygen batteries (SSLOBs). Light-assisted SSLOBs have been gradually explored as an ingenious system; however, the fundamental mechanisms of the SSCs interface behavior remain unclear. Here, we discovered that light assistance can enhance the fast inner-sphere charge transfer in SSCs and regulate the discharge products with spherical particles generated via the surface growth model. Moreover, the high photoelectron excitation and transportation capabilities of SSCs can retard cathodic catalytic decay by avoiding structural degradation of the cathode with a reduced charge voltage. The light-induced SSLOBs exhibited excellent stability (170 cycles) with a low discharge-charge polarization overpotential (0.27 V). Furthermore, transparent SSLOBs with exceptional flexibility, mechanical stability, and multiform shapes were fabricated for theory-to-practical applications in sunlight-induced batteries. Our study opens new opportunities for the introduction of solar energy into energy storage systems.

In vitro single-cell dissection revealing the interior structure of cable bacteria.

Filamentous Desulfobulbaceae bacteria were recently discovered as long-range transporters of electrons from sulfide to oxygen in marine sediments. The long-range electron transfer through these cable bacteria has created considerable interests, but it has also raised many questions, such as what structural basis will be required to enable micrometer-sized cells to build into centimeter-long continuous filaments? Here we dissected cable bacteria cells in vitro by atomic force microscopy and further explored the interior, which is normally hidden behind the outer membrane. Using nanoscale topographical and mechanical maps, different types of bacterial cell-cell junctions and strings along the cable length were identified. More important, these strings were found to be continuous along the bacterial cells passing through the cell-cell junctions. This indicates that the strings serve an important function in maintaining integrity of individual cable bacteria cells as a united filament. Furthermore, ridges in the outer membrane are found to envelop the individual strings at cell-cell junctions, and they are proposed to strengthen the junctions. Finally, we propose a model for the division and growth of the cable bacteria, which illustrate the possible structural requirements for the formation of centimeter-length filaments in the recently discovered cable bacteria.

Visible-Light-Promoted C2 Selective Arylation of Quinoline and Pyridine N-Oxides with Diaryliodonium Tetrafluoroborate.

A protocol of visible-light-promoted C2 selective arylation of quinoline and pyridine N-oxides, with diaryliodonium tetrafluoroborate as an arylation reagent, using eosin Y as a photocatalyst for the construction of N-heterobiaryls was presented. This methodology provided an efficient way for the synthesis of 2-aryl-substituted quinoline and pyridine N-oxides. This strategy has the following advantages: specific regioselectivity, simple operation, good functional group tolerance, and high to moderate yields under mild conditions.

Fabrication of light, flexible and multifunctional graphene nanoribbon fibers via a 3D solution printing method.

Graphene oxide nanoribbons (GONRs) are one of the most promising carbon based materials. The integration of 2D GONR sheets into macroscopic materials, such as continuous fibers or film, leads the way in translating the good properties of individual GONR sheets into macroscopic and ordered materials for future applications. In this study, we first report the fabrication of GONR fibers utilizing GONR sheets as the raw material without any supporting surfactant or polymer. The method of fabricating fibers is referred to as '3D solution printing'. GONR fibers exhibit good mechanical and electrical properties, whose tensile strength and electrical conductivity could reach up to 95 MPa and 680 S cm-1, respectively. Hence, the fabricated 3D integrated circuits are lighter and smaller compared to traditional metal circuits, and with high electrical properties. The 3D integrated circuits, therefore, have a bright future prospect.

External Stimuli-Induced Welding of Dynamic Cross-Linked Polymer Networks.

Thermosets have been crucial in modern engineering for decades, finding applications in various industries. Welding cross-linked components are essential in the processing of thermosets for repairing damaged areas or fabricating complex structures. However, the inherent insolubility and infusibility of thermoset materials, attributed to their three-dimensional network structure, pose challenges to welding development. Incorporating dynamic chemical bonds into highly cross-linked networks bridges the gap between thermosets and thermoplastics presenting a promising avenue for innovative welding techniques. External stimuli, including thermal, light, solvent, pH, electric, and magnetic fields, induce dynamic bonds' breakage and reformation, rendering the cross-linked network malleable. This plasticity facilitates the seamless linkage of two parts to an integral whole, attracting significant attention for potential applications in soft actuators, smart devices, solid batteries, and more. This review provides a comprehensive overview of dynamic bonds employed in welding dynamic cross-linked networks (DCNs). It extensively discusses the classification and fabrication of common epoxy DCNs and acrylate DCNs. Notably, recent advancements in welding processes based on DCNs under external stimuli are detailed, focusing on the welding dynamics among covalent adaptable networks (CANs).

