One-Pot Etching Pyrolysis to Defect-Rich Carbon Nanosheets to Construct Multiheteroatom-Coordinated Iron Sites for Efficient Oxygen Reduction.

Constructing multiheteroatom coordination structure in carbonaceous substrates demonstrates an effective method to accelerate the oxygen reduction reaction (ORR) of supported single-atom catalyst. Herein, the novel etching route assisted by potassium thiocyanate (KCNS) is developed to convert metal-organic framework to 2D defect-rich porous N,S-co-doped carbon nanosheets for anchoring atomically dispersed iron sites as the high-performance ORR catalysts (Fe-SACs). The well-designed KCNS-assisted etching route can generate spatial confinement template to direct the carbon nanosheet formation, etching condition to form defect-rich structure, and additional sulfur atoms to coordinate iron species. Spectral and microscopy analysis reveals that the iron element in Fe-SACs is highly isolated on carbon nanosheet and anchored by nitrogen and sulfur atoms in unsymmetrical Fe-S1N3 structure. The optimized Fe-SACs with large specific surface area could show remarkable alkaline ORR performances with a high half-wave potential of 0.920 V versus RHE and excellent durability. The rechargeable zinc-air battery assembled with Fe-SACs air electrodes delivers a large power density of 350 mW cm-2 and a stable voltage platform during charge and discharge over more than 1300 h. This work proposes a novel strategy for the preparation of single-atom catalysts with multiheteroatom coordination structure and highly exposed active sites for efficient ORR.

Different Dual-Task Paradigm Reduce Postural Control Ability and Dynamic Stability of Healthy Young Adults during Stair Descent.

Objective: This study aimed to compare the impacts of different dual-task paradigms on the postural control ability and dynamic stability of the youth during stair descent. Method: Twenty young adults without regular exercise habits were randomly recruited to perform stair descent tasks with three different paradigms: single-task, cognitive dual-task, and manual dual-task. Kinematic and dynamic data were collected using an 8 Vicon motion analysis system and a Kistler force plate to evaluate postural control ability and dynamic stability during stair descent. Results: The variation trends of lower limb joint moment were similar under the three task models. Compared with a single-task, both dual-task paradigms significantly reduced the mechanical parameters and dynamic stability during stair descent. Conclusion: The dual-task paradigm increases the risk of stair-related falls. Both cognitive and manual tasks have similar impacts on postural control ability and dynamic stability during stair walking. It is recommended that people avoid performing dual tasks during stair descent.

Efficient O-O Coupling at Catalytic Interface to Assist Kinetics Optimization on Concerted and Sequential Proton-Electron Transfer for Water Oxidation.

A catalyst kinetics optimization strategy based on tuning active site intermediates adsorption is proposed. Construction of the M-OOH on the catalytic site before the rate-determining step (RDS) is considered a central issue in the strategy, which can optimize the overall catalytic kinetics by avoiding competition from other reaction intermediates on the active site. Herein, the kinetic energy barrier of the O-O coupling for as-prepared sulfated Co-NiFe-LDH nanosheets is significantly reduced, resulting in the formation of M-OOH on the active site at low overpotential, which is directly confirmed by in situ Raman and charge transfer fitting results. Moreover, catalysts constructed from active sites of highly efficient intermediates make a reliable model for studying the mechanism of the OER in proton transfer restriction. In weakly alkaline environments, a sequential proton-electron transfer (SPET) mechanism replaces the concerted proton-electron transfer (CPET) mechanism, and the proton transfer step becomes the RDS; high-speed consumption of reaction intermediates (M-OOH) induces sulfated Co-NiFe-LDH to exhibit excellent kinetics.

A semiconductor-electrocatalyst nano interface constructed for successive photoelectrochemical water oxidation.

