Enhanced Cycling Stability of All-Solid-State Lithium-Sulfur Battery through Nonconductive Polar Hosts.

All-solid-state lithium-sulfur batteries (ASSLSBs) are promising next-generation battery technologies with a high energy density and excellent safety. Because of the insulating nature of sulfur/Li2S, conventional cathode designs focus on developing porous hosts with high electronic conductivities such as porous carbon. However, carbon hosts boost the decomposition of sulfide electrolytes and suffer from sulfur detachment due to their weak bonding with sulfur/Li2S, resulting in capacity decays. Herein, we propose a counterintuitive design concept of host materials in which nonconductive polar mesoporous hosts can enhance the cycling life of ASSLSBs through mitigating the decomposition of adjacent electrolytes and bonding sulfur/Li2S steadily to avoid detachment. By using a mesoporous SiO2 host filled with 70 wt % sulfur as the cathode, we demonstrate steady cycling in ASSLSBs with a capacity reversibility of 95.1% in the initial cycle and a discharge capacity of 1446 mAh/g after 500 cycles at C/5 based on the mass of sulfur.

Fabrication of silicon-based nickel nanoflower-encapsulated gelatin microspheres as an active antimicrobial carrier.

Local antibiotic application might mitigate the burgeoning problem of rapid emergence of antibiotic resistance in pathogenic microbes. To accomplish this, delivery systems must be engineered. Hydrogels have a wide range of physicochemical properties and can mimic the extracellular matrix, rendering them promising materials for local antibacterial agent application. Here, we synthesized antibacterial silicon (Si)-based nickel (Ni) nanoflowers (Si@Ni) and encapsulated them in gelatin methacryloyl (GelMA) using microfluidic and photo-crosslink technology, constructing uniform micro-sized hydrogel spheres (Si@Ni-GelMA). Si@Ni and Si@Ni-GelMA were characterized using X-ray diffraction, transmission electron microscopy, and scanning electron microscopy. Injectable Si@Ni-GelMA exhibited excellent antibacterial activities owing to the antibiotic effect of Ni against Pseudomonas aeruginosa, Klebsiella pneumoniae, and methicillin-resistant Staphylococcus aureus, while showing negligible cytotoxicity. Therefore, the Si@Ni-GelMA system can be used as drug carriers owing to their injectability, visible light-mediated crosslinking, degradation, biosafety, and superior antibacterial properties.

Moisture-Induced Degradation of Quantum-Sized Semiconductor Nanocrystals through Amorphous Intermediates.

Elucidating the water-induced degradation mechanism of quantum-sized semiconductor nanocrystals is an important prerequisite for their practical application because they are vulnerable to moisture compared to their bulk counterparts. In-situ liquid-phase transmission electron microscopy is a desired method for studying nanocrystal degradation, and it has recently gained technical advancement. Herein, the moisture-induced degradation of semiconductor nanocrystals is investigated using graphene double-liquid-layer cells that can control the initiation of reactions. Crystalline and noncrystalline domains of quantum-sized CdS nanorods are clearly distinguished during their decomposition with atomic-scale imaging capability of the developed liquid cells. The results reveal that the decomposition process is mediated by the involvement of the amorphous-phase formation, which is different from conventional nanocrystal etching. The reaction can proceed without the electron beam, suggesting that the amorphous-phase-mediated decomposition is induced by water. Our study discloses unexplored aspects of moisture-induced deformation pathways of semiconductor nanocrystals, involving amorphous intermediates.

Magnesium: properties and rich chemistry for new material synthesis and energy applications.

Magnesium (Mg) has many unique properties suitable for applications in the fields of energy conversion and storage. These fields presently rely on noble metals for efficient performance. However, among other challenges, noble metals have low natural abundance, which undermines their sustainability. Mg has a high negative standard reduction potential and a unique crystal structure, and its low melting point at 650 °C makes it a good candidate to replace or supplement numerous other metals in various energy applications. These attractive features are particularly helpful for improving the properties and limits of materials in energy systems. However, knowledge of Mg and its practical uses is still limited, despite recent studies which have reported Mg's key roles in synthesizing new structures and modifying the chemical properties of materials. At present, information about Mg chemistry has been rather scattered without any organized report. The present review highlights the chemistry of Mg and its uses in energy applications such as electrocatalysis, photocatalysis, and secondary batteries, among others. Future perspectives on the development of Mg-based materials are further discussed to identify the challenges that need to be addressed.

