Enhanced Activities in Alkaline Hydrogen and Oxygen Evolution Reactions on MoS2 Electrocatalysts by In-Plane Sulfur Defects Coupled with Transition Metal Doping.

2D transition metal disulfides (TMDs) are promising and cost-effective alternatives to noble-metal-based catalysts for hydrogen production. Activation of the inert basal plane of TMDs is crucial to improving the catalytic efficiency. Herein, introduction of in-plane sulfur vacancies (Sv ) and 3d transition metal dopants in concert activates the basal planes of MoS2 (M-Sv -MoS2 ) to achieve high activities in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Acetate introducing mild wet chemical etching removes surface S atoms facilitating subsequent cation exchange between the exposed Mo atoms and targeted metal ions in solution. Density-functional theory calculation demonstrates that the exposed 3d transition metal dopants in MoS2 basal planes serve as multifunctional active centers, which not only reduce ΔGH* but also accelerate water oxidation. As a result, the optimal Ni-Sv -MoS2 and Co-Sv -MoS2 electrocatalysts show excellent stability and alkaline HER and OER characteristics such as low overpotentials of 101 and 190 mV at 10 mA cm-2 , respectively. The results reveal a strategy to activate the inert MoS2 basal planes by defect and doping co-engineering and the technique can be extended to other types of TMDs for high-efficiency electrocatalysis beyond water splitting.

In-Situ Synthesis of Heterostructured Carbon-Coated Co/MnO Nanowire Arrays for High-Performance Anodes in Asymmetric Supercapacitors.

Structural design is often investigated to decrease the electron transfer depletion in/on the pseudocapacitive electrode for excellent capacitance performance. However, a simple way to improve the internal and external electron transfer efficiency is still challenging. In this work, we prepared a novel structure composed of cobalt (Co) nanoparticles (NPs) embedded MnO nanowires (NWs) with an N-doped carbon (NC) coating on carbon cloth (CC) by in situ thermal treatment of polydopamine (PDA) coated MnCo2O4.5 NWs in an inert atmosphere. The PDA coating was carbonized into the NC shell and simultaneously reduced the MnCo2O4.5 to Co NPs and MnO NWs, which greatly improve the surface and internal electron transfer ability on/in MnO boding well supercapacitive properties. The hybrid electrode shows a high specific capacitance of 747 F g-1 at 1 A g-1 and good cycling stability with 93% capacitance retention after 5,000 cycles at 10 A g-1. By coupling with vanadium nitride with an N-doped carbon coating (VN@NC) negative electrode, the asymmetric supercapacitor delivers a high energy density of 48.15 Wh kg-1 for a power density of 0.96 kW kg-1 as well as outstanding cycling performance with 82% retention after 2000 cycles at 10 A g-1. The electrode design and synthesis suggests large potential in the production of high-performance energy storage devices.

In Situ Synthesis of MoP Nanoflakes Intercalated N-Doped Graphene Nanobelts from MoO3 -Amine Hybrid for High-Efficient Hydrogen Evolution Reaction.

Molybdenum phosphide (MoP) is a promising non-noble-metal electrocatalyst in the hydrogen evolution reaction (HER), but practical implementation is impeded by the sluggish HER kinetics and poor chemical stability. Herein, a novel high-efficiency HER electrocatalyst comprising MoP nanoflakes intercalated nitrogen-doped graphene nanobelts (MoP/NG), which are synthesized by one-step thermal phosphiding organic-inorganic hybrid dodecylamine (DDA) inserted MoO3 nanobelts, is reported. The intercalated DDA molecules are in situ carbonized into the NG layer and the sandwiched MoO3 layer is converted into MoP nanoflakes which are intercalated between the NG layers forming the alternatingly stacked MoP/NG hybrid nanobelts. The MoP nanoflakes provide abundant edge sites and the sandwiched MoP/NG hybrid enables rapid ion/electron transport thus yielding excellent electrochemical activity and stability for HER. The MoP/NG shows a low overpotential of 94 mV at 10 mA cm-2 , small Tafel slope of 50.1 mV dec-1 , and excellent electrochemical stability with 99.5% retention for over 22 h.

