One-dimensional porous La0.5Sr0.5CoO2.91 nanotubes as a highly efficient electrocatalyst for rechargeable lithium-oxygen batteries

The electrochemical performance of one-dimensional porous La_0.5Sr_0.5CoO_2.91 nanotubes as a cathode catalyst for rechargeable nonaqueous lithium-oxygen (Li-O₂) batteries is reported here for the first time. In this study, one-dimensional porous La_0.5Sr_0.5CoO_2.91 nanotubes were prepared by a simple and efficient electrospinning technique. These materials displayed an initial discharge capacity of 7205 mAh g<sup>-1sup> with a plateau at around 2.66 V at a current density of 100 mA g<sup>-1sup>. It was found that the La_0.5Sr_0.5CoO_2.91 nanotubes promoted both oxygen reduction and oxygen evolution reactions in alkaline media and a nonaqueous electrolyte, thereby improving the energy and coulombic efficiency of the Li-O₂ batteries. The cyclability was maintained for 85 cycles without any sharp decay under a limited discharge depth of 1000 mAh g<sup>-1sup>, suggesting that such a bifunctional electrocatalyst is a promising candidate for the oxygen electrode in Li-O₂ batteries.

In situ preparation of 3D graphene aerogels@hierarchical Fe3O4 nanoclusters as high rate and long cycle anode materials for lithium ion batteries

We describe a novel strategy for in situ fabrication of hierarchical Fe₃O₄ nanoclusters-GAs. Fe₃O₄ NCs-GAs deliver excellent rate capability (the reversible capacities obtained were 1442, 392 and 118 mA h g<sup>-1sup> at 0.1C, 12C and 35C rates), and a high reversible capacity of 577 mA h g<sup>-1sup> over 300 cycles at the current density of 5.2 A g<sup>-1sup> (6C).

Three-dimensional graphene-Co3O4 cathodes for rechargeable Li-O2 batteries

A three-dimensional (3D) graphene-Co₃O₄ electrode was prepared by a two-step method in which graphene was initially deposited on a Ni foam with Co₃O₄ then grown on the resulting graphene structure. Cross-linked Co₃O₄ nanosheets with an open pore structure were fully and vertically distributed throughout the graphene skeleton. The free-standing and binder-free monolithic electrode was used directly as a cathode in a Li-O₂ battery. This composite structure exhibited enhanced performance with a specific capacity of 2453 mA h g<sup>-1sup> at 0.1 mA cm<sup>-2sup> and 62 stable cycles with 583 mA h g<sup>-1sup> (1000 mA h g_carbon<sup>-1sup>). The excellent electrochemical performance is associated with the unique architecture and superior catalytic activity of the 3D electrode. 

Investigation into the effect of molybdenum-site substitution on the performance of Sr2Fe1.5Mo0.5O6-δ for intermediate temperature solid oxide fuel cells

In this paper, niobium doping is evaluated as a means of enhancing the electrochemical performance of a Sr₂Fe_1.5Mo_0.5O_6-δ (SFM) perovskite structure cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs) applications. As the radius of Nb approximates that of Mo and exhibits +4/+5 mixed valences, its substitution is expected to improve material performance. A series of Sr₂Fe_1.5Mo_0.5-xNb_xO_6-δ (x = 0.05, 0.10, 0.15, 0.20) cathode materials are prepared and the phase structure, chemical compatibility, microstructure, electrical conductivity, polarization resistance and power generation are systematically characterized. Among the series of samples, Sr₂Fe_1.5Mo_0.4Nb_0.10O_6-δ (SFMNb_0.10) exhibits the highest conductivity value of 30 S cm<sup>-1sup> at 550°C, and the lowest area specific resistance of 0.068 Ω cm<sup>2sup> at 800°C. Furthermore, an anode-supported single cell incorporating a SFMNb_0.10 cathode presents a maximum power density of 1102 mW cm<sup>-2sup> at 800°C. Furthermore no obvious performance degradation is observed over 15 h at 750°C with wet H₂(3% H₂O) as fuel and ambient air as the oxidant. These results demonstrate that SFMNb shows great promise as a novel cathode material for IT-SOFCs.

