Enhancing capacity and transport kinetics of C@TiO2core-shell composite anode by phase interface engineering.

In nanocomposite electrodes, besides the synergistic effect that takes advantage of the merits of each component, phase interfaces between the components would contribute significantly to the overall electrochemical properties. However, the knowledge of such effects is far from being well developed up to now. The present work aims at a mechanistic understanding of the phase interface effect in C@TiO2core-shell nanocomposite anode which is both scientifically and industrially important. Firstly, amorphous C, anatase TiO2and C@anatse-TiO2electrodes are compared. The C@anatase-TiO2shows an obvious higher specific capacity (316.5 mAh g-1at a current density of 37 mA g-1after 100 cycles) and Li-ion diffusion coefficient (4.0 × 10-14cm2s-1) than the amorphous C (178 mAh g-1and 2.9 × 10-15cm2s-1) and anatase TiO2(120 mAh g-1and 1.6 × 10-15cm2s-1) owing to the C/TiO2phase interface effect. Then, C@anatase/rutile-TiO2is obtained by a heat treatment of the C@anatase-TiO2. Due to an anatase-to-rutile phase transformation and diffusion of C along the anatase/rutile phase interface, additional abundant C/TiO2phase interfaces are created. This endows the C@anatase/rutile-TiO2with further boosted specific capacity (409.4 mAh g-1at 37 mA g-1after 100 cycles) and Li-ion diffusion coefficient (3.2 × 10-13cm2s-1), and excellent rate capability (368.6 mAh g-1at 444 mA g-1). These greatly enhanced electrochemical properties explicitly reveal phase interface engineering as a feasible way to boost the electrochemical performance of nanocomposite anodes for Li-ion batteries.

TDP43 Exacerbates Atherosclerosis Progression by Promoting Inflammation and Lipid Uptake of Macrophages.

OBJECTIVE: Atherosclerosis (AS), characterized by cholesterol overloaded-macrophages accumulation and plaque formation in blood vessels, is the major cause of cardiovascular disease. Transactive response DNA-binding protein∼43 kDa (TDP43) has recently been identified as an independent driver of neurodegenerative diseases through triggering inflammatory response. This study investigated whether TDP43 is involved in AS development, especially in macrophages-mediated-foam cell formation and inflammatory responses. METHODS: Transactive response DNA-binding protein∼43 kDa expressions in oxidized low-density lipoprotein (oxLDL)-treated macrophages and peripheral blood mononuclear cells (PBMCs) from patients with coronary artery disease (CAD) were detected by real time-polymerase chain reaction (RT-PCR), Western blot, and immunofluorescence. Gene gain or loss of function was used to investigate the effects of TDP43 on macrophages-mediated lipid untake and inflammation with ELISA, protein immunoprecipitation, RT-PCR, Western blot, and immunofluorescence. Macrophage TDP43 specific knockout mice with ApoE-/- background were fed with western diet for 12 weeks to establish AS model, and used to explore the role of TDP43 on AS progression. RESULTS: Transactive response DNA-binding protein∼43 kDa expression increases in oxLDL-treated macrophages and PBMCs from patients with CAD. Furthermore, we find that TDP43 promotes activation of NF-κB to increase inflammatory factor expression in macrophages through triggering mitochondrial DNA release to activate cGAS-STING signaling. Moreover, TDP43 strengthens lipid uptake of macrophages through regulating ß-catenin and PPAR-γ complex to promote scavenger receptor gene CD36 transcription. Finally, using macrophage TDP43 specific knockout mice with ApoE-/- background fed with western diet for 12 weeks to establish AS model, we find that specific knockout of TDP43 in macrophages obviously alleviates western diet-induced AS progression in mice. CONCLUSIONS: Transactive response DNA-binding protein∼43 kDa exacerbates atherosclerosis progression by promoting inflammation and lipid uptake of macrophages, suggesting TDP43 as a potential target for developing atherosclerotic drug.

Nanostructured Lateral Boryl Substitution Conjugated Donor-Acceptor Oligomers for Visible-Light-Driven Hydrogen Production.