Flexible Nb4N5/rGO Electrode for High-Performance Solid State Supercapacitors.

Flexible supercapacitors (SCs) are desirable for elastic and clothing electronic products owning to their considerable safety, high foldability and outstanding power density. Herein, multilayered films composed of alternating mesoporous Nb4N5 nanobelts and rGO nanosheets (Nb4N5/rGO) are designed and fabricated exhibiting good flexibility. The folding Nb4N5/rGO film electrode reveals an areal capacitance of 141 mF cm-2 (at 1 mA cm-2) along with remarkable cycling stability (the capacitance retention is 90% after 6,000 cycles). The flexible SCs devices were constructed by interlayer couple films of Nb4N5/rGO electrodes with PVA/H2SO4 gel as the electrolyte, which exhibited huge volumetric capacitance of 19 F cm-3 (at 0.1 A cm-3) and a considerable energy density of 0.98 mW h cm-3 with a power density of 0.029 W cm-3. Additionally, the as-obtained folding devices bode outstanding cycling stability with capacitance retention of 89% after 4,000 cycles measured by cyclic voltammetry method (at 100 mV s-1). Above results about niobium nitride based flexible electrodes and devices exploit a platform for wearable electronics and flexible devices.

A novel implant surface modification mode of Fe3O4-containing TiO2 nanorods with sinusoidal electromagnetic field for osteoblastogenesis and angiogenesis.

Implants made of Ti and its alloys are widely utilized in orthopaedic surgeries. However, insufficient osseointegration of the implants often causes complications such as aseptic loosening. Our previous research discovered that disordered titanium dioxide nanorods (TNrs) had satisfactory antibacterial properties and biocompatibility, but TNrs harmed angiogenic differentiation, which might retarded the osseointegration process of the implants. Magnetic nanomaterials have a certain potential in promoting osseointegration, electromagnetic fields within a specific frequency and intensity range can facilitate angiogenic and osteogenic differentiation. Therefore, this study used Fe3O4 to endow magnetism to TNrs and explored the regulation effects of Ti, TNrs, and Fe3O4-TNrs under 1 â€‹mT 15 â€‹Hz sinusoidal electromagnetic field (SEMF) on osteoblastogenesis, osseointegration, angiogenesis, and its mechanism. We discovered that after the addition of SEMF treatment to VR-EPCs cultured on Fe3O4-TNrs, the calcineurin/NFAT signaling pathway was activated, which then reversed the inhibitory effect of Fe3O4-TNrs on angiogenesis. Besides, Fe3O4-TNrs with SEMF enhanced osteogenic differentiation and osseointegration. Therefore, the implant modification mode of Fe3O4-TNrs with the addition of SEMF could more comprehensively promote osseointegration and provided a new idea for the modification of implants.

Recyclable and high-sensitivity electrochemical biosensing platform composed of carbon-doped TiO2 nanotube arrays.

Electrode fouling and passivation are the main reasons for attenuated signals as well as reduced sensitivity and selectivity over time in electrochemical analysis. We report here a refreshable electrode composed of carbon-doped TiO(2) nanotube arrays (C-doped TiO(2)-NTAs), which not only has excellent electrochemical activity for simultaneous determination of 5-hydroxytryptamine and ascorbic acid but also can be easily photocatalytically refreshed to maintain the high selectivity and sensitivity. The C-doped TiO(2)-NTAs are fabricated by rapid annealing of as-anodized TiO(2)-NTAs in argon. The residual ethylene glycol absorbed on the nanotube wall acts as the carbon source and no foreign carbon precursor is thus needed. The morphology, structure, and composition the C-doped TiO(2)-NTAs are determined, and the corresponding doping mechanism is investigated by thermal analysis and in situ mass spectroscopy. Because of the high photocatalytic activity of the C-doped TiO(2)-NTAs electrode, the electrode surface can be readily regenerated by ultraviolet or visible light irradiation. This photoassisted regenerating technique does not damage the electrode microstructure while rendering high reproducibility and stability.