Investigation into the effect of Fe-site substitution on the performance of Sr2Fe1.5Mo0.5O6-δ anodes for SOFCs

Ni-substituted Sr₂Fe_1.5-xNi_xMo_0.5O_6-δ (SFNM) materials have been investigated as anode catalysts for intermediate temperature solid oxide fuel cells. Reduced samples (x = 0.05 and 0.1) maintained the initial perovskite structure after reduction in H₂, while metallic nickel particles were detected on the grain surface for x = 0.2 and 0.3 using transmission electron microscopy. Temperature programmed reduction results indicate that the stable temperature for SFNM samples under reduction conditions decreases with Ni content. In addition, X-ray photoelectron spectroscopy analysis suggests that the incorporation of Ni affects the conductivity of SFNM through changing the ratios of Fe<sup>3+sup>/Fe<sup>2+sup> and Mo<sup>6+sup>/Mo<sup>5+sup>. Sr₂Fe_1.4Ni_0.1Mo_0.5O_6-δ shows the highest electrical conductivity of 20.6 S cm<sup>-1sup> at 800 °C in H₂. The performance of this anode was further tested with electrolyte-supported cells, giving 380 mW cm<sup>-2sup> at 750 °C in H₂, hence demonstrating that Ni doping in the B-site is beneficial for Sr₂Fe_1.5Mo_0.5O_6-δ anode performance. 

Surface modification of LiV3O8 nanosheets via layer-by-layer self-assembly for high-performance rechargeable lithium batteries

In this work, an economical route based on hydrothermal and layer-by-layer (LBL) self-assembly processes has been developed to synthesize unique Al ₂O₃-modified LiV₃O₈ nanosheets, comprising a core of LiV₃O₈ nanosheets and a thin Al ₂O₃ nanolayer. The thickness of the Al₂O ₃ nanolayer can be tuned by altering the LBL cycles. When evaluated for their lithium-storage properties, the 1 LBL Al₂O ₃-modified LiV₃O₈ nanosheets exhibit a high discharge capacity of 191 mA h g<sup>-1sup> at 300 mA g<sup>-1sup> (1C) over 200 cycles and excellent rate capability, demonstrating that enhanced physical and/or chemical properties can be achieved through proper surface modification. © 2014 Elsevier B.V. All rights reserved.

Facile synthesis of nanocrystalline LiFePO4/graphene composite as cathode material for high power lithium ion batteries

We describe a simple strategy, which is based on the idea of space confinement, for the synthesis of carbon coating on LiFePO₄ nanoparticles/graphene nanosheets composites in a water-in-oil emulsion system. The prepared composite displayed high performance as a cathode material for lithium-ion battery, such as high reversible lithium storage capacity (158 mA h g<sup>-1sup> after 100 cycles), high coulombic efficiency (over 97%), excellent cycling stability and high rate capability (as high as 83 mA h g <sup>-1sup> at 60 C). Very significantly, the preparation method employed can be easily adapted and be extended as a general approach to sophisticated compositions and structures for the preparation of highly dispersed nanosized structure on graphene. 

An in situ ionic-liquid-assisted synthetic approach to iron fluoride/graphene hybrid nanostructures as superior cathode materials for lithium ion batteries

A tactful ionic-liquid (IL)-assisted approach to in situ synthesis of iron fluoride/graphene nanosheet (GNS) hybrid nanostructures is developed. To ensure uniform dispersion and tight anchoring of the iron fluoride on graphene, we employ an IL which serves not only as a green fluoride source for the crystallization of iron fluoride nanoparticles but also as a dispersant of GNSs. Owing to the electron transfer highways created between the nanoparticles and the GNSs, the iron fluoride/GNS hybrid cathodes exhibit a remarkable improvement in both capacity and rate performance (230 mAh g<sup>-1sup> at 0.1 C and 74 mAh g<sup>-1sup> at 40 C). The stable adhesion of iron fluoride nanoparticles on GNSs also introduces a significant improvement in long-term cyclic performance (115 mAh g<sup>-1sup> after 250 cycles even at 10 C). The superior electrochemical performance of these iron fluoride/GNS hybrids as lithium ion battery cathodes is ascribed to the robust structure of the hybrid and the synergies between iron fluoride nanoparticles and graphene. © 2013 American Chemical Society.