Photoelectrochemical water splitting has long been considered an ideal approach to producing green hydrogen by utilizing solar energy. However, the limited photocurrents and large overpotentials of the anodes seriously impede large-scale application of this technology. Here, we use an interfacial engineering strategy to construct a nanostructural photoelectrochemical catalyst by incorporating a semiconductor CdS/CdSe-MoS2 and NiFe layered double hydroxide for the oxygen evolution reaction. Impressively, the as-prepared photoelectrode requires an low potential of 1.001 V vs. reversible hydrogen electrode for a photocurrent density of 10 mA cm-2, and this is 228 mV lower than the theoretical water splitting potential (1.229 vs. reversible hydrogen electrode). Additionally, the generated current density (15 mA cm-2) of the photoelectrode at a given overpotential of 0.2 V remains at 95% after long-term testing (100 h). Operando X-ray absorption spectroscopy revealed that the formation of highly oxidized Ni species under illumination provides large photocurrent gains. This finding opens an avenue for designing high-efficiency photoelectrochemical catalysts for successive water splitting.

Tuning Carbon Defect in Copper Single-Atom Catalysts for Efficient Oxygen Reduction.

Defect chemistry in carbon matrix shows great potential for promoting the oxygen reduction reaction (ORR) of metal single-atom catalysts. Herein, a modified pyrolysis strategy is proposed to tune carbon defects in copper single-atom catalysts (Cu-SACs) to fully understand their positive effect on the ORR activity. The optimized Cu-SACs with controllable carbon defect degree and enhanced active specific surface area can exhibit improved ORR activity with a half-wave potential of 0.897 VRHE , ultrahigh limiting current density of 6.5 mA cm-2 , and superior turnover frequency of 2.23 e site-1 s-1 . The assembled Zn-air batteries based on Cu-SACs can also show well-retained reversibility and voltage platform over 1100 h charge/discharge period. Density functional theory calculations reveal that suitable carbon defects can redistribute charge density of Cu-N4 active sites to weaken the O-O bond in adsorbed OOH* intermediate and thus reduce its dissociation energy. This discovery offers a universal strategy for fabricating superior single-atom catalysts with high-efficiency active sites toward energy-directed applications.

One-step pyrolysis synthesis of ternary (P,S,N)-doped graphene as an efficient metal-free electrocatalyst for the oxygen reduction reaction.

Graphene-based materials have been regarded recently as a promising substance for electrochemical energy conversion and storage devices owing to their unique structure and extraordinary properties. Herein, an enormously facile one-step pyrolysis approach is reported for the fabrication of ternary (P,S,N)-doped graphene, which is further investigated as an efficient metal-free electrocatalyst for the oxygen reduction reaction (ORR). Furthermore, optimized ternary-doped graphene can deliver excellent ORR catalytic activity that favors the four-electron ORR process and outstanding long-term durability (90.54% current retention after 20000 s which is far superior to that of commercial Pt/C) owing to the preferable synergetic coupling effect between P, S and N. Density functional theory (DFT) calculations were performed to reveal the synergetic coupling effect between doping elements in the ORR process. This work provides an extremely simple one-step pyrolysis method for the synthesis of P,S,N-doped graphene for electrochemical energy conversion and storage devices.

Transformation mechanism of high-valence metal sites for the optimization of Co- and Ni-based OER catalysts in an alkaline environment: recent progress and perspectives.

As an important semi-reaction process in electrocatalysis, oxygen evolution reaction (OER) is closely associated with electrochemical hydrogen production, CO2 electroreduction, electrochemical ammonia synthesis and other reactions, which provide electrons and protons for the related applications. Considering their fundamental mechanism, metastable high-valence metal sites have been identified as real, efficient OER catalytic sites from the recent observation by in situ characterization technology. Herein, we review the transformation mechanism of high-valence metal sites in the OER process, particularly transition metal materials (Co- and Ni-based). In particular, research progress in the transformation process and role of high-valence metal sites to optimize OER performance is summarized. The key challenges and prospects of the design of high-efficiency OER catalysts based on the above-mentioned mechanism and some new in situ characterizations are also discussed.

The Lower Limb Stiffness, Moments, and Work Mode During Stair Descent Among the Older Adults.

OBJECTIVE: Lower limb stiffness strategies and work mode changes between young and older adults during stair descent are unclear. This study investigated the effect of aging on the lower limb stiffness, moments, and joint work mode during stair descent. DESIGN: Twenty young adults and 20 older adults were recruited from the local community for stair descent test. Kinematics and kinetics data were collected by Vicon system and Kistler force plate. The lower limb stiffness, moments, and work mode were calculated and assess between groups. RESULTS: No significant differences in gait parameters were detected between groups. Compared with young adults, older adults have decreased leg stiffness, knee and ankle stiffness, increased peak hip extension moment, hip stiffness, and ankle work contribution. CONCLUSIONS: The older adults actively reduce the lower limb stiffness to reduce the risk of injury during stair descent. The hip joint strategy reduces the risk of forwarding falls and ankle joint compensation work mode to make up for the lack of knee extension strength. This provides a reference for the focus of exercise intervention and rehabilitation strategies for older adults.