Poor charge separation is the main factor that limits the photocatalytic hydrogen generation efficiency of organic conjugated polymers. In this work, a series of linear donor-acceptor (D-A) type oligomers are synthesized by a palladium-catalyzed Sonogashira-Hagihara coupling of electron-deficient diborane unit and different dihalide substitution sulfur functionalized monomers. Such diborane-based A unit exerts great impact on the resulting oligomers, including distinct semiconductor characters with isolated lowest unoccupied molecular orbital (LUMO) orbits locating in diborane-containing fragment, and elevated LUMO level higher than water reduction potential. Relative to A-A type counterpart, the enhanced dipole polarization effect in D-A oligomers facilitates separation of photogenerated charge carriers, as evidenced by notably prolonged electron lifetime. Owing to π-π stacking of rigid backbone, the oligomers can aggregate into an interesting 2D semicrystalline nanosheet (≈2.74 nm), which is rarely reported in linear polymeric photocatalysts prepared by similar carbon-carbon coupling reaction. Despite low surface area (30.3 m2 g-1 ), such ultrathin nanosheet D-A oligomer offers outstanding visible light (λ > 420 nm) hydrogen evolution rate of 833 µmol g-1 h-1 , 14 times greater than its A-A analogue (61 µmol g-1 h-1 ). The study highlights the great potential of using boron element to construct D-A type oligomers for efficient photocatalytic hydrogen generation.

2.6 V aqueous symmetric supercapacitors based on phosphorus-doped TiO2 nanotube arrays.

Increasing the voltage window of an electrode material is effective for improving the energy density of aqueous symmetric supercapacitors. Herein, a novel aqueous symmetric supercapacitor equipped with a high cell voltage window of 2.6 V was assembled by P-doped TiO2 nanotube arrays on a Ti sheet. The arrays exhibit a wide potential range of about 1.2 V as the cathode, and a stable wide potential range of 1.4 V as the anode was also obtained. These wide potential windows in the cathode and anode render the symmetric supercapacitor with a very large working voltage window reaching 2.6 V, and thus a high volumetric energy density (1.65 mW h cm-3). These results suggest that P-doped TiO2 nanotube arrays can be promising candidates for energy storage devices.

High-Performance Photoelectrochemical Water Oxidation with Phosphorus-Doped and Metal Phosphide Cocatalyst-Modified g-C3 N4 Formation Through Gas Treatment.

Graphitic carbon nitride (g-C3 N4 ) has been widely explored as a photocatalyst for water splitting. The anodic water oxidation reaction (WOR) remains a major obstacle for such processes, with issues such as low surface area of g-C3 N4 , poor light absorption, and low charge-transfer efficiency. In this work, such longtime concerns have been partially addressed with band gap and surface engineering of nanostructured graphitic carbon nitride (g-C3 N4 ). Specifically, surface area and charge-transfer efficiency are significantly enhanced through architecting g-C3 N4 on nanorod TiO2 to avoid aggregation of layered g-C3 N4 . Moreover, a simple phosphide gas treatment of TiO2 /g-C3 N4 configuration not only narrows the band gap of g-C3 N4 by 0.57 eV shifting it into visible range but also generates in situ a metal phosphide (M=Fe, Cu) water oxidation cocatalyst. This TiO2 /g-C3 N4 /FeP configuration significantly improves charge separation and transfer capability. As a result, our non-noble-metal photoelectrochemical system yields outstanding visible light (>420 nm) photocurrent: approximately 0.3 mA cm-2 at 1.23 V and 1.1 mA cm-2 at 2.0 V versus RHE, which is the highest for a g-C3 N4 -based photoanode. It is expected that the TiO2 /g-C3 N4 /FeP configuration synthesized by a simple phosphide gas treatment will provide new insight for producing robust g-C3 N4 for water oxidation.

Tubular morphology preservation and doping engineering of Sn/P-codoped hematite for photoelectrochemical water oxidation.

Tubular hematite with high-concentration, uniform doping is regarded as a promising material for photoelectrochemical water oxidation. However, the high-temperature annealing commonly used for activating doped hematite inevitably causes deformation of the tubular structure and an increase in the trap states. In the present work, Sn-doped tubular hematite on fluorine-doped tin oxide (FTO) is successfully obtained at 750 °C from a Sn-coated FeOOH tube precursor. Sn/P codoping, which is rarely considered for hematite, is also achieved via a gas phase reaction in phosphide atmosphere. The tubular morphology allows the dopant to diffuse from both the inner and outer surfaces, thus decreasing the doping profile in the radial direction. The even distribution of Sn and P synergetically increases the carrier density of hematite by one order of magnitude, which shortens the width of the depletion layer to ca. 2.3 nm (compared with 19.3 nm for the pristine sample) and leads to prolonged carrier lifetime and efficient charge separation. In addition, this codoping protocol does not introduce additional surface trap states, as evidenced by the increased charge injection efficiency and surface kinetic analysis using intensity modulated photocurrent spectroscopy (IMPS). As a result, the morphology- and doping-engineered hematite exhibits photocurrents of 0.9 mA cm-2 at 1.23 V and 3.8 mA cm-2 at 2.0 V vs. RHE under AM 1.5 G illumination (100 mW cm-2) in 1.0 M NaOH, representing 4.5-fold and 4.8-fold enhancements, respectively, compared with the photocurrents of undoped hematite. The present method is shown to be effective for preparing multi-element-doped hematite nanotubes and may find broad application in the development of other nanotubular photoelectrodes with or without doping for efficient and robust water oxidation.