Direct Observation of Off-Stoichiometry-Induced Phase Transformation of 2D CdSe Quantum Nanosheets.

Crystal structures determine material properties, suggesting that crystal phase transformations have the potential for application in a variety of systems and devices. Phase transitions are more likely to occur in smaller crystals; however, in quantum-sized semiconductor nanocrystals, the microscopic mechanisms by which phase transitions occur are not well understood. Herein, the phase transformation of 2D CdSe quantum nanosheets caused by off-stoichiometry is revealed, and the progress of the transformation is directly observed by in situ transmission electron microscopy. The initial hexagonal wurtzite-CdSe nanosheets with atomically uniform thickness are transformed into cubic zinc blende-CdSe nanosheets. A combined experimental and theoretical study reveals that electron-beam irradiation can change the stoichiometry of the nanosheets, thereby triggering phase transformation. The loss of Se atoms induces the reconstruction of surface atoms, driving the transformation from wurtzite-CdSe(11 2 ¯ $\bar{2}$ 0) to zinc blende-CdSe(001) 2D nanocrystals. Furthermore, during the phase transformation, unconventional dynamic phenomena occur, including domain separation. This study contributes to the fundamental understanding of the phase transformations in 2D quantum-sized semiconductor nanocrystals.

Development of high-energy non-aqueous lithium-sulfur batteries via redox-active interlayer strategy.

Lithium-sulfur batteries have theoretical specific energy higher than state-of-the-art lithium-ion batteries. However, from a practical perspective, these batteries exhibit poor cycle life and low energy content owing to the polysulfides shuttling during cycling. To tackle these issues, researchers proposed the use of redox-inactive protective layers between the sulfur-containing cathode and lithium metal anode. However, these interlayers provide additional weight to the cell, thus, decreasing the practical specific energy. Here, we report the development and testing of redox-active interlayers consisting of sulfur-impregnated polar ordered mesoporous silica. Differently from redox-inactive interlayers, these redox-active interlayers enable the electrochemical reactivation of the soluble polysulfides, protect the lithium metal electrode from detrimental reactions via silica-polysulfide polar-polar interactions and increase the cell capacity. Indeed, when tested in a non-aqueous Li-S coin cell configuration, the use of the interlayer enables an initial discharge capacity of about 8.5 mAh cm-2 (for a total sulfur mass loading of 10 mg cm-2) and a discharge capacity retention of about 64 % after 700 cycles at 335 mA g-1 and 25 °C.

Strained Pt(221) Facet in a PtCo@Pt-Rich Catalyst Boosts Oxygen Reduction and Hydrogen Evolution Activity.

Over the last years, the development of highly active and durable Pt-based electrocatalysts has been identified as the main target for a large-scale industrial application of fuel cells. In this work, we make a significant step ahead in this direction by preparing a high-performance electrocatalyst and suggesting new structure-activity design concepts which could shape the future of oxygen reduction reaction (ORR) catalyst design. For this, we present a new one-dimensional nanowire catalyst consisting of a L10 ordered intermetallic PtCo alloy core and compressively strained high-index facets in the Pt-rich shell. We find the nanoscale PtCo catalyst to provide an excellent turnover for the ORR and hydrogen evolution reaction (HER), which we explain from high-resolution transmission electron microscopy and density functional theory calculations to be due to the high ratio of Pt(221) facets. These facets include highly active ORR and HER sites surprisingly on the terraces which are activated by a combination of sub-surface Co-induced high Miller index-related strain and oxygen coverage on the step sites. The low dimensionality of the catalyst provides a cost-efficient use of Pt. In addition, the high catalytic activity and durability are found during both half-cell and proton exchange membrane fuel cell (PEMFC) operations for both ORR and HER. We believe the revealed design concepts for generating active sites on the Pt-based catalyst can open up a new pathway toward the development of high-performance cathode catalysts for PEMFCs and other catalytic systems.

