Showing papers on "Ion published in 2009"
TL;DR: The results clearly indicate that the metal-free g-C(3)N(4) has good performance in photodegradation of organic pollutant.
Abstract: The g-C3N4 photocatalyst was synthesized by directly heating the low-cost melamine. The methyl orange dye (MO) was selected as a photodegrading goal to evaluate the photocatalytic activity of as-prepared g-C3N4. The comparison experiments indicate that the photocatalytic activity of g-C3N4 can be largely improved by the Ag loading. The strong acid radical ion (SO42− or NO3−) can promote the degrading rate of MO for g-C3N4 photocatalysis system. The MO degradation over the g-C3N4 is mainly attributed to the photoreduction process induced by the photogenerated electrons. Our results clearly indicate that the metal-free g-C3N4 has good performance in photodegradation of organic pollutant.
2,362 citations
TL;DR: In this article, a review of recent progress dedicated to the anode and cathode materials that have the potential to fulfil the crucial factors of cost, safety, lifetime, durability, power density, and energy density is presented.
Abstract: In order to address power and energy demands of mobile electronics and electric cars, Li-ion technology is urgently being optimized by using alternative materials. This article presents a review of our recent progress dedicated to the anode and cathode materials that have the potential to fulfil the crucial factors of cost, safety, lifetime, durability, power density, and energy density. Nanostructured inorganic compounds have been extensively investigated. Size effects revealed in the storage of lithium through micropores (hard carbon spheres), alloys (Si, SnSb), and conversion reactions (Cr(2)O(3), MnO) are studied. The formation of nano/micro core-shell, dispersed composite, and surface pinning structures can improve their cycling performance. Surface coating on LiCoO(2) and LiMn(2)O(4) was found to be an effective way to enhance their thermal and chemical stability and the mechanisms are discussed. Theoretical simulations and experiments on LiFePO(4) reveal that alkali metal ions and nitrogen doping into the LiFePO(4) lattice are possible approaches to increase its electronic conductivity and does not block transport of lithium ion along the 1D channel.
1,596 citations
TL;DR: Results from Diffraction Experiments 1351 and results from Spectroscopic Measurements 1354 4.3.1.
Abstract: 4. Structure of Ionic Hydration Shells 1351 4.1. Results from Diffraction Experiments 1351 4.1.1. X-ray Diffraction 1351 4.1.2. Neutron Diffraction 1351 4.2. Results from Computer Simulations 1352 4.3. Results from Spectroscopic Measurements 1354 4.3.1. Vibrational Spectroscopic Measurements 1354 4.3.2. EXAFS Spectroscopy 1354 4.3.3. NMR Relaxation Studies 1355 4.3.4. Dielectric Relaxation Studies 1355 4.4. Summary of the Structure of Ionic Hydration Shells 1355
1,445 citations
TL;DR: Li et al. as discussed by the authors reported that highly disordered graphene nanosheets can find promising applications in high-capacity Li ion batteries because of their exceptionally high reversible capacities and good cyclic stability.
Abstract: Graphene has aroused intensive interest because of its unique structure, superior properties, and various promising applications. Graphene nanostructures with significant disorder and defects have been considered to be poor materials because disorder and defects lower their electrical conductivity. In this paper, we report that highly disordered graphene nanosheets can find promising applications in high-capacity Li ion batteries because of their exceptionally high reversible capacities (794−1054 mA h/g) and good cyclic stability. To understand the Li storage mechanism of graphene nanosheets, we have prepared graphene nanosheets with structural parameters tunable via different reduction methods including hydrazine reduction, low-temperature pyrolysis, and electron beam irradiation. The effects of these parameters on Li storage properties were investigated systematically. A key structural parameter, Raman intensity ratio of D bands to G bands, has been identified to evaluate the reversible capacity. The gr...
944 citations
TL;DR: The following processes are considered: Creation of charge droplets at the capillary tip; Electrical potentials required and possibility of gas discharges; Evolution of charged droplets, due to solvent evaporation and Coulomb explosions, to very small droplets that are the precursors of the gas phase ions.
Abstract: There is an advantage for users of electrospray and nanospray mass spectrometry to have an understanding of the processes involved in the conversion of the ions present in the solution to ions in the gas phase. The following processes are considered: Creation of charge droplets at the capillary tip; Electrical potentials required and possibility of gas discharges; Evolution of charged droplets, due to solvent evaporation and Coulomb explosions, to very small droplets that are the precursors of the gas phase ions; Production of gas phase ions from these droplets via the Ion Evaporation and Charge residue models; Analytical uses of ESIMS of small ions, qualitative and quantitative analysis; Effects of the ESI mechanism on the analysis of proteins and protein complexes; Determination of stability constants of protein complexes; Role of additives such as ammonium acetate on the observed mass spectra.