Facilitating the mechanical properties of a high-performance pH-sensitive membrane by cross-linking graphene oxide and polyacrylic acid.

Graphene represents a two-dimensional material having extraordinary physical properties, which make it a prospective material for many applications. In particular, graphene oxide (GO), with abundant chemical functional groups, further extends the new functions of graphene-based materials. However, the preparation of GO materials through chemical reactions remains a challenge to materials science. Here, using suitable cross-linkable polymers, a GO-polyacrylic acid (PAA) composite membrane was prepared by a gel-desiccation approach. The fabricated membrane displays both well controlled mechanical characteristics and unique multiple pH response.

Effect of Clay Minerals on Carbonate Precipitation Induced by Cyanobacterium Synechococcus sp.

Carbonate precipitation induced by cyanobacteria is an important factor in lacustrine fine-grained carbonate rock genesis. As key components of these rocks, clay minerals play an important role in aggregating cyanobacteria. However, the formation mechanism of fine-grained carbonate under the effect of clay minerals is unclear. In this study, we investigated carbonate precipitation by Synechococcus cells under the influence of clay minerals. The results showed that clay minerals can accelerate Synechococcus aggregation, and the aggregation rate of the kaolinite group was significantly higher than that of montmorillonite. The aggregate size and Synechococcus cell content increased with an increase in clay minerals, resulting in increasing organic matter and carboxyl content in the aggregates. Due to the high affinity between carboxyl and Ca2+, the presence of Synechococcus sp. could improve the Mg/Ca molar ratio in the microenvironment of aggregates, which is conducive to aragonite precipitation. Thus, aragonite 5 to 10 µm in size precipitated when Synechococcus and clay minerals coexisted, whereas low-magnesium calcite (15 to 60 µm) was the main carbonate only in the presence of Synechococcus. This study provides important insights into the mechanisms of microbial-induced carbonate precipitation under the effect of clay minerals, which might offer theoretical support for the genesis of fine-grained lacustrine carbonate. IMPORTANCE The biogenesis of lacustrine fine-grained carbonates is of great significance to the exploitation of shale oil. Clay minerals are an important component of lacustrine fine-grained sedimentary rocks, which is conductive to the aggregation and settlement of cyanobacteria. We investigated the precipitation of carbonate induced by Synechococcus sp. with the addition of kaolinite and montmorillonite. The pH and calcium carbonate saturation of the environment increased under the effect of cyanobacteria photosynthesis. The aggregation of cyanobacteria cells increased the Mg/Ca molar ratio of the microenvironment, creating a favorable condition for the precipitation of aragonite, which was similar in size to the micritic calcite of fine-grained sedimentary rocks. This study provides theoretical support for the genesis of fine-grained carbonates.

Magnetic Field Enhanced Electrocatalytic Oxygen Evolution of NiFe-LDH/Co3 O4 p-n Heterojunction Supported on Nickel Foam.

Here, a strategy to regulate the electron density distribution by integrating NiFe layered double hydroxides (NiFe-LDH) nanosheets with Co3 O4 nanowires to construct the NiFe-LDH/Co3 O4 p-n heterojunction supported on nickel foam (NiFe-LDH/Co3 O4 /NF) for electrocatalytic oxygen evolution reaction (OER) is proposed. The p-n heterojunction can induce the charge redistribution in the heterogeneous interface to reach Fermi level alignment, thus modifying the adsorption free energy of *OOH and improving the intrinsic activity of the catalyst. As a result, NiFe-LDH/Co3 O4 /NF exhibits outstanding OER performance with a low overpotential of 274 mV at a current density of 50 mA cm-2 and long-time stability over 90 h. Moreover, NF can serve as a magnetic core that induces the exchange bias effect between the magnetic substrate and the active species under the action of the magnetic field, resulting in decreased magnetoresistance and weakened scattering of spin electrons, which further lowers the OER overpotential by 25 mV @ 50 mA cm-2 under a 10 000 G magnetic field. This work provides a new perspective on the design of p-n heterojunction catalysts and a deeper understanding of the magnetic field-enhanced electrocatalytic reactions.

