Updated Metal Compounds (MOFs, ?S, ?OH, ?N, ?C) Used as Cathode Materials for Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have the potential to be as efficient and as widespread as lithium‐ion (Li‐ion) batteries, since sulfur electrode has high theoretical capacity (1672 mA h g_sul^?1) and this element is affordable. However, unlike their ubiquitous lithium ion (Li‐ion) counterparts, it is difficult to realize the commercialization of Li‐S battery. Because the shuttle effect of polysulfide inevitably results in the serious capacity degradation. Tremendous progress is devoted to approach this problem from the aspect of physical confinement and chemisorption of polysulfide. Owing to weak intermolecular interactions, physical confinement strategy, however is not effective when the battery is cycled long‐term. Chemisorption of polysulfide that derived from polar–polar interaction, Lewis acid–base interaction, and sulfur‐chain catenation, are proven to significantly suppress the shuttle effect of polysulfide. It is also discovered that the metal compounds have strong chemical interactions with polysulfide. Therefore, this review focuses on latest metal–organic frameworks metal sulfides, metal hydroxides, metal nitrides, metal carbides, and discusses how the chemical interactions couple with the unique properties of these metal compounds to tackle the problem of polysulfide shuttle effect.     

Updated Metal Compounds (MOFs, S, OH, N, C) Used as Cathode Materials for Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have the potential to be as efficient and as widespread as lithium‐ion (Li‐ion) batteries, since sulfur electrode has high theoretical capacity (1672 mA h g_sul^?1) and this element is affordable. However, unlike their ubiquitous lithium ion (Li‐ion) counterparts, it is difficult to realize the commercialization of Li‐S battery. Because the shuttle effect of polysulfide inevitably results in the serious capacity degradation. Tremendous progress is devoted to approach this problem from the aspect of physical confinement and chemisorption of polysulfide. Owing to weak intermolecular interactions, physical confinement strategy, however is not effective when the battery is cycled long‐term. Chemisorption of polysulfide that derived from polar–polar interaction, Lewis acid–base interaction, and sulfur‐chain catenation, are proven to significantly suppress the shuttle effect of polysulfide. It is also discovered that the metal compounds have strong chemical interactions with polysulfide. Therefore, this review focuses on latest metal–organic frameworks metal sulfides, metal hydroxides, metal nitrides, metal carbides, and discusses how the chemical interactions couple with the unique properties of these metal compounds to tackle the problem of polysulfide shuttle effect.     

A Concentrated Ternary‐Salts Electrolyte for High Reversible Li Metal Battery with Slight Excess Li

Li metal can potentially deliver much higher specific capacity than commercially used anodes. Nevertheless, because of its poor reversibility, abundant excess Li (usually more than three times) is required in Li metal batteries, leading to higher costs and decreased energy density. Here, a concentrated lithium bis(trifluoromethane sulfonyl) imide (LiTFSI)–lithium nitrate (LiNO₃)–lithium bis(fluorosulfonyl)imide (LiFSI) ternary‐salts electrolyte is introduced to realize a high stable Li metal full‐cell with only a slight excess of Li. LiNO₃ and LiFSI contribute to the formation of stable Li₂O–LiF‐rich solid electrolyte interface layers, and LiTFSI helps to stabilize the electrolyte under high concentration. Li metal in the electrolyte remains stable over 450 cycles and the average Coulombic efficiency reaches 99.1%. Moreover, with 0.5 × excess Li metal, the Coulombic efficiency of Li metal in the LiTFSI–LiNO₃–LiFSI reaches 99.4%. The electrolyte also presents high stability to the LiFePO₄ cathode, the capacity retention after 500 cycles is 92.0% and the Coulombic efficiency is 99.8%. A Li metal full‐cell with only 0.44 × excess Li is also assembled, it remains stable over 70 cycles and 83% of the initial capacity is maintained after 100 cycles.     

Analysis and Optimum Design of Hybrid Plasmonic Slab Waveguides

Propagation properties of hybrid plasmonic slab waveguides are studied in detail using transfer matrix method considering structural and material aspects. Hybrid metal–insulator, hybrid metal–insulator–metal, and hybrid insulator–metal–insulator waveguides are considered. Propagation length (L _p), spatial length (L _s), and mode length (L _m) are utilized as three common figures of merit to compare and optimize the waveguides according to the layer thicknesses and metal/dielectric materials. The effect of constituting materials including metals (such as silver, gold, copper, and aluminum) and dielectrics (common dielectric materials used in photonic integrated circuit technologies such as silicon and silicon compounds, III–V compounds, and polymers) are discussed. It is found that hybrid waveguides are partially to completely superior to conventional plasmonic waveguides, providing a better balance between confinement and loss.     