Ammonium-Modified Synthesis of Vanadium Sulfide Nanosheet Assemblies toward High Sodium Storage.

The weak van der Waals interactions of the one-dimensional (1D) chainlike VS4 crystal structure can enable fast charge-transfer kinetics in metal ion batteries, but its potential has been rarely exploited in depth. Herein, a thermodynamics-driven morphology manipulation strategy is reported to tailor VS4 nanosheets into 3D hierarchical self-assembled architectures including nanospheres, hollow nanospheres, and nanoflowers. The ultrathin VS4 nanosheets are generated via 2D anisotropic growth by the strong driving force of coordination interaction from ammonium ions under microwave irradiation and then evolve into 3D sheet-assembled configurations by adjusting the thermodynamic factors of temperature and reaction time. The as-synthesized VS4 nanomaterials present good electrochemical performances as the anode materials for sodium-ion batteries. In particular, the hollow VS4 nanospheres show a specific capacity of 1226.7 mAh g-1 at 200 mA g-1 current density after 100 cycles. The hierarchical nanostructures with large specific surface area and structural stability can overcome the difficulty of sodium ions embedding into the bulk material interior and provide more reactive materials at the same material mass loading compared with other morphologies. Both experiment and DFT calculations suggest that VS4 nanosheets reduce reaction kinetic impediment of sodium ion in battery operating. This work demonstrates a way of the morphological design of 2D VS4 nanosheets and application in sodium ion storage.

One-pot synthesis of sodium-doped willow-shaped graphitic carbon nitride for improved photocatalytic activity under visible-light irradiation.

Graphitic carbon nitride (g-C3N4) is considered as a promising low-cost polymeric semiconductor as conjugated photocatalyst for energy and environmental application. This study exhibits a Na-doped g-C3N4 with willow-leaf-shaped structure and high degree of crystallinity, which was synthesized with a convenient thermal polymerization using sodium carbonate (Na2CO3) as the sodium source. The π-conjugated systems of g-C3N4 were improved by doping sodium, which could accelerate the electron transport efficiency resulting in outstanding photocatalytic properties. Furthermore, optimum Na-doped g-C3N4 (CN-0.05) attributed its enhanced irradiation efficiency of light energy to its narrower band gap and significant improvement in charge separation. Consequently, the H2 evolution rate catalyzed with CN-0.05 can achieve 3559.8 µmol g-1 h-1, which is about 1.9 times higher than that with pristine g-C3N4. The rate of CN-0.05 for reduction of CO2 to CO (3.66 µmol g-1 h-1) is 6.6 times higher than that of pristine g-C3N4. In experiments of pollutants degradation, the reaction constants of degradation of rhodamine B (RhB) and methyl orange (MO) with CN-0.05 were 0.0271 and 0.0101 min-1, respectively, which are 4.7 and 7.2 times more efficient than pristine g-C3N4, respectively. This work provides a simple preparation method for tailoring effective photocatalyst for the sustainable solution of environmental issues.

A facile and simple microwave-assisted synthesis method for mesoporous ultrathin iron sulfide nanosheets as an efficient bifunctional electrocatalyst for overall water splitting.