Brand new 1D branched CuO nanowire arrays for efficient photoelectrochemical water reduction.

Developing high surface area nanostructured electrodes with fast charge separation is one of the main challenges for exploring cupric oxide (CuO)-based photocathodes in solar-driven hydrogen production applications. Herein, brand new 1D branched CuO nanowire arrays have been achieved on fluorine-doped tin oxide-coated glass (FTO) through a two-step wet chemical redox reaction. X-ray diffraction patterns, Raman spectra and X-ray photoelectron spectroscopy confirm the pure phase characteristic of the resulting branched CuO. In addition to the enlarged surface area of this advanced functional structure as compared with that of the 1D wire trunk, the charge injection and separation have been improved by rationally controlling the density of defects and size of branches. As a result, the optimized branched CuO exhibits photocurrent as high as 3.6 mA·cm-2 under AM 1.5G (100 mW·cm-2) illumination and 3.0 mA·cm-2 under visible light (λ > 420 nm) at 0.2 V vs. RHE in 0.5 M Na2SO4, which are 2.8- and 3.0-fold greater than those of 1D wire samples, respectively. In addition, the solution-processed approach established herein seems quite favourable for large-scale and low-cost manufacturing.

Theoretical prediction of high electron mobility in multilayer MoS2 heterostructured with MoSe2.

Two-dimensional (2D) MoS2 has been considered to be one of the most promising semiconducting materials with the potential to be used in novel nanoelectronic devices. High carrier mobility in the semiconductor is necessary to guarantee a low power dissipation and a high switch speed of the corresponding electronic device. Strain engineering in 2D materials acts as an important approach to tailor and design their electronic and carrier transport properties. In this work, strain is introduced to MoS2 through perpendicularly building van der Waals heterostructures MoSe2-MoS2. Our first-principles calculations demonstrate that acoustic-phonon-limited electron mobility can be significantly enhanced in the heterostructures compared with that in pure multilayer MoS2. It is found that the effective electron mass and the deformation potential constant are relatively smaller in the heterostructures, which is responsible for the enhancement in the electron mobility. Overall, the electron mobility in the heterostructures is about 1.5 times or more of that in pure multilayer MoS2 with the same number of layers for the studied structures. These results indicate that MoSe2 is an excellent material to be heterostructured with multilayer MoS2 to improve the charge transport property.

Fe2 PO5 -Encapsulated Reverse Energetic ZnO/Fe2 O3 Heterojunction Nanowire for Enhanced Photoelectrochemical Oxidation of Water.

Zinc oxide is regarded as a promising candidate for application in photoelectrochemical water oxidation due to its higher electron mobility. However, its instability under alkaline conditions limits its application in a practical setting. Herein, we demonstrate an easily achieved wet-chemical route to chemically stabilize ZnO nanowires (NWs) by protecting them with a thin layer Fe2 O3 shell. This shell, in which the thickness can be tuned by varying reaction times, forms an intact interface with ZnO NWs, thus protecting ZnO from corrosion in a basic solution. The reverse energetic heterojunction nanowires are subsequently activated by introducing an amorphous iron phosphate, which substantially suppressed surface recombination as a passivation layer and improved photoelectrochemical performance as a potential catalyst. Compared with pure ZnO NWs (0.4 mA cm-2 ), a maximal photocurrent of 1.0 mA cm-2 is achieved with ZnO/Fe2 O3 core-shell NWs and 2.3 mA cm-2 was achieved for the PH3 -treated NWs at 1.23 V versus RHE. The PH3 low-temperature treatment creates a dual function, passivation and catalyst layer (Fe2 PO5 ), examined by X-ray photoelectron spectroscopy, TEM, photoelectrochemical characterization, and impedance measurements. Such a nano-composition design offers great promise to improve the overall performance of the photoanode material.