Arsenic is not stored as arsenitephytochelatin complexes in the seaweeds Fucus spiralis and Hizikia fusiforme

Environmental context Seaweeds hyperaccumulate the toxic metalloid arsenic, but seemingly achieve detoxification by transformation to arsenosugars. The edible seaweed hijiki is a notable exception because it contains high levels of toxic arsenate and arsenite. Terrestrial plants detoxify arsenic by forming arsenitephytochelatin complexes. The hypothesis that seaweeds also synthesise phytochelatins to bind arsenite as a means of detoxification before arsenosugar synthesis is tested in this investigation. Abstract Phytochelatins (PCs), generic structure [-Glu-Cys]n-Gly, are peptides synthesised by terrestrial plants to bind toxic metal(loid)s such as cadmium and arsenic. Seaweeds are arsenic hyperaccumulators, seemingly achieving detoxification via arsenosugar biosynthesis. Whether seaweeds synthesise PCs to aid detoxification during arsenic exposure is unknown. Hizikia fusiforme (hijiki) and Fucus spiralis were used as model seaweeds: the former is known for its large inorganic arsenic concentration, whereas the latter contains mainly arsenosugars. F. spiralis was exposed to 0, 1 and 10mgL <sup>-1sup> arsenate solutions for 24h, whereas hijiki was analysed fresh. All samples contained As <sup>IIIsup>, glutathione and reduced PC ₂, identified using HPLC-ICP-MS/ES-MS. Although hijiki contained no As <sup>IIIsup>PC complexes, arsenate exposed F. spiralis generated traces of numerous arsenic compounds that might be As <sup>IIIsup>GS or As <sup>IIIsup>PC ₂ complexes. As <sup>IIIsup>PC complexes seem not to be a principal storage form for long-term arsenic storage within seaweeds. However, 40 times higher glutathione concentrations were found in hijiki than F. spiralis, which may explain how hijiki deals with its high inorganic arsenic burden. © 2011 CSIRO.

A field and reactive transport model study of arsenic in a basaltic rock aquifer

The use of geothermal energy as a source for electricity and district heating has increased over recent decades. Dissolved As can be an important constituent of the geothermal fluids brought to the Earth's surface. Here the field application of laboratory measured adsorption coefficients of aqueous As species on basaltic glass surfaces is discussed. The mobility of As species in the basaltic aquifer in the Nesjavellir geothermal system, Iceland was modelled by the one-dimensional (1D) reactive transport model PHREEQC ver. 2, constrained by a long time series of field measurements with the chemical composition of geothermal effluent fluids, pH, Eh and, occasionally, Fe- and As-dissolved species measurements. Di-, tri- and tetrathioarsenic species (As(OH)S22-, AsS₃H<sup>2-sup>, AsS33- and As(SH)4-) were the dominant form of dissolved As in geothermal waters exiting the power plant (2.556μM total As) but converted to some extent to arsenite (H₃AsO₃) and arsenate HAsO42- oxyanions coinciding with rapid oxidation of S2- to S2O32- and finally to SO42- during surface runoff before feeding into a basaltic lava field with a total As concentration of 0.882μM following dilution with other surface waters. A continuous 25-a data set monitoring groundwater chemistry along a cross section of warm springs on the Lake Thingvallavatn shoreline allowed calibration of the 1D model. Furthermore, a series of ground water wells located in the basaltic lava field, provided access along the line of flow of the geothermal effluent waters towards the lake. The conservative ion Cl<sup>-sup> moved through the basaltic lava field (4100m) in less than10a but As was retarded considerably due to surface reactions and has entered a groundwater well 850m down the flow path as arsenate in accordance to the prediction of the 1D model. The 1D model predicted a complete breakthrough of arsenate in the year 2100. In a reduced system arsenite should be retained for about 1ka. © 2011 Elsevier Ltd.

Influence of phosphate addition on the arsenic uptake by wheat (Triticum Durum) grown in arsenic polluted soils

Arsenic (As) uptake and distribution in the roots, shoots, and grain of wheat (Triticum durum) grown in 2 As polluted soils (192 and 304 mg kg <sup>-1sup> respectively), and an uncontaminated soil (14 mg kg<sup>-1sup> ), collected from Scarlino plain (Tuscany, Italy), was investigated with respect with phosphorus fertilization. Three different level of phosphorus (P) fertilization: PO [0 kg ha<sup>-1sup>], Pl [75 kg ha<sup>-1sup>], and P2 [150 kg ha<sup>-1sup>], as KH₂PO₄ of P, were applied. The presence of high concentrations of As in soils reduced plants growth, decreased grain yield and increased root, shoot and grain As concentrations, especially in the absence of P fertilization. The P fertilization decreased the As concentration in all the tissues as well as the translocation of As to the shoot and grain. This observation may be useful in certain areas of the world with high levels of As in soils, to reduce the potential risk posed to human health by As entering the food-chain. © by PSP.

