Physical properties of a new Deep Eutectic Solvent based on lithium bis[(trifluoromethyl)sulfonyl]imide and N-methylacetamide as superionic suitable electrolyte for lithium ion batteries and electric double layer capacitors

Herein we present a study on the physical/chemical properties of a new Deep Eutectic Solvent (DES) based on N-methylacetamide (MAc) and lithium bis[(trifluoromethyl)sulfonyl]imide (LiTFSI). Due to its interesting properties, such as wide liquid-phase range from -60°C to 280°C, low vapor pressure, and high ionic conductivity up to 28.4mScm at 150°C and at x=1/4, this solution can be practically used as electrolyte for electrochemical storage systems such as electric double-layer capacitors (EDLCs) and/or lithium ion batteries (LiBs). Firstly, relationships between its transport properties (conductivity and viscosity) as a function of composition and temperature were discussed through Arrhenius' Law and Vogel-Tamman-Fulcher (VTF) equations, as well as by using the Walden classification. From this investigation, it appears that this complex electrolyte possesses a number of excellent transport properties, like a superionic character for example. Based on which, we then evaluated its electrochemical performances as electrolyte for EDLCs and LiBs applications by using activated carbon (AC) and lithium iron phosphate (LiFePO) electrodes, respectively. These results demonstrate that this electrolyte has a good compatibility with both electrodes (AC and LiFePO) in each testing cell driven also by excellent electrochemical properties in specific capacitance, rate and cycling performances, indicating that the LiTFSI/MAc DES can be a promising electrolyte for EDLCs and LiBs applications especially for those requiring high safety and stability. © 2013 Elsevier Ltd.

The Influence of Cation Structure on the Chemical-Physical Properties of Protic Ionic Liquids

In this study we investigated the influence of five different cations on the physical-chemical properties of protic ionic liquids (PILs) based on bis(trifluoromethanesulfonyl)imide (TFSI-). We showed that the viscosities, ionic conductivities, densities and thermal properties of these PIL are strongly affected by the structure of the protic cation. Furthermore, the influence of the cation structure on the lithium coordination was investigated by Raman spectroscopy for all investigated PIL-based electrolytes for lithium-ion batteries (LIBs). This investigation clearly demonstrates, that the lithium average coordination number in PIL-based electrolytes is strongly affected by (ring) size and the number of protons on the cations structure and, more importantly, it might be significantly lower (more than 60 of that of electrolytes containing aprotic ionic liquids (AILs). Electrochemical performances of these PILs-based electrolytes were then also investigated to dress some conclusion on their applicability for LIB.

Polycyclic aromatic hydrocarbon (PAH) dispersion and deposition to vegetation and soil following a large scale chemical fire

Polycyclic aromatic hydrocarbons (PAHs) were determined in soil and vegetation following a large scale chemical fire involving 10,000 ton of polypropylene. In comparison with sites outside the plume from the fire, PAH concentrations were elevated in grass shoots (by up to 70-fold) and in soil (by up to 370-fold). The pattern of PAH dispersion under the plume was dependent on the physical-chemical properties of individual PAHs. The lighter, least hydrophobic PAHs were dispersed into the environment at greater distances than heavier, more hydrophobic PAHs. At the most distant sampling point (4.5 km) under the plume, the low molecular weight PAHs were still considerably elevated in vegetation samples compared to control sites. Dispersion appeared to be regulated by the compounds partitioning between the vapour and particulate phase, with dry particulate deposition occurring closer to the fire source than gaseous deposition. For all PAHs, the fire resulted in greater contamination of soils compared to grasses, with the relative ratio of plant/soil contamination decreasing as hydrophobicity increased.