Injectable hyaluronic acid hydrogel encapsulated with Si-based NiO nanoflower by visible light cross-linking: Its antibacterial applications.

Bacterial infections have become a severe threat to human health and antibiotics have been developed to treat them. However, extensive use of antibiotics has led to multidrug-resistant bacteria and reduction of their therapeutic effects. An efficient solution may be localized application of antibiotics using a drug delivery system. For clinical application, they need to be biodegradable and should offer a prolonged antibacterial effect. In this study, a new injectable and visible-light-crosslinked hyaluronic acid (HA) hydrogel loaded with silicon (Si)-based nickel oxide (NiO) nanoflowers (Si@NiO) as an antibacterial scaffold was developed. Si@NiO nanoflowers were synthesized using chemical bath deposition before encapsulating them in the HA hydrogel under a mild visible-light-crosslinking conditions to generate a Si@NiO-hydrogel. Si@NiO synthesis was confirmed using scanning electron microscopy, transmission electron microscopy, and powder X-ray diffraction. As-prepared Si@NiO-hydrogel exhibited enhanced mechanical properties compared to a control bare hydrogel sample. Moreover, Si@NiO-hydrogel exhibits excellent antibacterial properties against three bacterial strains (P. aeruginosa, K. pneumoniae, and methicillin-resistant Staphylococcus aureus (>99.9% bactericidal rate)) and negligible cytotoxicity toward mouse embryonic fibroblasts. Therefore, Si@NiO-hydrogel has the potential for use in tissue engineering and biomedical applications owing to its injectability, visible-light crosslink ability, degradability, biosafety, and superior antibacterial property.

Biocompatible Core-Shell-Structured Si-Based NiO Nanoflowers and Their Anticancer Activity.

Compared to most of nano-sized particles, core-shell-structured nanoflowers have received great attention as bioactive materials because of their high surface area with the flower-like structures. In this study, core-shell-structured Si-based NiO nanoflowers, Si@NiO, were prepared by a modified chemical bath deposition method followed by thermal reduction. The crystal morphology and basic structure of the composites were characterized by powder X-ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), specific surface area (BET) and porosity analysis (BJT), and inductively coupled plasma optical emission spectrometry (ICP-OES). The electrochemical properties of the Si@NiO nanoflowers were examined through the redox reaction of ascorbic acid with the metal ions present on the surface of the core-shell nanoflowers. This reaction favored the formation of reactive oxygen species. The Si@NiO nanoflowers showed excellent anticancer activity and low cytotoxicity toward the human breast cancer cell line (MCF-7) and mouse embryonic fibroblasts (MEFs), respectively, demonstrating that the anticancer activities of the Si@NiO nanoflowers were primarily derived from the oxidative capacity of the metal ions on the surface, rather than from the released metal ions. Thus, this proves that Si-based NiO nanoflowers can act as a promising candidate for therapeutic applications.

Self-Templated Formation of Fluffy Graphene-Wrapped Ni5P4 Hollow Spheres for Li-Ion Battery Anodes with High Cycling Stability.

Transition-metal phosphides have gained great importance in the field of energy conversion and storage such as electrochemical water splitting, fuel cells, and Li-ion batteries. In this study, a rationally designed novel fluffy graphene (FG)-wrapped monophasic Ni5P4 (Ni5P4@FG) is in-situ-synthesized using a chemical vapor deposition method as a Li-ion battery anode material. The porous and hollow structure of Ni5P4 core is greatly helpful for lithium-ion diffusion, and at the same time, the cilia-like graphene nanosheet shell provides an electron-conducting layer and stabilizes the solid electrolyte interface formed on the Ni5P4 surface. The Ni5P4@FG sample shows a high reversible capacity of 739 mAh g-1 after 300 cycles at a specific current density of 500 mA g-1. The high capacity, superior cycling stability, and improved rate capability of Ni5P4@FG are ascribed to its unique hierarchical structure. Moreover, the present efficient fabrication methodology of Ni5P4@FG has potential to be developed as a general method for the synthesis of other transition-metal phosphides.