768 citations
TL;DR: In this paper, the authors used regular solution theory and group contributions to predict and explain CO2 solubility and selectivity in room-temperature ionic liquids (RTILs).
Abstract: Room-temperature ionic liquids (RTILs) are nonvolatile, tunable solvents that have generated significant interest across a wide variety of engineering applications. The use of RTILs as media for CO2 separations appears especially promising, with imidazolium-based salts at the center of this research effort. The solubilities of gases, particularly CO2, N2, and CH4, have been studied in a number of RTILs. Process temperature and the chemical structures of the cation and anion have significant impacts on gas solubility and gas pair selectivity. Models based on regular solution theory and group contributions are useful to predict and explain CO2 solubility and selectivity in imidazolium-based RTILs. In addition to their role as a physical solvent, RTILs might also be used in supported ionic liquid membranes (SILMs) as a highly permeable and selective transport medium. Performance data for SILMs indicates that they exhibit large permeabilities as well as CO2/N2 selectivities that outperform many polymer membra...
680 citations
TL;DR: In vitro and in planta evaluations of silver indicated that both silver ions and nanoparticles influence colony formation of spores and disease progress of plant-pathogenic fungi, which is much greater with preventative application.
Abstract: Silver in ionic or nanoparticle forms has a high antimicrobial activity and is therefore widely used for various sterilization purposes including materials of medical devices and water san...
609 citations
TL;DR: The CHIANTI database as mentioned in this paper provides a set of atomic data for the interpretation of astrophysical spectra emitted by collisionally dominated, high temperature, optically thin sources.
Abstract: Aims. The goal of the CHIANTI atomic database is to provide a set of atomic data for the interpretation of astrophysical spectra emitted by collisionally dominated, high temperature, optically thin sources. Methods. A complete set of ground level ionization and recombination rate coefficients has been assembled for all atoms and ions of the elements of H through Zn and inserted into the latest version of the CHIANTI database, CHIANTI 6. Ionization rate coefficients are taken from the recent work of Dere (2007, A&A, 466, 771) and recombination rates from a variety of sources in the literature. These new rate coefficients have allowed the calculation of a new set of ionization equilibria and radiative loss rate coefficients. For some ions, such as Fe viii and Fe ix, there are significant differences from previous calculations. In addition, existing atomic parameters have been revised and new atomic parameters inserted into the database. Results. For each ion in the CHIANTI database, elemental abundances, ionization potentials, atomic energy levels, radiative rates, electron and proton collisional rate coefficients, ionization and recombination rate coefficients, and collisional ionization equilibrium populations are provided. In addition, parameters for the calculation of the continuum due to bremsstrahlung, radiative recombination and two-photon decay are provided. A suite of programs written in the Interactive Data Language (IDL) are available to calculate line and continuum emissivities and other properties. All data and programs are freely available at http://wwwsolar.nrl.navy.mil/ chianti
513 citations
TL;DR: In this paper, a dipolarization front was detected in the central plasma sheet sequentially at X = -20.1 R E (THEMIS P1 probe), at x = -16.7 R E(P2 probe), and at X= -11.0 RE (P3/P4 pair), suggesting its earthward propagation as a coherent structure over a distance more than 10 R E at a velocity of 300 km/s.
Abstract: [1] We report THEMIS observations of a dipolarization front, a sharp, large-amplitude increase in the Z-component of the magnetic field. The front was detected in the central plasma sheet sequentially at X = -20.1 R E (THEMIS P1 probe), at X = -16.7 R E (P2), and at X = -11.0 R E (P3/P4 pair), suggesting its earthward propagation as a coherent structure over a distance more than 10 R E at a velocity of 300 km/s. The front thickness was found to be as small as the ion inertial length. Comparison with simulations allows us to interpret the front as the leading edge of a plasma fast flow formed by a burst of magnetic reconnection in the midtail.
504 citations
TL;DR: The correlations among the various properties led to the following conclusions: (1) the reliability of the ion force fields is significantly affected by the specific choice of water model, and (2) Ion−ion interactions are very important to accurately simulate the properties, especially solubility.
Abstract: The dynamic and energetic properties of the alkali and halide ions were calculated using molecular dynamics (MD) and free energy simulations with various different water and ion force fields including our recently developed water-model-specific ion parameters. The properties calculated were activity coefficients, diffusion coefficients, residence times of atomic pairs, association constants, and solubility. Through calculation of these properties, we can assess the validity and range of applicability of the simple pair potential models and better understand their limitations. Due to extreme computational demands, the activity coefficients were only calculated for a subset of the models. The results qualitatively agree with experiment. Calculated diffusion coefficients and residence times between cation−anion, water−cation, and water−anion showed differences depending on the choice of water and ion force field used. The calculated solubilities of the alkali−halide salts were generally lower than the true s...