Accumulation of Trace Metals by Mangrove Plants in Indian Sundarban Wetland: Prospects for Phytoremediation

The work investigates on the potential of ten mangrove species for absorption, accumulation and partitioning of trace metal(loid)s in individual plant tissues (leaves, bark and root/pneumatophore) at two study sites of Indian Sundarban Wetland. The metal(loid) concentration in host sediments and their geochemical characteristics were also considered. Mangrove sediments showed unique potential in many- fold increase for most metal(loid)s than plant tissues due to their inherent physicochemical properties. The ranges of concentration of trace metal(loid)s for As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn in plant tissue were 0.006–0.31, 0.02–2.97, 0.10–4.80, 0.13–6.49, 4.46–48.30, 9.2–938.1, 0.02–0.13, 9.8–1726, 11–5.41, 0.04–7.64, 3.81–52.20 μg g ^?1respectively. The bio- concentration factor (BCF) showed its maximum value (15.5) in Excoecaria agallocha for Cd, suggesting that it can be considered as a high-efficient plant for heavy metal bioaccumulation. Among all metals, Cd and Zn were highly bioaccumulated in E. agallocha (2.97 and 52.2 μg g ^?1 respectively. Our findings suggest that the species may be classified as efficient metal trap for Cd in aerial parts, as indicated by higher metal accumulation in the leaves combined with BCF and translocation factor (TF) values.     

Biomonitoring of airborne metals using the Lichen Xanthoria parietina in Kocaeli Province,Turkey

Airborne metal deposition in the major urban and the industrial districts of Kocaeli was monitored using Xanthoria parietina lichen specimen as a biomonitoring organism. Lichen samples were analyzed for Al, As, Co, Cd, Cu, Fe, Hg, Mn, Ni, Pb, Ti, Tl, V and Zn contents to determine the relationship between the potential pollutant sources in the region and the degree of airborne metal deposition. Results showed that airborne metal deposition in the Kocaeli province was widespread and environmental alteration was serious near the industrial facilities. Mean metal concentrations of lichen samples in the industrial district (Dilovası) of Kocaeli were two to seven folds higher than those in the urban districts of Kocaeli: Mn (7), Pb–Cd–Zn (6), Fe–Ni–Cu (3) and Al–Co–Ti–Hg–As–V (2). Environmental alteration in Dilovası region was severe in terms of all metals analyzed. Cluster analysis showed that metal industry (iron–steel, aluminum, zinc) in Dilovası, fossil fuel combustion processes related to the industry and power plant and heavy traffic contributed significantly to the metal emission in Dilovası region. Airborne metal deposition in the urban districts of Kocaeli was high especially around the coal-fired cement plant in Hereke and petroleum refinery in Körfez. Fossil fuel combustion and traffic emission were among the important sources of airborne metals in the urban–suburban districts.     

Metal–Air Batteries: From Static to Flow System

As an emerging battery technology, metal–air flow batteries inherit the advantageous features of the unique structural design of conventional redox flow batteries and the high energy density of metal–air batteries, thus showing great potential as efficient electrochemical systems for large‐scale electrical energy storage. This review summarizes the operating principles and recent progress of metal–air flow batteries from a materials and chemistry perspective, with particular emphasis on the latest advanced materials design and cell configuration engineering, which the authors divide into three categories based on the anode species: vanadium–air, zinc–air, and lithium–air flow batteries. Since some of the capabilities developed for metal–air static batteries can be leveraged for next‐generation flow systems, classical works on conventional metal–air batteries are selected and compared with the metal–air flow systems, highlighting the prominent advantages of the latter in achieving high energy capacity and long cycle performance. At the end, a general perspective on current challenges/opportunities and future research directions to promote the commercial application of the metal–air flow battery technology is provided. The aim is to provide a comprehensive overview and to set up a road map for guiding development from conventional static to advanced flow technologies of metal–air batteries.     