The engineering of inexpensive, high-efficiency and stable electrodes related to both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is highly desired for full water splitting devices to promote future advances in this energy technology. Therefore, a large surface area, rich in exposed surface atoms, and mesoporosity are very effective parameters in electrochemical reactions. Herein, we have, for the first time, synthesized free-standing mesoporous Fe3S4 nanosheets with a large surface area of 129.65 m2 g-1 through a microwave-assisted synthetic technique. Our present synthesis strategy demonstrates a facile and cost-effective method to overcome the obstacles of fabricating ultrathin two-dimensional graphene-like transition metal sulfide nanosheets. The as-synthesized Fe3S4 nanosheets are applied as both cathodic and anodic electrodes for full water electrolysis. Remarkably, Fe3S4 nanosheets can exhibit a small overpotential (η = 103 mV) to provide the required 10 mA cm-2 current density during the HER process. Meanwhile, a low overpotential of 230 mV is also exhibited for the OER process to allow a 10 mA cm-2 current density. Furthermore, the assembled full water splitting device can achieve potentials of 1.43 and 1.65 V at 10 and 100 mA cm-2 current densities, respectively, in an alkaline electrolyte with excellent cycling stability over 24 h. Our current study may provide an advanced channel for transition metal sulfide catalysts towards commercial water splitting applications.

Anionic Te-Substitution Boosting the Reversible Redox in CuS Nanosheet Cathodes for Magnesium Storage.

The conversion-type copper chalcogenide cathode materials hold great promise for realizing the competitive advantages of rechargeable magnesium batteries among next-generation energy storage technologies; yet, they suffer from sluggish kinetics and low redox reversibility due to large Coulombic resistance and ionic polarization of Mg2+ ions. Here we present an anionic Te-substitution strategy to promote the reversible Cu0/Cu+ redox reaction in Te-substituted CuS1-xTex nanosheet cathodes. X-ray absorption fine structure analysis demonstrates that Te dopants occupy the anionic sites of sulfur atoms and result in an improved oxidation state of the Cu species. The kinetically favored CuS1-xTex (x = 0.04) nanosheets deliver a specific capacity of 446 mAh g-1 under a 20 mA g-1 current density and a good long-life cycling stability upon 1500 repeated cycles with a capacity decay rate of 0.0345% per cycle at 1 A g-1. Furthermore, the CuS1-xTex (x = 0.04) nanosheets can also exhibit an enhanced rate capability with a reversible specific capacity of 100 mAh g-1 even under a high current density of 1 A g-1. All the obtained electrochemical characteristics of CuS1-xTex nanosheets significantly exceed those of pristine CuS nanosheets, which can contribute to the improved redox reversibility and favorable kinetics of CuS1-xTex nanosheets. Therefore, anionic Te-substitution demonstrates a route for purposeful cathode chemistry regulation in rechargeable magnesium batteries.

General metal-organic framework-derived strategy to synthesize yolk-shell carbon-encapsulated nickelic spheres for sodium-ion batteries.

Transition-metal compounds have attracted enormous attention as potential energy storage materials for their high theoretical capacity and energy density. However, the most present transition-metal compounds still suffer from severe capacity decay and limited rate capability due to the lack of robust architectures. Herein, a general metal-organic framework-derived route is reported to fabricate hierarchical carbon-encapsulated yolk-shell nickelic spheres as anode materials for sodium-ion batteries. The nickelic metal-organic framework (Ni-MOF) precursors can be in situ converted into hierarchical carbon-encapsulated Ni2P (Ni2P/C), NiS2 (NiS2/C) and NiSe2 (NiSe2/C) by phosphorization, sulfuration, and selenation reaction, respectively, and maintain their yolk-shell sphere-like morphology. The as-synthesized Ni2P/C sample can deliver much lower polarization and discharge platform, smaller voltage gap, and faster kinetics in comparison with that of the other two counterparts, and thus achieve higher initial specific capacity (3222.1/1979.3 mAh g-1) and reversible capacity of 765.4 mAh g-1 after 110 cycles. This work should provide new insights into the phase and structure engineering of carbon-encapsulated transition-metal compound electrodes via MOFs template for advanced battery systems.

Facile One-Step Microwave-Assisted Method to Synthesize Nickel Selenide Nanosheets for High-Performance Hybrid Supercapacitor.

Nanosheets structures can be employed as the most promising electrode material to enhance electrochemical performance for supercapacitors. Nickel Selenide (Ni0.85Se) nanosheets are synthesized using a rapid microwave synthesis method in a single step. The Ni0.85Se nanosheets possess a high surface area (125 m2g-1) with a hexagonal crystalline structure. It shows magnificent electrochemical properties, such as splendid specific capacitance (2530 Fg-1 at 0.5 Ag-1). An asymmetric hybrid supercapacitor is fabricated with nickel selenide nanosheets as a positive electrode and activated carbon as a negative electrode. The assembled hybrid supercapacitor displays a high energy density of 63.5 WhKg-1 at a power density of 404 WKg-1, and after 8000 cycles, only 5% capacitance is lost along with the better voltage window at 0-1.6 V.