Self-Limiting Growth of Single-Layer N-Doped Graphene Encapsulating Nickel Nanoparticles for Efficient Hydrogen Production.

Effective nonprecious metal catalysts are urgently needed for hydrogen evolution reaction (HER). The hybridization of N-doped graphene and a cost-effective metal is expected to be a promising approach for enhanced HER performance but faces bottlenecks in controllable fabrication. Herein, a silica medium-assisted method is developed for the high-efficient synthesis of single-layer N-doped graphene encapsulating nickel nanoparticles (Ni@SNG), where silica nanosheets molecule sieves tactfully assist the self-limiting growth of single-layer graphene over Ni nanoparticles by depressing the diffusion of gaseous carbon radical reactants. The Ni@SNG sample synthesized at 800 °C shows excellent activity for HER in alkaline medium with a low overpotential of 99.8 mV at 10 mA cm-2, which is close to that of the state-of-the-art Pt/C catalyst. Significantly, the Ni@SNG catalyst is also developed as a binder-free electrode in magnetic field, exhibiting much improved performance than the common Nafion binder-based electrode. Therefore, the magnetism adsorption technique will be a greatly promising approach to overcome the high electron resistance and poor adhesive stability of polymer binder-based electrodes in practical applications.

Heterostructured Titanium Oxynitride-Manganese Cobalt Oxide Nanorods as High-Performance Electrode Materials for Supercapacitor Devices.

Metal oxynitrides have been considered recently as emerging electrode materials for supercapacitors. Herein, we converted titanate nanotubes into a series of titanium oxynitride (TiON) nanorods at nitridation temperatures of 800, 900, and 1000 °C in ammonia gas and tested them as supercapacitor electrodes. TiON-800, TiON-900, and TiON-1000 showed capacities of 60, 140, and 71 F g-1, respectively, at a current density of 1 A g-1. However, because of TiON's low capacity, a heterostructure (TiON-900/MnCo2O4) was designed based on the optimized TiON with MnCo2O4 (MCO). The heterostructure TiON-900-MCO and MCO electrode materials showed specific capacities of 515 and 381 F g-1, respectively, at a current density of 1 A g-1. The cycling stability retention of TiON-900 and MCO were 75 and 68%, respectively; moreover, the heterostructure of TiON-900-MCO reached 78% at a current density of 5 A g-1 over 5000 cycles. The increased capacity and sustained cycling stability retention are attributable to the synergistic effect of TiON-900 and MCO. A coin cell (CC)-type symmetric supercapacitor prototype of TiON-900-MCO was fabricated and tested in the voltage range of 0.0-2.0 V in 1 M LiClO4 in propylene carbonate/dimethyl carbonate electrolyte, and a 79% cycling retention capacity of TiON-900-MCO-CC was achieved over 10 000 cycles at a current density of 250 mA g-1. We demonstrated a prototypical single cell of TiON-900-MCO-CC as a sustained energy output by powering a red-light emitting diode that indicated TiON-900-MCo electrode materials' potential application in commercial supercapacitor devices.

Real-time monitored photocatalytic activity and electrochemical performance of an rGO/Pt nanocomposite synthesized via a green approach.