Controllable growth of conical and cylindrical TiO2-carbon core-shell nanofiber arrays and morphologically dependent electrochemical properties.

Quasi-aligned cylindrical and conical core-shell nanofibers consisting of carbon shells and TiO(2) nanowire cores are produced in situ on Ti foils without using a foreign metallic catalyst and template. A cylindrical nanofiber has a TiO(2) nanowire core 30-50 nm in diameter and a 5-10 nm-thick cylindrical carbon shell, while in the conical nanostructure the TiO(2) nanowire core has a diameter of 20-40 nm and the thickness of the carbon shell varies from about 200 nm at the bottom to about 5 nm at the tip. Electrochemical analysis reveals well-defined redox peaks of the [Fe(CN)(6)](3-/4-) redox couple and heterogeneous charge-transfer rate constants of 0.010 and 0.062 cm s(-1) for the cylindrical and conical nanofibers, respectively. The coverage of exposed edge planes on the cylindrical and conical carbon shells is estimated to be 2.5 and 15.5 % respectively. The more abundant exposed edge planes on the conical nanofiber decrease the overpotential and increase the voltammetric resolution during electrochemical detection of uric acid and ascorbic acid. Our results suggest that the density of edge-plane sites estimated from Raman scattering is not necessarily equal to the density of exposed edge-plane sites, and only carbon electrodes with a large density of exposed edge planes or free graphene sheet ends exhibit better electrochemical performance.

Resveratrol-loaded titania nanotube coatings promote osteogenesis and inhibit inflammation through reducing the reactive oxygen species production via regulation of NF-κB signaling pathway.

Although titanium and its alloys are widely used in bone surgeries, the implantation failures caused by sterile inflammation still occur. The excessive reactive oxygen species (ROS) in the peri-implant region are considered to cause inflammation and impede the osseointegration of titanium implants. In this study, a coating of resveratrol-loaded titania nanotube (TNT-Res) for eliminating ROS was fabricated on titanium surface through electrochemical anodization and following surface adsorption of resveratrol. The resveratrol concentration of released from TNT-Res coating was controlled by modulating the loading amount. The ROS production in macrophage cell lineage RAW 264.7 and bone mesenchymal stem cells (BMSCs) were significantly decreased when cultured on TNT-Res coatings. The pro-inflammatory factors, including tumor necrosis factor α (TNF-α) and interleukin 1ß (IL-1ß), and NO produced by RAW 264.7 cells were reduced when cells were cultured on TNT-Res coatings. These results proved that the TNT-Res coating can effectively eliminate ROS and inhibit inflammation. Moreover, the osteogenic indicators, including alkaline phosphatase (ALP) production, extracellular calcium deposition, and osteogenesis-related gene expression, including collagen І (Col-І), osteocalcin (OCN), osteopontin (OPN), and runt-related transcription factor 2 (Runx2), were significantly promoted for TNT-Res groups, which demonstrated that the TNT-Res coating can enhance the osteogenic differentiation of BMSCs. Additionally, the phosphorylation of nuclear factor κ-B (NF-κB) were down-regulated both in RAW 264.7 cells and BMSCs, which indicated that the TNT-Res coating could inhibit inflammation and promote osteogenesis by inhibiting the activation of NF-κB signaling pathway. The TNT-Res coating could be an effective implant surface for improving osseointegration ability of titanium implants.

Phase-equilibrium-dominated vapor-liquid-solid growth mechanism.

The vapor-liquid-solid (VLS) growth model has been widely used to direct the growth of one-dimensional (1D) nanomaterials, but the origin of the proposed process has not been experimentally confirmed. Here we report the experimental evidence of the origin of VLS growth. Al(69)Ni(31) alloyed particles are used as "catalysts" for growing AlN nanowires by nitridation reaction in N(2)-NH(3) at different temperatures. The nanowire growth occurs following the emergence of the catalyst droplets as revealed by in situ X-ray diffraction and thermal analysis. The physicochemical process involved has been elucidated by quantitative analysis on the evolution of the lattice parameters and relative contents of the nitridation products. These direct experimental results reveal that VLS growth of AlN nanowires is dominated by the phase equilibrium of the Al-Ni alloy catalyst. The in-depth insight into the VLS mechanism indicates the general validity of this growth model and may facilitate the rational design and controllable growth of 1D nanomaterials according to the corresponding phase diagrams.