A nanostructured hematite film prepared by a facile "top down" method for application in photoelectrochemistry.

To overcome tough conditions currently used for the preparation of nanostructured hematite films on a conducting substrate, a rational and easy method of chemical etching involving Fe3+ release and material growth in the presence of OH- has been developed. By carefully tuning the parameters influencing the morphologies of hematite, including the synthetic procedure, the concentration of etching solution, temperature, etching time and the morphology controlling surfactant, hematite films grown on iron foil with various morphologies (e.g. nanorod, nanowire, ultrathin nanoflake and cauliflower-like shape) have been achieved. In particular, it is found that F- is an effective surfactant to control the morphology as well as the crystallization process of hematite. Ultrathin nanoflakes having a minimized feature size exhibit the best photocurrent of 0.5 mA cm-2 (1.23 V vs. RHE, RHE is reversible hydrogen electrode) among the samples tested as a result of facilitated hole diffusion to the electrolyte and thus lowered carrier recombination. Compared with pristine hematite, a nearly tripled photocurrent is observed when H2O2 is added in the electrolyte as a hole scavenger, suggesting the presence of a charge injection barrier in the surface of samples. According to this, the strategy of Co2+ treatment is utilized and the improved photocurrent is seen, likely due to the improved water oxidation kinetics and surface state passivation. We believe that this convenient and economical method can be extended to the synthesis of other alkaline metal oxide nanomaterials as long as the redox potential of S2O82-/SO42- is higher than Mn+/M (M refers to metal).

Excellent nonlinearity of a selection device based on anti-series connected Zener diodes for ultrahigh-density bipolar RRAM arrays.

A crossbar array is usually used for the high-density application of a resistive random access memory (RRAM) device. However, the cross-talk interference limits the increase in the integration density. In this paper, anti-series connected Zener diodes as a selection device are proposed for bipolar RRAM arrays. Simulation results show that, by using the anti-series connected Zener diodes as a selection device, the readout margin is sufficiently improved compared to that obtained without a selection device or with anti-parallel connected diodes as the selection device. The maximum size of the crossbar arrays with anti-series connected Zener diodes as a selection device over 1 TB is estimated by theoretical simulation. In addition, the feasibility of using the anti-series connected Zener diodes as a selection device for bipolar RRAM is demonstrated experimentally. These results indicate that anti-series connected Zener diodes as a selection device opens up great opportunities to realize ultrahigh-density bipolar RRAM arrays.

Coexistence of diode-like volatile and multilevel nonvolatile resistive switching in a ZrO2/TiO2 stack structure.

Diode-like volatile resistive switching as well as nonvolatile resistive switching behaviors in a Cu/ZrO2/TiO2/Ti stack are investigated. Depending on the current compliance during the electroforming process, either volatile resistive switching or nonvolatile resistive switching is observed. With a lower current compliance (<10 µA), the Cu/ZrO2/TiO2/Ti device exhibits diode-like volatile resistive switching with a rectifying ratio over 10(6). The permanent transition from volatile to nonvolatile resistive switching can be obtained by applying a higher current compliance of 100 µA. Furthermore, by using different reset voltages, the Cu/ZrO2/TiO2/Ti device exhibits multilevel memory characteristics with high uniformity. The coexistence of nonvolatile multilevel memory and diode-like volatile resistive switching behaviors in the same Cu/ZrO2/TiO2/Ti device opens areas of applications in high-density storage, logic circuits, neural networks, and passive crossbar memory selectors.

Reduced monoclinic BiVO4 for improved photoelectrochemical oxidation of water under visible light.

A monoclinic BiVO4 film was grown on a transparent conducting substrate for photoelectrochemical oxidation of water. A photocurrent up to 2.3 mA cm(-2) under visible light (λ > 420 nm) was achieved after treating the sample simply by electrochemical reduction followed by NaBH4. The high photocurrent is believed to be due to the improved carrier separation and transportation as a result of increased donor density.

Dense layers of vertically oriented WO3 crystals as anodes for photoelectrochemical water oxidation.

Films of crystalline WO(3) nanosheets oriented perpendicular to tungsten substrates were grown by a surfactant-free hydrothermal method, followed by sintering. The films exhibit photoelectrochemical oxygen evolution at low overpotential.