471 citations
TL;DR: It is found from the d dependence of r (1) that the optimal range of d for the maximal r(1), which may be used as an advanced T(1) MRI contrast agent, is 1-2.5 nm.
Abstract: Paramagnetic ultrasmall gadolinium oxide (Gd(2)O(3)) nanoparticles with particle diameters (d) of approximately 1 nm were synthesized by using three kinds of Gd(III) ion precursors and by refluxing each of them in tripropylene glycol under an O(2) flow. A large longitudinal relaxivity (r(1)) of water proton of 9.9 s(-1) mM(-1) was estimated. As a result, high contrast in vivo T(1) MR images of the brain tumor of a rat were observed. This large r(1) is discussed in terms of the huge surface to volume ratio (S/V) of the ultrasmall gadolinium oxide nanoparticles coupled with the cooperative induction of surface Gd(III) ions for the longitudinal relaxation of a water proton. It is found from the d dependence of r(1) that the optimal range of d for the maximal r(1), which may be used as an advanced T(1) MRI contrast agent, is 1-2.5 nm.
TL;DR: The first two families of polyoxometalate-based single-molecule magnets (SMMs) are reported here and the ligand-field parameters and the splitting of the J ground-state multiplet of the lanthanide ions have been also estimated.
Abstract: The first two families of polyoxometalate-based single-molecule magnets (SMMs) are reported here. Compounds of the general formula [Ln(W5O18)2]9− (LnIII = Tb, Dy, Ho, and Er) and [Ln(SiW11O39)2]13− (LnIII = Tb, Dy, Ho, Er, Tm, and Yb) have been magnetically characterized with static and dynamic measurements. Slow relaxation of the magnetization, typically associated with SMM-like behavior, was observed for [Ln(W5O18)2]9− (LnIII = Ho and Er) and [Ln(SiW11O39)2]13− (LnIII = Dy, Ho, Er, and Yb). Among them, only the [Er(W5O18)2]9− derivative exhibited such a behavior above 2 K with an energy barrier for the reversal of the magnetization of 55 K. For a deep understanding of the appearance of slow relaxation of the magnetization in these types of mononuclear complexes, the ligand-field parameters and the splitting of the J ground-state multiplet of the lanthanide ions have been also estimated.
TL;DR: It will be shown that IR spectroscopy of mass-selected (bio)molecular systems is now well-placed to address specific questions on the individual effect of charge carriers (protons and metal ions), as well as solvent molecules on the overall structure.
Abstract: The low density of ions in mass spectrometers generally precludes direct infrared (IR) absorption measurements. The IR spectrum of an ion can nonetheless be obtained by inducing photodissociation of the ion using a high-intensity tunable laser. The emergence of free electron lasers (FELs) and recent breakthroughs in bench-top lasers based on nonlinear optics have now made it possible to routinely record IR spectra of gas-phase ions. As the energy of one IR photon is insufficient to cause dissociation of molecules and strongly bound complexes, two main experimental strategies have been developed to effect photodissociation. In infrared multiple-photon dissociation (IR-MPD) many photons are absorbed resonantly and their energy is stored in the bath of vibrational modes, leading to dissociation. In the "messenger" technique a weakly bound van der Waals atom is detached upon absorption of a single photon. Fundamental, historical, and practical aspects of these methods will be presented. Both of these approaches make use of very different methods of ion preparation and manipulation. While in IR-MPD ions are irradiated in trapping mass spectrometers, the "messenger" technique is generally carried out in molecular beam instruments. The main focus of this review is the application of IR spectroscopy to biologically relevant molecular systems (amino acids, peptides, proteins). Particular issues that will be addressed here include gas-phase zwitterions, the (chemical) structures of peptides and their collision-induced dissociation (CID) products, IR spectra of gas-phase proteins, and the chelation of metal-ligand complexes. Another growing area of research is IR spectroscopy on solvated clusters, which offer a bridge between the gas-phase and solution environments. The development of state-of-the-art computational approaches has gone hand-in-hand with advances in experimental techniques. The main advantage of gas-phase cluster research, as opposed to condensed-phase experiments, is that the systems of interest can be understood in detail and structural effects can be studied in isolation. It will be shown that IR spectroscopy of mass-selected (bio)molecular systems is now well-placed to address specific questions on the individual effect of charge carriers (protons and metal ions), as well as solvent molecules on the overall structure.