Are Alkyl Sulfate-Based Protic and Aprotic Ionic Liquids Stable with Water and Alcohols? A Thermodynamic Approach

The knowledge of the chemical stability as a function of the temperature of ionic liquids (ILs) in the presence of other molecules such as water is crucial prior to developing any no GO industrial application and process involving these novel materials. Fluid phase equilibria and density over a large range of temperature and composition can give basic information on IL purity and chemical stability. The IL scientific community requires accurate measurements accessed from reference data. In this work, the stability of different alkyl sulfate-based ILs in the presence of water and various alcohols (methanol, ethanol, 1-butanol, and 1-octanol) was investigated to understand their stability as a function of temperature up to 423.15 K over the hydrolysis and transesterification reactions, respectively. From this investigation, it was clear that methyl sulfate- and ethyl sulfate-based ILs are not stable in the presence of water, since hydrolysis of the methyl sulfate or ethyl sulfate anions to methanol or ethanol and hydrogenate anion is undoubtedly observed. Such observations could help to explain the differences observed for the physical properties published in the literature by various groups. Furthermore, it appears that a thermodynamic equilibrium process drives these hydrolysis reactions. In other words, these hydrolysis reactions are in fact reversible, providing the possibility to re-form the desired alkyl sulfate anions by a simple transesterification reaction between hydrogen sulfate-based ILs and the corresponding alcohol (methanol or ethanol). Additionally, butyl sulfate- and octyl sulfate-based ILs appear to follow this pattern but under more drastic conditions. In these systems, hydrolysis is observed in both cases after several months for temperatures up to 423 K in the presence of water. Therein, the partial miscibility of hydrogen sulfate-based ILs with long chain alcohols (1-butanol and 1-octanol) can help to explain the enhanced hydrolytic stability of the butyl sulfate- and octyl sulfate-based ILs compared with the methyl or ethyl sulfate systems. Additionally, rapid transesterification reactions are observed during liquid-liquid equilibrium studies as a function of temperature for binary systems of (hydrogen sulfate-based ionic liquids + 1-butanol) and of (hydrogen sulfate-based ionic liquids + 1-octanol). Finally, this atom-efficient catalyst-free transesterification reaction between hydrogen sulfate-based ILs and alcohol was then tested to provide a novel way to synthesize new ILs with various anion structures containing the alkyl sulfate group.

Stability and hydration studies of Y-Doped Ba(Ce,Zr)O3

BaC_e1-xYxO_3-δ (BCY) and BaCe_0.8-yZr_yY_0.2O_3-δ (BCZY) compounds were synthesised via an aqueous sol-gel method and two different calcination processes were tested for BCZY synthesis. The highest hydration capacity was recorded for the compound that contained the highest Y-doping level (x=0.2). Further substitution of Ce⁴⁺ by Zr⁴⁺ enhanced the chemical stability especially for y≥0.2, although decreased proton conductivity. However, BaCe_0.6-0.2Zr_0.2Y_0.2O_2.9 (BCZ20Y20) which presented adequate water uptake and high chemical stability in presence of CO₂, was found to be the best candidate compound to be used in applications such as electrocatalytic CO₂ hydrogenation.

Mixing Enthalpy for Binary Mixtures Containing Ionic Liquids

A complete review of the published data on the mixing enthalpies of mixtures containing ionic liquids, measured directly using calorimetric techniques, is presented in this paper. The field of ionic liquids is very active and a number of research groups in the world are dealing with different applications of these fluids in the fields of chemistry, chemical engineering, energy, gas storage and separation or materials science. In all these fields, the knowledge of the energetics of mixing is capital both to understand the interactions between these fluids and the different substrates and also to establish the energy and environmental cost of possible applications. Due to the relative novelty of the field, the published data is sometimes controversial and recent reviews are fragmentary and do not represent a set of reliable data. This fact can be attributed to different reasons: (i) difficulties in controlling the purity and stability of the ionic liquid samples; (ii) availability of accurate experimental techniques, appropriate for the measurement of viscous, charged, complex fluids; and (iii) choice of an appropriate clear thermodynamic formalism to be used by an interdisciplinary scientific community. In this paper, we address all these points and propose a critical review of the published data, advise on the most appropriate apparatus and experimental procedure to measure this type of physical-chemical data in ionic liquids as well as the way to treat the information obtained by an appropriate thermodynamic formalism.