Localized Surface Plasmon Resonance and Refractive Index Sensitivity of Metal–Dielectric–Metal Multilayered Nanostructures

The localized surface plasmon resonances of multilayered nanostructures are studied using finite difference time domain simulations and plasmon hybridization method. Concentric metal–dielectric–metal (MDM) structure with metal core and nanoshell separated by a thin dielectric layer exhibits a strong coupling between the core and nanoshell plasmon resonance modes. The coupled resonance mode wavelengths show dependence on the dielectric layer thickness and composition of core and outer layer metal. The aluminum-based MDM structures show lower plasmon wavelength compared with Ag- and Au-based MDM nanostructures. The calculated refractive index sensitivity (RIS) factor is in the order Ag–Air–Ag>Au–Air–Au>Al–Air–Al for monometallic multilayered nanostructures. Bimetallic multilayered nanostructures support strong and tunable plasmon resonance wavelengths as well as high RIS factor of 510 nm/refractive index unit (RIU) and 470 nm/RIU for Al–Air–Au and Ag-Air-Au, respectively. The MDM structures not only exhibit higher index sensitivity but also cover a wide ultraviolet–near-infrared wavelengths, making these structures very promising for index sensing, biomolecule sensing, and surface-enhanced Raman spectroscopy.     

A model for the homogeneous isospecific Ziegler–Natta polymerization of olefins: Enantioselectivity in the deuteration and deuteriooligomerization of 1-alkenes

The enantioselectivity found in homogeneous isospecific Ziegler–Natta catalysts for the insertion of 1-alkenes in metal–deuterium or in metalisobutyl bonds is discussed from a theoretical point of view. Nonbonded energy calculations, based on a model of the catalytic site previously proposed by us, indicate that the strong enantioselectivity found in the insertion of 1-alkenes in a metal–isobutyl bond is drastically reduced in the presence of a metal–deuterium bond. In particular, a weak enantioselectivity in favour of a monomer coordinated with the opposite chirality (lower for the case of 1-butene, higher for the case of styrene) is shown to occur in the latter case.     

Performance of density functionals for the structure and energetics of (M–O)0,± (M=Al,Si, Sc–Zn)

We report the results of the performance of 20 exchange–correlation functionals of density functional theory (DFT) in the structure (Metal–Oxygen bond length) and energetical properties (bond dissociation energy, adiabatic ionisation energy, and adiabatic electron affinity) of twelve metal monoxides (M–O, M=Al, Si, Sc–Zn). The calculated results show that the selected DFT functionals have the ability to reproduce the M–O bond length with a mean deviation of 0.01–0.05 Å, the energy values are reproduced with a mean deviation of 0.20–1.00?eV. In general, the functionals with significant HF exchange show decent performance in the calculation of bond length and harmonic vibrational frequency. These functionals show poor performance in energetics. Our calculated results show that the M06-L, B3LYP, and TPSSh functionals give good performance in both structure and energetical properties of metal monoxides. These functionals are recommended for the studies of structure and energetics in metal oxide systems. Further, our studies indicate that M06-L can be used for the studies in larger molecular systems. Among the 20 DFT functionals, the recently developed N12 functional gives poor performance in the studies of metal monoxides. Hence this functional is not recommended for the studies of structure and energetics in metal oxide systems.     

Dynamically Switchable Multispectral Plasmon-Induced Transparency in Stretchable Metamaterials

We propose dynamically switchable multispectral plasmon-induced transparency (PIT) with high modulation depth in a three-dimensional metamaterial standing on a flexible substrate. The proposed metamaterial is composed of a pair of metal–insulator–metal (MIM) nano-cut-wires and a pair of insulator–metal–insulator (IMI) nano-cut-wires. Results show that two PIT windows can be achieved because of the near-field coupling between the dipole supported by the IMI nano-cut-wire and two quadrupoles supported by the MIM structures. These two PIT windows can be blue-shifted or even flipped over by stretching the substrate along one direction, or be switched off by stretching along the other direction. A classical coupled oscillator model is developed to quantitatively describe and explain these results. We expect this work will find promising applications in multispectral sensors, slow light devices and nonlinear optical devices.