Herein, we have reported the real-time photodegradation of methylene blue (MB), an organic pollutant, in the presence of sunlight at an ambient temperature using a platinum-decorated reduced graphene oxide (rGO/Pt) nanocomposite. The photocatalyst was prepared via a simple, one-pot and green approach with the simultaneous reduction of GO and Pt using aqueous honey as a reducing agent. Moreover, the honey not only simultaneously reduced Pt ions and GO but also played a key role in the growth and dispersion of Pt nanoparticles on the surface of rGO. Various rGO/Pt nanocomposites with different percentages of Pt nanoparticles loaded on rGO were obtained by tuning the concentration of the Pt source. The high percentage of Pt nanoparticles with an average size of 2.5 nm dispersed on rGO has shown excellent electrochemical performance. The photocatalytic activity of the rGO/Pt composite was enhanced by increasing the weight percent of the Pt particles on rGO, which led to the formation of a highly efficient photocatalyst. The optimized photocatalyst exhibited remarkable photocatalytic activity and degraded 98% MB in 180 minutes; thus, it can be used for industrial and environmental applications.

Sub 10 nm CoO nanoparticle-decorated graphitic carbon nitride for solar hydrogen generation via efficient charge separation.

Solar hydrogen generation is one of the most compelling concepts in modern research to address both the energy and environmental issues simultaneously for the survival of the human race. A Type II heterojunction (CoO-GCN) was fabricated by decorating sub 10 nm CoO nanoparticles (NPs) on the graphitic carbon nitride (GCN) surface. It exhibited improved absorption of UV-VIS light and efficiently separate the photogenerated electrons and holes in opposite directions. A maximum hydrogen generation rate of 9.8 mmol g-1 h-1 was recorded using CoO-GCN from 10% aqueous triethanolamine under simulated sunlight in the presence of 1 wt% Pt. The rate is 3.8 times higher than that of bare GCN. Furthermore, it showed excellent stability for up to five repeated uses. Interestingly, the study also revealed that untreated seawater could replace the deionized water. The cooperative participation of the uniform shape and size of CoO NPs firmly grafted on GCN resulted in remarkable performance for solar hydrogen generation.

Stable and sustainable photoanodes using zinc oxide and cobalt oxide chemically gradient nanostructures for water-splitting applications.

Amorphous cobalt oxide (CoO) encapsulated zinc oxide (ZnO) nanostructures were developed by adopting three low-temperature methods respectively atomic layer deposition, chemical bath deposition, and electrochemical deposition. The impact of CoO growth on the physical and chemical properties of ZnO nanostructures was investigated. Then, the ZnO/CoO core/shell nanostructures grown under optimized conditions were adopted for the fabrication of photoelectrochemical (PEC) water-splitting devices. The catalytic performance of ZnO nanostructures is substantially improved after their encapsulation with CoO layers. In addition, the chemical stability and durability of the structures are significantly enhanced. Under typical measurement conditions, these surface-modified ZnO nanostructures exhibited incident photon to charge carrier conversion efficiency (IPCE) higher than 16%, and a stable photocurrent density of 1.25 mA cm-2. Further, these ZnO/CoO nanostructured photoanodes showed a high illumination to dark current density ratio, ~2910.

Electron transfer interpretation of the biofilm-coated anode of a microbial fuel cell and the cathode modification effects on its power.

Biofilm-coated electrodes and outer cell membrane-mimicked electrodes were examined to verify an extracellular electron transfer mechanism using Marcus theory for a donor-acceptor electron transfer. Redox couple-bound membrane electrodes were prepared by impregnating redox coenzymes into Nafion films on carbon cloth electrodes. The electron transfer was believed to occur sequentially from acetate to nicotinamide adenine dinucleotide (NAD), c-type cytochrome, flavin mononucleotide (FMN) (or riboflavin (RBF)) and the anode substrate. Excellent polarisation and power density characteristics were contributed by the modification of the cathode with a high-surface-area ordered mesoporous carbon or a hollow core-mesoporous shell carbon. The maximum power density of the microbial fuel cell (MFC) could be improved by a factor of two mainly due to the accelerated electron consumption by modifying the cathode surfaces within three-dimensionally interconnected mesoporous carbon particles, and the anode was coated with a mixed culture of anaerobic bacteria.

Silicon core-mesoporous shell carbon spheres as high stability lithium-ion battery anode.