High precision C-14 dating of Holocene peat deposits: A comparison of Bayesian calibration and wiggle-matching approaches

The chronologies of five northern European ombrotrophic peat bogs subjected to a large ANIS C-14 dating effort (32-44 dates/site) are presented here. The results of Bayesian calibration (BCal) of dates with a prior assumption of chronological ordering were compared with a Bayesian wiggle-match approach (Bpeat) which assumes constant linear accumulation over sections of the peat profile. Interpolation of BCal age estimates of dense sequences of C-14 dates showed variable patterns of peat accumulation with time, with changes in accumulation occurring at intervals ranging from 20 to 50 cm. Within these intervals, peat accumulation appeared to be relatively linear. Close analysis suggests that some of the inferred variations in accumulation rate were related to the plant macrofossil composition of the peat. The wiggle-matched age-depth models had relatively high chronological uncertainty within intervals of closely spaced 14 C dates, suggesting that the premise of constant linear accumulation over large sections of the peat profile is unrealistic. Age models based on the assumption of linear accumulation over large parts of a peat core (and therefore only effective over millennial timescales), are not compatible with studies examining environmental change during the Holocene, where variability often occurs at decadal to centennial time-scales. Ideally, future wiggle-match age models should be constrained, with boundaries between sections based on the plant macrofossil composition of the peat and physical-chemical parameters such as the degree of decomposition. Strategies for the selection of material for dating should be designed so that there should be enough C-14 dates to accurately reconstruct the peat accumulation rate of each homogeneous stratigraphic unit. (c) 2006 Elsevier Ltd. All rights reserved.

Exploitation of inherited weakness in fire-damaged building sandstone: the ‘fatiguing’ of ‘shocked’ stone

The problem of the long-term impact of historical fire on masonry is not clearly understood. Much research focuses on the damage that is caused by fire in isolation, and omits to investigate the subsequent exploitation of weaknesses inherited from fire events. Fire can, for example, cause significant physical, chemical and mineralogical change to sandstone, which may then be exploited by background environmental factors such as salt and freeze–thaw weathering. To explore this experimentally, blocks of Peakmoor Sandstone were subjected to a real fire (as well as lime rendering/removal and frost cycle pre-treatments), and their subsequent response to salt weathering cycles was monitored by weight loss and visual assessment of the pattern of surface damage. Results illustrate that the post-fire deterioration of sandstone is strongly conditioned by fracture networks and soot cover inherited from the fire. The exploitation of fractures can lead to spalling during salt weathering cycles — this takes place as granular dissagregation steadily widens cracks and salts concentrate and crystallise in areas of inherited weakness. Soot cover can have a profound effect on subsequent performance. It reduces surface permeability and can be hydrophobic in character, limiting salt ingress and suppressing decay in the short term. However, as salt crystals concentrate under the soot crust, detachment of this layer can occur, exposing fire-damaged stone beneath. Understanding the subsequent exploitation of stone exposed to fire damage by background environmental factors (for example, salt weathering/ temperature cycling) is key to the post-fire management of stone decay.

An Update on Sedimentary Pigments in Victoria Land Lakes (East Antarctica)

Antarctic ice-free areas contain lakes and ponds that have interesting limnological features and are of wide global significance as early warning indicators of climatic and environmental change. However, most linmological and paleolimnological studies in continental Antarctica are limited to certain regions. There are several ice-free areas in Victoria Land that have not yet been studied well. There is therefore a need to extend limnological studies in space and time to understand how different geological and climatic features affect the composition and biological activity of freshwater communities. With the aim of contributing to a better limnological characterization of Victoria Land, this paper reports data on sedimentary pigments (used to identify the main algal taxa) obtained through a methodology that is more sensitive and selective than that of previous studies. Analyses were extended to 48 water bodies in ice-free areas with differing lithology, latitude, and altitude, and with different morphometry and physical, chemical, and biological characteristics in order to identify environmental factors affecting the distribution and composition of freshwater autotrophic communities. A wider knowledge of lakes in a limnologically important region of Antarctica was obtained. Cyanophyta was found to be the most important algal group, followed by Chlorophyta and Bacillariophyta, whereas latitude and altitude are the main factors affecting pigment distribution.