     

Strategies Toward Stable Nonaqueous Alkali Metal–O2 Batteries

Alkali metal–O₂ batteries, by coupling high‐capacity alkali metal anodes with gaseous oxygen, possess extremely high gravimetric energy density that is comparable to gasoline and are potential energy storage technologies beyond lithium–ion batteries. The development of alkali metal–O₂ batteries has achieved great progress in recent years, from materials to prototype devices and on fundamental mechanisms. The stability of alkali metal–O₂ batteries is still poor, however, leading to a huge gap between laboratory research and commercial applications. A series of parasitic reactions result in the instability, which occur during electrochemical discharging and charging. The ubiquitous active oxygen species attack both the organic electrolyte and the carbon cathode, triggering various parasitic reactions. Meanwhile, dendrite growth and volume expansion upon repeated plating/stripping and O₂ crossover severely limit the reversibility of alkali metal anodes. Here, an overview of the strategies against these issues is given to improve the stability of nonaqueous alkali metal–O₂ batteries, which is discussed from three aspects: air cathodes, alkali metal anodes, and aprotic electrolytes. Furthermore, perspectives for future research of stable alkali metal–O₂ batteries are outlined.     

In Vitro Penetration of Pig Skin by Heavy Metals in Soil

The potential health risk from exposure to heavy metal contaminated soil is often based on the quantity of metal that can be removed from soil by vigorous extraction procedures. This approach can overestimate risk since it ignores complex interactions between metals and soil that can result in a reduction in the amount of metal that desorbs from soil and is subsequently absorbed by the body. The aim of this research was to determine the relative contribution of the soil matrix and heavy metal sequestration in soil with time (“aging”) on the dermal penetration of arsenic, mercury, and nickel, respectively, as arsenic acid, mercuric chloride, and nickel chloride. In vitro flow-through diffusion cell studies were performed utilizing dermatomed male pig skin and radioactive compounds to measure total penetration (the sum of each metal in receptor fluid and skin). For arsenic and nickel, the soil matrix produced a 78–87% reduction in dermal penetration compared to 12–19% after aging. A greater effect was observed with aged mercury (52–56% decrease in dermal penetration) than in freshly spiked soil (40–43%). The results indicate that the potential health risk from dermal exposure to the metals can be significantly reduced by soil and aging.     

Thermal behaviour of Pd clusters inside carbon nanotubes: insights into the cluster-size,tube-size and metal–tube interaction effects

Molecular dynamics simulations were used to investigate the cluster-size, tube-size and metal–tube interaction effects on the melting of Pd clusters encapsulated inside carbon nanotubes (CNTs). The second moment approximation to the tight-binding potential was used to model Pd–Pd metal–metal interaction and the Tersoff potential was used for C–C interactions. Pd–C interaction was modelled by the typical weak van der Waals Lennard-Jones (VDW-LJ) potential to understand the cluster-size and tube-size effects on the thermal behaviour of supported Pd clusters. Linear decrease in cluster melting point with the inverse in cluster diameter is predicted for the CNT containing Pd clusters, well known as Pawlow's law. It is also found that the melting temperature of the supported Pd cluster is much lower than that of free one, and the rearrangement and transformation of the cluster at higher temperatures before melting are responsible for this lowering. In this case, the downward shift is independent of the CNT diameter for the same Pd cluster. In addition, the Pd–C interaction was redefined to assess the metal–tube interaction effect on the thermal evolution of the CNT-containing Pd clusters by fitting to first-principle calculations. Using the fitted strong density functional theory-Morse Pd–C potential, deformation for the CNT and structural transformation from the icosahedral to the stacked for the Pd cluster inside the CNT are found, which is not shown by using the VDW-LJ potential.     

Sol–gel transition of alginate solution by the addition of various divalent cations: 13C-nmr spectroscopic study

¹³C-NMR spectroscopic studies have been made on alginate solutions undergoing sol–gel transition induced by four different divalent cations: Ca, Cu, Co, and Mn. From the analysis of nmr spectra and relaxation times, we have found different interaction modes existing between the Ca–alginate systems and the transition metal (Cu, Co, and Mn)–alginate systems. In the Ca–alginate systems, there exists a specific interaction characterized by a strong autocooperative binding between guluronate residues and calcium ions, and all functional groups in guluronate residues are considered to involve the interaction with calcium ions. On the other hand, in transition metal (Cu, Co, and Mn)–alginate systems, sol–gel transition is characterized by a complex formation in which the carboxyl groups in both mannuronate and guluronate residues are coordinated to metal ions. The other functional groups, like hydroxyl groups, do not participate in the binding to metal ions. It is suggested by relaxation time measurements that from a microscopic point of view the sol–gel transition phenomena can be explained as a dynamic process in which the low frequency molecular motions are dominant and increase their proportions with the formation of three-dimensional cross-links. © 1993 John Wiley & Sons, Inc.     