Growth of well-aligned ZnO nanorod arrays on Si substrates by thermal evaporation of Cu-Zn alloy powders.

Well-aligned ZnO nanorod arrays with uniform diameters and lengths have been fabricated on a Si substrate by simple thermal evaporation of Cu-Zn alloy powders in the presence of oxygen without using a template, catalyst, or pre-deposited ZnO seed layer. The ZnO nanorods are characterized by X-ray diffraction, electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy and the growth mechanism is suggested. The nanorods have a single-crystal hexagonal structure and grow along the (0001) direction. Their diameters range from 200 to 400 nm and the lengths are up to several micrometers. The photoluminescence (PL) and Raman spectra disclose the optical properties of the products. The PL spectra show intense near-band ultraviolet emission at 378 nm from the nanorod arrays. The well-aligned ZnO nanorod arrays have a low turn-on field of 6.1 V/microm, suggesting good field emission properties. The simple synthesis methodology in conjunction with the good field emission and optical properties make the study both scientifically and technologically interesting.

Large-scale synthesis of mullite nanowires by molten salt method.

Single-crystalline mullite (3Al2O3 2SiO2) nanowires have been produced in large quantities by a low cost and environmentally benign molten salt synthesis (MSS) method. The raw materials, Al2(SO4)3 and SiO2 powders, react in molten Na2SO4 at 1000 degrees C to produce mullite nanowires without the use of surfactants or templates. After the synthesis, the remaining salts can be easily separated from the products by washing with water. The final products are characterized by X-ray powder diffraction, field emission scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, selected-area electron diffraction, and inductively coupled plasma-atomic emission spectrometry. The thermal and chemical behavior of the raw materials is investigated by heating at a rate of 10 degrees C/min up to 1200 degrees C in air followed by thermogravimetric and differential scanning calorimetry analyses. The single-crystalline mullite nanowires have diameters of 30-80 nm and lengths from several hundreds of nanometers to micrometers and the growth mechanism is discussed.

Fast preparation of LiFePO4 nanoparticles for lithium batteries by microwave-assisted hydrothermal method.

Nanomaterial for lithium batteries can decrease mechanical strain upon lithium intercalation/ deintercalation from lattice, and lead to high rate capability. The currently available microwave technology permits the development and implantation of a temperature-controlled microwave-assisted hydrothermal synthesis (TCMH) of nano-sized cathode material for lithium batteries. Unlike in previous reported traditional hydrothermal synthesis of cathode material LiFePO4, the pure phase of LiFePO4 can be simply and rapidly synthesized for 5 minutes in water under hydrothermal treatment with microwave irradiation. The homogeneous effects induced by microwave irradiation could create a uniform seeding condition. The colloid precursor Li3PO4 plays the key role to be the nucleation center for the new phase while the formation energy for LiFePO4 would be decreased during the following microwave irradiation. The as-prepared pristine LiFePO4 without carbon coating are characterized by X-ray diffraction, Raman, scanning and transmission electron microscopy, and tested as the cathode in lithium batteries. The particle sizes of pristine LiFePO4 are dependent on hydrothermal and microwave-assisted hydrothermal condition and the electrochemical performance are relatively determined.

Biofunctional Elements Incorporated Nano/Microstructured Coatings on Titanium Implants with Enhanced Osteogenic and Antibacterial Performance.

Bone fracture is prevalent among athletes and senior citizens and may require surgical insertion of bone implants. Titanium (Ti) and its alloys are widely used in orthopedics due to its high corrosion resistance, good biocompatibility, and modulus compatible with natural bone tissues. However, bone repair and regrowth are impeded by the insufficient intrinsic osteogenetic capability of Ti and Ti alloys and potential bacterial infection. The physicochemical properties of the materials and nano/microstructures on the implant surface are crucial for clinical success and loading with biofunctional elements such as Sr, Zn, Cu, Si, and Ag into nano/microstructured TiO2 coating has been demonstrated to enhance bone repair/regeneration and bacterial resistance of Ti implants. In this review, recent advances in biofunctional element-incorporated nano/microstructured coatings on Ti and Ti alloy implants are described and the prospects and limitations are discussed.