A hierarchically porous TiO2@C membrane with oxygen vacancies: a novel platform for enhancing the catalytic conversion of polysulfides.

In cases involving high levels of sulfur loading or high levels of current discharge, constructing sulfur composite cathodes via traditional coating preparation processes is an unsuitable way to overcome intractable problems relating to cathodes for use in lithium-sulfur batteries, such as poor conductivity, severe volume expansion, and the detrimental shuttle effect. Herein, a novel three-dimensional self-supported TiO2@C membrane with hierarchical interlinked porosity and oxygen vacancies was prepared via a phase-inversion method to act as a sulfur host. The procured TiO2-x@C membrane facilitates the infiltration of electrolyte, provides fast lithium-ion and electron transport channels and abundant sulfur loading sites, and shows superb structural buffering against the large volume changes during the conversion process between sulfur and lithium sulfide. More importantly, the introduction of oxygen vacancies not only enhances the conductivity of the original TiO2, but it also improves the corresponding adsorption abilities toward polysulfides and the subsequent transformation dynamics. Therefore, the TiO2-x@C membrane can significantly inhibit the polysulfide shuttle effect through polar chemisorption and conversion catalysis. Based on the above superiorities, the TiO2-x@C/S membrane electrode exhibits an impressive lifespan of more than 500 cycles at 2 C with a prominent ultimate specific discharge capacity of 715.2 mA h g-1.

Anti-freezing, moisturizing, resilient and conductive organohydrogel for sensitive pressure sensors.

Conductive hydrogels have attracted significant attention in the area of wearable pressure sensors due to their mechanical flexibility, conductivity and self-healing capability. At subzero temperatures, water-based conductive hydrogels unavoidably lose their elasticity and conductivity which limits their practical usages at low temperatures. However, traditional conductive hydrogels are short of moisturizing and anti-freezing ability due to the limitation of pure water solvent, which greatly restricts their application in extreme environments. In this study, an anti-freezing and moisturizing conductive double network organohydrogel was prepared by incorporating thioctic acid (TA) with polyvinyl alcohol-borate (PVA-PB) in carbon nanotubes (CNTs) that were dispersed in water (H2O) and ethylene glycol (EG). The as-prepared PVA-B-TA-CNTs organohydrogel presented outstanding anti-freezing performance (-60 oC), long-term moisturizing property (30 days), excellent stability (400 cycles) and fascinating conductive sensitivity (S = 0.625 kPa-1). The occurrence of dynamic covalent disulfide bonds and noncovalent hydrogen bonds endow the conductive organohydrogels with brilliant remoldability and self-healing ability, which are significant for practical applications. These remarkable advantages make PVA-B-TA-CNTs organohydrogel to have enormous potential in the application of wearable and flexible pressure sensors, human-healthy monitor, and intelligence devices.

Biomorphic structural batteries for robotics.

Batteries with conformal shape and multiple functionalities could provide new degrees of freedom in the design of robotic devices. For example, the ability to provide both load bearing and energy storage can increase the payload and extend the operational range for robots. However, realizing these kinds of structural power devices requires the development of materials with suitable mechanical and ion transport properties. Here, we report biomimetic aramid nanofibers-based composites with cartilage-like nanoscale morphology that display an unusual combination of mechanical and ion transport properties. Ion-conducting membranes from these aramid nanofiber composites enable pliable zinc-air batteries with cyclic performance exceeding 100 hours that can also serve as protective covers in various robots including soft and flexible miniaturized robots. The unique properties of the aramid ion conductors are attributed to the percolating network architecture of nanofibers with high connectivity and strong nanoscale filaments designed using a graph theory of composite architecture when the continuous aramid filaments are denoted as edges and intersections are denoted as nodes. The total capacity of these body-integrated structural batteries is 72 times greater compared with a stand-alone Li-ion battery with the same volume. These materials and their graph theory description enable a new generation of robotic devices, body prosthetics, and flexible and soft robotics with nature-inspired distributed energy storage.