Cuprous Self-Doping Regulated Mesoporous CuS Nanotube Cathode Materials for Rechargeable Magnesium Batteries.

Copper sulfides are broadly explored as the possible cathode materials for rechargeable magnesium batteries on account of their high theoretical capacity of 560 mAh g-1. However, the CuS cathodes usually suffer from serious capacity decay caused by structure collapse during the repeated magnesiation/demagnesiation process. Herein, we present a cuprous self-doping strategy to synthesize mesoporous CuS nanotubes with robust structural stability for rechargeable magnesium batteries and regulate their electrochemical magnesium storage behavior. Electrochemical results show that the mesoporous CuS nanotubes can exhibit high specific capacity, remarkable cycling performance, and good rate capability. The observed discharge capacity of the mesoporous CuS nanotubes could reach about 281.2 mAh g-1 at 20 mA g-1 and 168.9 mAh g-1 at 500 mA g-1. Furthermore, a remarkable ultralong-term cyclic stability with a reversible capacity of 72.5 mAh g-1 at 1 A g-1 is obtained after 550 cycles. These results demonstrate that the mesoporous nanotube structure and the simple cuprous self-doping effect could promote the practical application of copper sulfide cathode materials for rechargeable magnesium batteries.

Dihydromyricetin attenuates Escherichia coli lipopolysaccharide-induced ileum injury in chickens by inhibiting NLRP3 inflammasome and TLR4/NF-κB signalling pathway.

Lipopolysaccharide (LPS) as a major component of Escherichia coli cell wall can cause inflammation and cell death. Dihydromyricetin (ampelopsin, DHM) is a natural flavonoid compound with anti-inflammatory, anti-oxidant and anti-bacterial effects. The preventive effects of DHM against ileum injury remain unclear. Here, we explored the protective role of DHM against LPS-induced ileum injury in chickens. In this study, DHM significantly attenuated LPS-induced alteration in diamine oxidase, malondialdehyde, reduced glutathione, glutathione peroxidase and superoxide dismutase levels in chicken plasma and ileum. Histology evaluation showed that the structure of blood vessels in ileum was seriously fragmented and presence of necrotic tissue in the lumen in the LPS group. Scanning electron microscopic observation revealed that the surface of the villi was rough and uneven, the structure was chaotic, and the normal finger shape was lost in the LPS group. In contrast, 0.05% and 0.1% DHM treatment partially alleviated the abnormal morphology. Additionally, DHM maintained the barrier function by restoring the protein expression of occludin, claudin-1 and zonula occludens protein-1. DHM inhibited apoptosis through the reduction of the expression of bax and caspase-3 and restored the expression of bcl-2. Importantly, DHM could reduce ileum NLR family pyrin domain-containing 3 (NLRP3), caspase-1, interleukin (IL)-1ß and IL-18 expression to protect tissues from pyroptosis and inhibited toll-like receptor 4 (TLR4)/nuclear factor kappa-B (NF-κB) signalling pathway. In summary, DHM attenuated the ileum mucosal damage, oxidative stress and apoptosis, maintained barrier function, inhibited NLRP3 inflammasome and TLR4/NF-κB signalling pathway activation triggered by Escherichia coli LPS.

Facile synthesis of 3D silk fibroin scaffolds with tunable properties for regenerative medicine.

Silk fibroin (SF) porous scaffolds provide mechanical support and biochemical signals to encourage cell attachment and modify biological performance. The available methods for the preparation of SF scaffolds are still required. The crosslinkers used are likely to impact the biocompatibility. Herein, water-insoluble SF scaffolds were prepared by physical methods. The phosphate solution promoted SF molecules aggregate from SF/heparin mixed solution. Then SF scaffolds were prepared in centrifuge tubes under different centrifugal speed. The phosphate was leached from the scaffolds, leaving porous structure. The centrifugal force produced shear-induced silk crystallinity to tune the mechanical performance like the natural silkworm gland. The relationship between performance and second structure of the scaffolds have been revealed by X-ray Diffraction (XRD) and deconvoluting Fourier Transform Infrared spectroscopy (FTIR). Due to changes in the ß-sheet content, pore structure, mechanical strength, and drug-loaded behavior was adjustable. The scaffolds performed excellent on the Activated Partial Thromboplastin Time (APTT) value, and it can keep sustainable released for 7 days. The scaffolds prepared in mild environment showed tunable stiffness, good anticoagulation, and improved cell compatibility, suggesting its potential application in regenerative medicine.