Improved Immunoregulation of Ultra-Low-Dose Silver Nanoparticle-Loaded TiO2 Nanotubes via M2 Macrophage Polarization by Regulating GLUT1 and Autophagy.

INTRODUCTION: The bone regeneration of endosseous implanted biomaterials is often impaired by the host immune response, especially macrophage-related inflammation which plays an important role in the bone healing process. Thus, it is a promising strategy to design an osteo-immunomodulatory biomaterial to take advantage of the macrophage-related immune response and improve the osseointegration performance of the implant. METHODS: In this study, we developed an antibacterial silver nanoparticle-loaded TiO2 nanotubes (Ag@TiO2-NTs) using an electrochemical anodization method to make the surface modification and investigated the influences of Ag@TiO2-NTs on the macrophage polarization, osteo-immune microenvironment as well as its potential molecular mechanisms in vitro and in vivo. RESULTS: The results showed that Ag@TiO2-NTs with controlled releasing of ultra-low-dose Ag+ ions had the excellent ability to induce the macrophage polarization towards the M2 phenotype and create a suitable osteo-immune microenvironment in vitro, via inhibiting PI3K/Akt, suppressing the downstream effector GLUT1, and activating autophagy. Moreover, Ag@TiO2-NTs surface could improve bone formation, suppress inflammation, and promote osteo-immune microenvironment compared to the TiO2-NTs and polished Ti surfaces in vivo. These findings suggested that Ag@TiO2-NTs with controlled releasing of ultra-low-dose Ag+ ions could not only inhibit the inflammation process but also promote the bone healing by inducing healing-associated M2 polarization. DISCUSSION: Using this surface modification strategy to modulate the macrophage-related immune response, rather than prevent the host response, maybe a promising strategy for implant surgeries in the future.

Direct growth of quasi-aligned ultrafine ZnS nanowire arrays on conducting zinc foils and their field emission properties.

Quasi-aligned ultrafine ZnS nanowire arrays have been grown directly on zinc substrates via a simple hydrothermal method. The morphology, structure, and composition are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. The single-crystalline ultrafine ZnS nanowires have a hexagonal structure with typical diameters of 5-15 nm and lengths of up to micrometers. A possible growth mechanism is proposed. Since the Zn foil serves as both the Zn source and substrate, direct synthesis and assembly of ZnS nanowires on an electrically conductive Zn substrate are accomplished in one step. Optical properties of the product are studied by photoluminescence. Field emission measurements disclose that the synthesized nanostructures possess good electron emission properties with a low turn-on field of about 5.4 V/microm at a current density of 10 microA/cm2. The materials are potentially useful as cathode materials in field emission devices.

Direct growth of hexagonal Cd(OH)2 nanoplates from and on cadmium substrate.

Uniform hexagonal Cd(OH)2 nanoplates have been produced directly on Cd substrates by a hydrothermal process in alkaline solution containing (NH4)2S2)8 without the use of templates or surfactants. The Cd foil serves as both the Cd source and substrate. The morphology, structure, and composition of the Cd(OH)2 nanoplates are characterized by X-ray diffraction, electron microscopy, selected area electron diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The Cd(OH)2 nanoplates are single-crystalline and possess a well defined hexagonal shape. The thicknesses of hexagonal Cd(OH)2 nanoplates range from 30 to 80 nm and the lateral lengths are about 80-200 nm. The growth mechanism is also discussed.

Field emission and optical properties of ZnO nanowires grown directly on conducting brass substrates.