Rational design of MXene@TiO2 nanoarray enabling dual lithium polysulfide chemisorption towards high-performance lithium-sulfur batteries.

Lithium-sulfur (Li-S) batteries face a few vital issues, including poor conductivity, severe volume expansion/contraction, and especially the detrimental shuttle effect during the long-term electrochemical process. Herein, we designed a hierarchical MXene@TiO2 nanoarray via in situ solvothermal strategies followed by heat treatment. The MXene@TiO2 heterostructure achieves superior charge transfer and sulfur encapsulation. Based on the polar-polar and Lewis acid-base mechanism, the robust dual chemisorption capability to trap polysulfides can be synergistically realized through the intense polarity of TiO2 and the abundant acid metal sites of MXene. Hence, the MXene@TiO2 nanoarray as a sulfur host retains a substantially stable discharge capacity of 612.7 mA h g-1 after 500 cycles at a rate of 2 C, which represents a low fading rate of 0.058% per cycle.

Use of Grafted Voltage Stabilizer to Enhance Dielectric Strength of Cross-Linked Polyethylene.

Aromatic voltage stabilizers can improve the dielectric properties of cross-linked polyethylene (XLPE); however, their poor compatibility with XLPE hinders their practical application. Improving the compatibility of aromatic voltage stabilizers with XLPE has, therefore, become a new research goal. Herein 1-(4-vinyloxy)phenylethenone (VPE) was prepared and characterized. It can be grafted onto polyethylene molecules during the cross-linking processes to promote stability of the aromatic voltage stabilizers in XLPE. Fourier transform infrared spectroscopy confirmed that VPE was successfully grafted onto XLPE, and effectively inhibited thermal migration. Thermogravimetric analysis showed that the grafted VPE/XLPE composite exhibits a better thermal stability than a VPE/PE blend composite. Evaluation of the electrical properties showed that the breakdown strength and electrical tree initiation voltage of the VPE/XLPE composite were increased by 15.5% and 39.6%, respectively, when compared to those of bare XLPE. After thermal aging, the breakdown strength and electrical tree initiation voltage of the VPE/XLPE composite were increased by 9.4% and 25.8%, respectively, in comparison to those of bare XLPE, which indicates that the grafted voltage stabilizer can effectively inhibit its migration and enhance the stability of the composite material.

Acetylated SEBS Enhanced DC Insulation Performances of Polyethylene.

Acetophenone can significantly improve the dielectric properties of polyethylene (PE) insulation materials. However, it easily migrates from the PE due to its poor compatibility with the material, which limits its application. In this paper, the functional units of acetophenone were modified in polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) by an acetylation reaction, and SEBS was used as the carrier to inhibit the migration of acetophenone. The number of functional units in the acetylated SEBS (Ac-SEBS) was measured by 1H NMR and the effect of the acetylation degree of SEBS on its compatibility with PE was studied. Meanwhile, the effects of Ac-SEBS on PE's direct current (DC) breakdown strength and space charge accumulation characteristics were investigated. It is demonstrated that Ac-SEBS can significantly improve the field strength of the DC breakdown and inhibit the accumulation of space charge in the PE matrix. This work provides a new approach for the application of aromatic compounds as voltage stabilizers in DC insulation cable materials.

A Facile Route to Synthesize Nanographene Reinforced PBO Composites Fiber via in Situ Polymerization.

The polymer matrix with introduced carbon-based nanofiber displays fascinating properties. They have inspired extensive research on the synthesis of polymer composites, which have been applied in catalysis, electronics, and energy storage. In this report, we reported a facile and efficient method to prepare poly(p-phenylene benzobisoxazole) (PBO)/nanographene (PNG) composites fibers via in-situ polymerization, accompanied by the reduction from (nanographene oxide) NGO to (nanographene) NG. By tuning the ratio of feeding PBO monomer to NGO, various composites fibers with 0.1⁻1 wt % contents of NG were obtained. The efficient PBO chains grafting made NG uniformly disperse in the PBO matrix, and it also increased the uniformity of the packing orientation of PBO chains. Consequently, the tensile strength, tensile modulus, and thermal stability of the obtained PNG composites fibers had been improved significantly. In addition, the composites fibers with 0.5 wt % NG exhibited a 25% increment in tensile strength, and a 41% enhancement in tensile modulus compared with neat PBO fibers. It reveals an excellent reinforcement to PBO composites fibers with NG.