Cobalt-doping SnS2 nanosheets towards high-performance anodes for sodium ion batteries.

Layered SnS2 is considered as a promising anode candidate for sodium-ion batteries yet suffers from low initial coulombic efficiency, limited specific capacity and rate capability. Herein, we report a cobalt metal cation doping strategy to enhance the electrochemical performance of a SnS2 nanosheet array anode through a facile hydrothermal method. Benefitting from this special structure and heteroatom-doping effect, this anode material displays a high initial coulombic efficiency of 57.4%, a superior discharge specific capacity as high as 1288 mA h g-1 at 0.2 A g-1 after 100 cycles and outstanding long-term cycling stability with a reversible capacity of 800.4 mA h g-1 even at 2 A g-1. These excellent performances could be ascribed to the Co-doping effect that can increase the interlayer spacing, produce rich defects, regulate the electronic environment and improve conductivity. Besides, a carbon cloth substrate can maintain the integrity of the electrode material framework and buffer its volume variation, thus boosting intrinsic dynamic properties and enhancing sodium storage performance.

Anionic Se-Substitution toward High-Performance CuS1- x Sex Nanosheet Cathode for Rechargeable Magnesium Batteries.

Rechargeable magnesium batteries (rMBs) are promising as the most ideal further energy storage systems but lack competent cathode materials due to sluggish redox reaction kinetics. Herein, developed is an anionic Se-substitution strategy to improve the rate capability and the cycling stability of 2D CuS1- x Sex nanosheet cathodes through an efficient microwave-induced heating method. The optimized CuS1- x Sex (X = 0.2) nanosheet cathode can exhibit high reversible capacity of 268.5 mAh g-1 at 20 mA g-1 and good cycling stability (140.4 mAh g-1 at 300 mA g-1 upon 100 cycles). Moreover, the CuS1- x Sex (X = 0.2) nanosheet cathode can deliver remarkable rate capability with a reversible capacity of 119.2 mAh g-1 at 500 mA g-1 , much higher than the 21.7 mAh g-1 of pristine CuS nanosheets. The superior electrochemical performance can be ascribed to the enhanced reaction kinetics, enriched cation storage active sites, and shortened ion diffusion pathway of the CuS1- x Sex nanosheet. Therefore, tuning anionic chemical composition demonstrates an effective strategy to develop novel cathode materials for rMBs.

Mo-Modified P2-type Manganese Oxide Nanoplates with an Oriented Stacking Structure and Exposed {010} Active Facets as a Long-Life Sodium-Ion Battery Cathode.

Layered manganese-based cathode materials are of great interest because of their high specific capacities for sodium-ion batteries. However, the Jahn-Teller effect and the inevitable phase transition are detrimental for achieving considerable cycling stability and rate capability. Herein, a P2-type manganese oxide nanoplate cathode material modified by Mo-substitution with an oriented stacking structure and exposed {010} active facets is reported. The manganese oxide nanoplate cathode yields remarkable capacity retention of 86% after 1200 cycles at 10 C (2000 mA g-1). The specific power density is estimated to be as high as 530 W kg-1 with a specific discharge capacity 143.9 mA h g-1 at 1 C and 89.6% capacity retention up to 100 cycles. The superior electrochemical performances can be attributed to the efficient chemical modification and the unique structural features of the present manganese oxide nanoplate. Mo-modification can endow the manganese oxide cathode with enlarged lattice space and average oxidation state and thus favorable Na+ diffusion to inhibit the Jahn-Teller effect and improve the structure stability, thereby achieving an extremely long cycling life. A multilayer oriented stacking nanoplate structure with exposed {010} active facets is also beneficial for providing more surface active sites and shortening the Na+ diffusion path, leading to better rate capability.