Au Nanoparticles for Applications in Analysis of Cellular and Biomolecular Recognitions

Au nanoparticles (AuNPs) have attracted a great interest in fabrication of various biosensor systems for analysis of cellular and biomolecular recognitions. In conjunction with vast conjugation chemistry available, the materials are easily coupled with biomolecules such as nucleic acids, antigens or antibodies in order to achieve their many potential applications as ligand carriers or transducing platforms for preparation, detection and quantification purposes. Furthermore, the nanoparticles possess easily tuned and unique optical/ physical/ chemical characteristics, and high surface areas, making them ideal candidates to this end. In this topic, sensing mechanisms based on localized surface plasmon resonance (LSPR), particle aggregation, catalytic property, and Fluorescence Resonance Energy Transfer (FRET) of AuNPs as well as barcoding technologies including DNA biobarcodes will be discussed.

Stress tolerance and virulence of insect-pathogenic fungi are determined by environmental conditions during conidial formation

The virulence to insects and tolerance to heat and UV-B radiation of conidia of entomopathogenic fungi are greatly influenced by physical, chemical, and nutritional conditions during mycelial growth. This is evidenced, for example, by the stress phenotypes of Metarhizium robertsii produced on various substrates. Conidia from minimal medium (Czapek's medium without sucrose), complex medium, and insect (Lepidoptera and Coleoptera) cadavers had high, moderate, and poor tolerance to UV-B radiation, respectively. Furthermore, conidia from minimal medium germinated faster and had increased heat tolerance and were more virulent to insects than those from complex medium. Low water-activity or alkaline culture conditions also resulted in production of conidia with high tolerance to heat or UV-B radiation. Conidia produced on complex media exhibited lower stress tolerance, whereas those from complex media supplemented with NaCl or KCl (to reduce water activity) were more tolerant to heat and UV-B than those from the unmodified complex medium. Osmotic and nutritive stresses resulted in production of conidia with a robust stress phenotype, but also were associated with low conidial yield. Physical conditions such as growth under illumination, hypoxic conditions, and heat shock before conidial production also induced both higher UV-B and heat tolerance; but conidial production was not decreased. In conclusion, physical and chemical parameters, as well as nutrition source, can induce great variability in conidial tolerance to stress for entomopathogenic fungi. Implications are discussed in relation to the ecology of entomopathogenic fungi in the field, and to their use for biological control. This review will cover recent technologies on improving stress tolerance of entomopathogenic fungi for biological control of insects.

Spatial and temporal influences of in-stream factors on the chemistry and epilithic biomasses of upland stream metal deposits

The density and composition of stream bed metal deposits are affected by physical, chemical and biological processes. In this paper we investigate the importance of these processes and their relation to algal and non-photosynthetic detrital (NPD) biomass in a set of upland streams in Northern Ireland. Deposit density and Fe, Mn, Al and P concentrations varied with stream pH across sites but not seasonally. No effects of stream bed erosion or photoreduction were detected on deposit densities. Seasonal variation in stream water metal concentrations was correlated with rainfall. NPD biomass was a significant predictor of both spatial and seasonal variation in deposit concentrations. There were strong, non-linear, relations between NPD biomass and deposit metal concentrations, with Fe and Mn becoming relatively more important and algal biomass declining above threshold deposit/NPD densities. The results suggest that NPD biomass influences deposit density and reduces the biomass of photosynthetic autotrophs above a threshold deposit density.

Structure and dynamics of aqueous 2-propanol: A THz-TDS, NMR and neutron diffraction study

Aqueous liquid mixtures, in particular, those involving amphiphilic species, play an important role in many physical, chemical and biological processes. Of particular interest are alcohol/water mixtures; however, the structural dynamics of such systems are still not fully understood. Herein, a combination of terahertz time-domain spectroscopy (THz-TDS) and NMR relaxation time analysis has been applied to investigate 2-propanol/water mixtures across the entire composition range; while neutron diffraction studies have been carried out at two specific concentrations. Excellent agreement is seen between the techniques with a maximum in both the relative absorption coefficient and the activation energy to molecular motion occurring at ∼90 mol% H₂O. Furthermore, this is the same value at which well-established excess thermodynamic functions exhibit a maximum/minimum. Additionally, both neutron diffraction and THz-TDS have been used to provide estimates of the size of the hydration shell around 2-propanol in solution. Both methods determine that between 4 and 5 H₂O molecules per 2-propanol are found in the 2-propanol/water clusters at 90 mol% H₂O. Based on the acquired data, a description of the structure of 2-propanol/water across the composition range is presented.