Effect of a new drug releasing system on microencapsulated islet transplantation.

OBJECTIVE: This study aimed to develop a novel release system for grafted islets. MATERIALS AND METHODS: A graphene oxide-FTY720 release system was constructed to test the drug loading and releasing capacity. The recipient rats were divided into four groups as following: Experiment group A (EG A) and B (EG B); Control group A (CG A) and B (CG B). In each group, (2000 ± 100) IEQ microencapsulated islets were implanted into the abdominal cavity of the recipients with oral FTY720, local graphene oxide-FTY720 injection, without immunosuppressants, and with graphene oxide-saturated solution respectively. We detected the immunological data, the blood glucose level, and pericapsular overgrowth to show the transplantation effect. RESULTS: 31% of adsorptive FTY720 was released within 6 h, and 82% of FTY720 was released within 48 h. From day 5 to 8, the amount of PBL in EG B was significantly less than those in EG A (P<0.01). The CD3+ and CD8+ T lymphocytes were suppressed 3 days longer in EG B than in EG A. On day 19 posttransplantation, the blood glucose level in EG B was much lower than that in EG A (P<0.01). On the same day, pericapsular overgrowth was grade I in EG B, grade II in other groups. CONCLUSIONS: Graphene oxide-FTY720 complex showed a drug releasing effect. Local application of graphene-FTY720 releasing system could decrease the amount of peripheral blood lymphocytes (PBL) and the percentage of CD3 and CD8 T lymphocytes in blood for longer time than oral drug application. This releasing system could achieve a better blood glucose control.

A Novel Intelligent Vascular Stent: Preparation and Characterization of Hydrophobic Steel Mesh Stent with Liquid Surface Tension Response.

An intelligent vascular stent was fabricated from a hydrophobic mesh tube, which cans in-situ release thrombolytic drugs only by an injection of nitroglycerin solution. The mesh with 80# pore size has the highest hydrophobic property and the most sensitive response performance after 3.00 wt% (Heptadecafluoro-1,1,2,2,-tetradecyl)trimethoxysilane (HFTES) treatment. This may be due to the larger hydrophobic effective area and more active fluorine groups of 80# mesh surface treated by 3.00 wt% HFTES. It was proved that the "thrombolytic medicine" could be easily and efficiently into the interior of the stent after triggered only by an injection of nitroglycerin liquid. The in-situ thrombolytic effect and the spent time were satisfactory. The thrombosis had been completely dissolved. This technology provides a potential therapy for vascular restenosis and has great potential applications in the therapy for in-stent restenosis.

Mechanical reinforcement fibers produced by gel-spinning of poly-acrylic acid (PAA) and graphene oxide (GO) composites.

Graphene oxide (GO) with extraordinary chemical, thermal and mechanical properties offers possibilities in a variety of applications. Many materials have been fabricated through physical blending of GO with other materials, while, the chemical functionalization of GO has generally been considered challenging. Here, we report the preparation of a novel GO-functionalized fibrous material in which individual compliant GO sheets are cross-linked by PAA chains in a near-vertical fashion. This new fibrous material outperforms many other common fibers in stiffness and strength. Combined with straightforward manufacturing methods, the fibers should find applications in a wide range of areas.

A highly efficient chemical sensor material for ethanol: Al2O3/Graphene nanocomposites fabricated from graphene oxide.

Al(2)O(3)/Graphene nanocomposites are firstly produced from GO solution by a one-step, green, facile, low-cost SC CO(2) method. The as-prepared nanocomposite papers display high CL sensitivity and high selectivity to the ethanol gas, which provides a facile, green and low-cost route for the preparation of ethanol nanoscopic sensing devices with wide applications.