An innovative and simple synthesis strategy of silicon nanoparticle (Si NP) core covered by mesoporous shell carbon (MSC) structure is demonstrated. The Si core@MSC (SCMSC) composite is developed for addressing the issues for Si anode material in lithium ion batteries (LIBs) such as high volume expansion and low electrical conductivity. Significant improvement in the electrochemical performance for the SCMSC anode is observed compared with bare Si anode. The SCMSC composite delivers an initial specific capacity of 2450 mAh g-1 at 0.166 A g-1 with Coulombic efficiency of 99.2% for 100 cycles. Compared to bare Si anode, the SCMSC anode exhibits much higher Li storage capacity, superior cyclability, and good rate capability, highlighting the advantages of hierarchical MSC in the SCMSC structure.

Hydrogenated MoS2 QD-TiO2 heterojunction mediated efficient solar hydrogen production.

Herein, we report the development of a hydrogenated MoS2 QD-TiO2 (HMT) heterojunction as an efficient photocatalytic system via a one-pot hydrothermal reaction followed by hydrogenation. This synthetic strategy facilitates the formation of MoS2 QDs with an enhanced band gap and a proper heterojunction between them and TiO2, which accelerates charge transfer process. Hydrogenation leads to oxygen vacancies in TiO2, enhancing the visible light absorption capacity through narrowing its band gap, and sulfur vacancies in MoS2, which enhance the active sites for hydrogen adsorption. Due to the band gap reduction of hydrogenated TiO2 and the band gap enhancement of the MoS2 QDs, the energy states are rearranged to create a reverse movement of electrons and holes facilitated the charge transfer process which enhance life-time of photo-generated charges. The photocatalyst showed stable, efficient and exceptionally high noble metal free sunlight-induced hydrogen production with a maximum rate of 3.1 mmol g-1 h-1. The developed synthetic strategy also provides flexibility towards the shape of the MoS2, e.g. QDs/single or few layers, on TiO2 and offers the opportunity to design novel visible light active photocatalysts for different applications.

Urine to highly porous heteroatom-doped carbons for supercapacitor: A value added journey for human waste.

Obtaining functionalized carbonaceous materials, with well-developed pores and doped heteroatoms, from waste precursors using environmentally friendly processes has always been of great interest. Herein, a simple template-free approach is devised to obtain porous and heteroatom-doped carbon, by using the most abundant human waste, "urine". Removal of inherent mineral salts from the urine carbon (URC) makes it to possess large quantity of pores. Synergetic effect of the heteroatom doping and surface properties of the URC is exploited by carrying out energy storage application for the first time. Suitable heteroatom content and porous structure can enhance the pseudo-capacitance and electric double layer capacitance, eventually generating superior capacitance from the URC. The optimal carbon electrode obtained particularly at 900 °C (URC-900) possesses high BET surface area (1040.5 m2g-1), good conductivity, and efficient heteroatom doping of N, S, and P, illustrating high specific capacitance of 166 Fg-1 at 0.5 Ag-1 for three-electrode system in inorganic electrolyte. Moreover, the URC-900 delivers outstanding cycling stability with only 1.7% capacitance decay over 5,000 cycles at 5 Ag-1. Present work suggests an economical approach based on easily available raw waste material, which can be utilized for large-scale production of new age multi-functional carbon nanomaterials for various energy applications.

Synthesis of Water-Dispersible Single-Layer CoAl-Carbonate Layered Double Hydroxide.

Despite extensive study on single-layer layered double hydroxides (SL-LDHs) with NO3- counterions, SL-LDHs with CO32- counterions (CO32- SL-LDHs) have never been prepared before. Herein, a CoAl-CO32- SL-LDH which stays stable in water and powdery state is first synthesized using ethylene glycol as a reaction medium. The SL-LDH, with thickness of ∼0.85 nm, is composed of one Co(Al)O6 layer sandwiched between two CO32- layers. The SL-LDH powder shows high specific surface area (∼289 m2/g) and excellent electrocatalytic oxygen evolution efficiency. This work provides the first simple way to prepare CO32- SL-LDHs and will open an avenue for synthesizing other SL-LDHs.