Large-area and uniform ZnO nanowires have been produced directly on a conducting brass substrate by annealing a Cu0.66Zn0.34 foil under a mixture of argon and oxygen. The morphology, structure, and composition of the ZnO nanowires are characterized by X-ray diffraction, electron microscopy, energy-dispersive X-ray spectrometry, and X-ray photoelectron spectroscopy. The ZnO nanowires with diameters of about 40-70 nm and lengths up to micrometers grow preferentially along the [001] direction. Since the Cu0.66Zn0.34 foil serves as both the Zn source and substrate, the synthesis and assembly of the ZnO nanowires on a conducting substrate is accomplished in one step, and good intrinsic adhesion and robust electrical contact between the ZnO nanowires and conducting substrate are realized. This ZnO configuration forms an ideal field emitter and good field emission properties are corroborated in this study. Photoluminescence studies indicate that these ZnO nanowires have good optical quality exhibiting strong ultraviolet (UV) emission at 383 nm and a weak visible emission band centered around 485 nm at room temperature. The good field emission and optical properties suggest that ZnO nanowires fabricated by this method have promising applications in nano-optoelectronic and field emission devices.

Synthesis of hierarchical tree-like and jellyfish-like silicon oxide nanostructures.

Hierarchical tree-like and jellyfish-like SiOx nanostructures have been synthesized by annealing a mixture of carbon coated Ni nanoparticles (Ni@C) and SiO2 powers under argon atmosphere at 1400 degrees C. The synthesized products were characterized by electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The tree-like SiOx nanostructures consisting of the trunks and many branches and subbranches with diminishing diameters have been observed for the first time. The diameters of the trunks are about 150-1000 nm, and the branches become more slender for each branching, ultimately to 20-40 nm in diameter for the ends. The jellyfish-like SiOx nanostructures are constructed by the catalyst heads with sizes of about 1-10 microm and many connected quasi-aligned SiOx nanowires with diameters about 20-40 nm. The Ni species of the Ni@C nanoparticles acts as the catalyst and the surface carbon as the reducing agent for carbothermal reduction of SiO2. The experimental results suggest that the formation of different SiOx nanostructures mainly depend on the dimensions of the congregated Ni catalyst droplets during the reaction process and the growth mechanism is reasonably discussed.

Synthesis and field emission properties of rutile TiO2 nanowires arrays grown directly on a Ti metal self-source substrate.

Large-area and uniform quasi-aligned titanium oxide (TiO2) nanowire arrays have been produced in situ on a titanium (Ti) foil by a simple high-temperature oxidation process with acetone as the oxidant. The products are characterized by X-ray diffraction, electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. The TiO2 nanowires have a rutile single-crystalline structure. The typical diameters range from 20 to 50 nm and lengths are up to a few micrometers. Since the Ti foil serves as both the source of Ti and substrate, direct synthesis and assembly of TiO2 nanowire arrays on a conductive Ti substrate is accomplished in a single step. Consequently, good intrinsic adhesion and electrical contact are achieved naturally between the nanowires and metal substrate. Such TiO2 nanowire arrays exhibit good field emission properties with a low turn-on field of 4.1 V/microm boding well for applications in vacuum microelectronics.

Scalable synthesis of ant-nest-like bulk porous silicon for high-performance lithium-ion battery anodes.

Although silicon is a promising anode material for lithium-ion batteries, scalable synthesis of silicon anodes with good cyclability and low electrode swelling remains a significant challenge. Herein, we report a scalable top-down technique to produce ant-nest-like porous silicon from magnesium-silicon alloy. The ant-nest-like porous silicon comprising three-dimensional interconnected silicon nanoligaments and bicontinuous nanopores can prevent pulverization and accommodate volume expansion during cycling resulting in negligible particle-level outward expansion. The carbon-coated porous silicon anode delivers a high capacity of 1,271 mAh g-1 at 2,100 mA g-1 with 90% capacity retention after 1,000 cycles and has a low electrode swelling of 17.8% at a high areal capacity of 5.1 mAh cm-2. The full cell with the prelithiated silicon anode and Li(Ni1/3Co1/3Mn1/3)O2 cathode boasts a high energy density of 502 Wh Kg-1 and 84% capacity retention after 400 cycles. This work provides insights into the rational design of alloy anodes for high-energy batteries.