The effect of heating temperature on the properties of vermiculites from Tanzania with respect to potential agronomic applications

This study was carried out to assess the properties of vermiculites from Tanzania with respect to the temperature used to expand them. Vermiculites from five locations in the Mozambique Belt of Tanzania were sampled and heated at 15, 200, 400, 600 and 800 °C in a muffle furnace. Palabora Europe Ltd provided one sample for comparison from their South Africa deposit which provides vermiculite used worldwide as a soil amendment. Water release characteristic, cation exchange capacity, pH, mass loss, and bulk density were among the properties assessed. All six vermiculites responded differently on heating, and had a significant variation in their agronomic properties. Water release characteristic varied with the degree of exfoliation and phase composition. Although vermiculites from Tanzania expanded on heating, their capacity to retain plant available water was relatively low as compared to vermiculite from Palabora. Disintegration on heating and the presence of a high amount of iron could be among the factors affecting their water release characteristic. Loss of hydroxyl water was higher in vermiculites than in hydrobiotites. Dehydroxylation enhanced the availability of exchangeable K<sup>+sup> and reduced significantly the cation exchange capacity of vermiculites. The optimum exchangeable K<sup>+sup> was obtained on heating at a temperature of 600 °C. The pH was unaffected by heating to a temperature of less than 600 °C. At higher temperature, the pH increased in some samples and was accompanied by substantial amounts of exchangeable Mg<sup>2+sup>. Thus, it was concluded that initial characterization of vermiculites is essential prior to potential agricultural applications in order to optimize their agronomic potential. © 2008 Elsevier B.V. All rights reserved.

Influence of phosphate on the arsenic uptake by wheat (Triticum durum L.) irrigated with arsenic solutions at three different concentrations

In this study we have investigated the uptake and distribution of arsenic (As) and phosphate (P_i) in roots, shoots, and grain of wheat grown in an uncontaminated soil irrigated with solutions containing As at three different concentrations (0.5, 1 and 2 mg l<sup>-1sup>) and in the presence or in the absence of P fertilization. Arsenic in irrigation water reduced plants growth and decreased grain yield. When P_i was not added (P-), plants were more greatly impacted compared to the plus P_i (P+) treatments. The differences in mean biomass between P- and P+ treatments at the higher As concentrations demonstrated the role of P_i in preventing As toxicity and growth inhibition. Arsenic concentrations in root, shoot and grain increased with increasing As concentration in irrigation water. It appears that P fertilization minimizes the translocation of As to the shoots and grain whilst enhancing P status of plant. The observation that P fertilization minimises the translocation of arsenic to the shoots and grain is interesting and may be useful for certain regions of the world that has high levels of As in groundwater or soils. © 2008 Springer Science+Business Media B.V.

The fate of 14C-naphthalene in soil microcosms containing Scots pine seedlings and enchytraeids

The fate of freshly spiked and aged <sup>14sup>C-naphthalene associated residues as investigated in the presence and absence of ectomycorrhizal Scots pine seedlings and enchytraeid worms, in a factorial experimental design. Microcosms were used which enabled the <sup>14sup>C-labelled naphthalene associated residues to be quantified, including plant lipids which acted as an additional naphthalene sink within the microcosms. The presence of plant roots altered the availability of the <sup>14sup>C-naphthalene and associated residues to degrading microbes. Mineralisation and volatilisation of <sup>14sup>C naphthalene in freshly spiked soil were lower in the presence of Scots pine. Conversely, in soil aged for 180 d, Scots pine increased mineralisation, and bioavailability of naphthalene. Root-mediated processes, microbial activity and enchytraeids interact with desorption, bioavailability and mineralisation of naphthalene. © 2006 Elsevier Ltd. All rights reserved.

Enchytraeid worms retard polycyclic aromatic hydrocarbon degradation in a coniferous forest soil

In this study the fate of naphthalene, fluorene and pyrene were investigated in the presence and absence of enchytraeid worms. Microcosms were used, which enabled the full fate of <sup>14sup>C-labelled PAHs to be followed. Between 60 and 70% of naphthalene was either mineralised or volatilised, whereas over 90% of the fluorene and pyrene was retained within the soil. Mineralisation and volatilisation of naphthalene was lower in the presence of enchytraeid worms. The hypothesis that microbial mineralisation of naphthalene was limited by enchytraeids because they reduce nutrient availability, and hence limit microbial carbon turnover in these nutrient poor soils, was tested. Ammonia concentrations increased and phosphorus concentrations decreased in all microcosms over the 56 d experimental period. The soil nutrient chemistry was only altered slightly by enchytraeid worms, and did not appear to be the cause of retardation of naphthalene mineralisation. The results suggest that microbial availability and volatilisation of naphthalene is altered as it passes through enchytraeid worms due to organic material encapsulation. © 2004 Elsevier Ltd. All rights reserved.