Large Plasmonic Resonance Shifts from Metal Loss in Slits

Plasmonics - The impact of loss on the plasmonic resonances in metal–insulator–metal slits is analyzed, particularly the significant effect of loss on the reflection phase. The...     

Toward Promising Cathode Catalysts for Nonlithium Metal–Oxygen Batteries

The success of Li–air/O₂ batteries has brought extensive attention to the development of various promising non‐Li metal–O₂ batteries, such as Zn–O₂, Al–O₂, Mg–O₂ batteries, etc., which have exhibited unique advantages, such as low production cost, high energy density, and much enhanced safety. The versatile non‐Li metal–O₂ batteries provide a better opportunity for meeting the practical requirements for sustainable energy supplies in various applications. A high‐performance cathode in non‐Li metal–O₂ batteries that can effectively trigger both oxygen reduction and evolution reactions and thus boost the overall battery performance is of great research interest. In this article, a comprehensive review on the development of Li‐free metal–O₂ batteries and particularly focusing on the oxygen catalytic cathodes for both primary and secondary non‐Li metal–O₂ batteries is carefully performed. The current challenges and potential solutions are also outlined and proposed. Through carefully selecting and rationally designing promising catalytic cathodes, a series of non‐Li metal–oxygen batteries toward practical energy storage applications are highly anticipated.     

Structural studies of the tethered N‐terminus of the Alzheimer's disease amyloid‐β peptide

Alzheimer's disease is the most common form of dementia in humans and is related to the accumulation of the amyloid‐β (Aβ) peptide and its interaction with metals (Cu, Fe, and Zn) in the brain. Crystallographic structural information about Aβ peptide deposits and the details of the metal‐binding site is limited owing to the heterogeneous nature of aggregation states formed by the peptide. Here, we present a crystal structure of Aβ residues 1–16 fused to the N‐terminus of the Escherichia coli immunity protein Im7, and stabilized with the fragment antigen binding fragment of the anti‐Aβ N‐terminal antibody WO2. The structure demonstrates that Aβ residues 10–16, which are not in complex with the antibody, adopt a mixture of local polyproline II‐helix and turn type conformations, enhancing cooperativity between the two adjacent histidine residues His13 and His14. Furthermore, this relatively rigid region of Aβ (residues, 10–16) appear as an almost independent unit available for trapping metal ions and provides a rationale for the His13‐metal‐His14 coordination in the Aβ_1–16 fragment implicated in Aβ metal binding. This novel structure, therefore, has the potential to provide a foundation for investigating the effect of metal ion binding to Aβ and illustrates a potential target for the development of future Alzheimer's disease therapeutics aimed at stabilizing the N‐terminal monomer structure, in particular residues His13 and His14, and preventing Aβ metal‐binding‐induced neurotoxicity.Proteins 2013; 81:1748–1758. © 2013 Wiley Periodicals, Inc.     

Assessment of Hazardous and Essential Elements in a Food Crop Irrigated with Municipal Sewage Water: Risk Appraisal for Public Health

To assess the impact of sewage water on metal accretion in selected diverse varieties of wheat (i.e., Lasani-2008, ARRI-10, Faisalabad-83, Punjab-85, Aas-2010, and Sehar-2006), their seeds were sown in pots containing soil. The results showed that the concentration of heavy metals in grains from the wheat plants supplied with sewage water was considerably higher than the plants supplied with canal irrigation water (control). In canal water irrigated wheat grains the metal concentrations (mg/kg) ranged from 2.20–3.5 for Cu, 12.50–32.4 for Zn, 22.45–35.22 for Mn, 0.05–0.15 for Pb, 0.012–0.029 for Cd, 2.5–5.3 for Ni, 18.16–29.63 for Fe, and 0.90–3.64 for Cr in different wheat varieties, whereas the wheat grains raised from sewage water, had metal concentrations (mg/kg): 3.8–5.30 for Cu, 29.60–40.50 for Zn, 32.9–50.40 for Mn, 1.14–7.50 for Pb, 0.26–0.42 for Cd, 3.90–7.55 for Ni, 32.21–40.35 for Fe, and 2.88–7.84 for Cr. Since these metals bioaccumulate in wheat grains with unremitting use of metal-enriched wastewater, care has to be taken for irrigating wheat plants with household wastewater for a longer time, particularly in those soils where this crop is grown regularly.