TL;DR: In this article, the authors developed an auroral precipitation model which separately categorizes the discrete aurora and both the electron and ion diffuse aurora, based on functional fits to the solar wind coupling function which best predicts auroral power.
Abstract: [1] We have developed an auroral precipitation model which separately categorizes the discrete aurora and both the electron and ion diffuse aurora. The discrete aurora includes acceleration by two distinct physical mechanisms, namely, quasi-static electric fields, producing monoenergetic peaks, and dispersive Alfven waves, producing broadband electron acceleration. The new model is not merely finer in magnetic latitude (MLAT) and magnetic local time (MLT) resolution than previous models but is parameterized by solar wind driving instead of Kp and is based on functional fits to the solar wind coupling function which best predicts auroral power. Each of the four auroral types in each MLAT and MLT bin is separately fitted, a departure from the traditional compilation of a handful of discrete models, each assigned to represent a Kp (or other activity index) range. The variation of any of these four types of aurora at any local time can be predicted on the basis of the specific solar wind history of an epoch. This approach permits perhaps the first comprehensive comparison of the hemispheric contribution of each type of aurora. It turns out that the diffuse aurora is surprisingly dominant, constituting 84% of the energy flux into the ionosphere during conditions of low solar wind driving (63% electrons, 21% ions). The diffuse aurora is far from quiescent, tripling in power dissipation from our low to high solar wind–driving conditions. Even under the latter condition, the diffuse aurora contains 71% of the hemispheric energy flux (57% electrons, 14% ions). The monoenergetic aurora contributes more energy flux (10% quiet, 15% active) than does broadband acceleration signatures (6% quiet, 13% active). However, the broadband aurora rises fastest with activity, increasing by a factor of 8.0 from low to high driving. Moreover, this most dynamic auroral type contributes very high number fluxes, even exceeding monoenergetic aurora under active conditions (28% of hemispheric precipitation versus 21%). Thus, dynamic ionospheric heating and ion outflow is likely heavily affected by the wave aurora. Although energy flux peaks on the nightside, number flux peaks on the dayside. The cusp, as previously reported, is much better defined by ions than electrons. Hence, the ion number flux peak is confined, corresponding to the cusp, while the region with high electron number flux is broad (a cleft, corresponding to the boundary layers, including the closed low-latitude boundary layer).
TL;DR: In this article, a systematic study of densities and refractive indices of 17 room temperature ionic liquids is presented at four different temperatures ranging from 293 K to 333 K. The ionic liquid are grouped into four families: 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, [C n mim ][N tf 2 ], ionic fluids (with n ǫ = 2, 4, 6, 8, 10, 12, and 14); 1-ALKyl- 3-
TL;DR: Small anions can be used to modulate the physical properties of supramolecular gels by interacting with the low-molecular-weight gelators from which such materials are composed, and a better understanding will aid in the rational design of responsive gels that may prove useful for a number of practical applications.
Abstract: Small anions can be used to modulate the physical properties of supramolecular gels by interacting with the low-molecular-weight gelators from which such materials are composed. A better understanding of this anion-tuning effect will aid in the rational design of responsive gels that may prove useful for a number of practical applications.
TL;DR: The tunability of the chemical composition of ionic liquids (ILs), achieved by pairing various organic cations with numerous anions, allows for fine control of their physicochemical properties and has been widely used for the adjustment of the IL solvent characteristics.
Abstract: The tunability of the chemical composition of ionic liquids (ILs), achieved by pairing various organic cations with numerous anions, allows for fine control of their physicochemical properties and has been widely used for the adjustment of the IL solvent characteristics. Exploitation of IL structural modularity coupled with chemical modification of the cation or anion to incorporate polymerizable groups is now an active area of research, resulting in the development of polymeric ionic liquids (poly(IL)s). The emergence of poly(IL)s as functional materials in the areas of polymer electrolytes, sorbents, dispersing agents, and nanomaterials is reviewed.
TL;DR: To the best of the knowledge, this is the first example of a single DNA-based sensor that allows the detection of both Hg(2+) and Pb( 2+) ions.
Abstract: We have developed a technique for the highly selective and sensitive detection of Pb(2+) and Hg(2+) using a thrombin-binding aptamer (TBA) probe labeled with the donor carboxyfluorescein (FAM) and the quencher 4-([4-(dimethylamino)phenyl]azo)benzoic acid (DABCYL) at its 5' and 3' termini, respectively. The TBA has a random coil structure that changes into a G-quartet structure and a hairpin-like structure upon binding Pb(2+) and Hg(2+) ions, respectively. As a result, the fluorescence decreases through fluorescence resonance energy transfer (FRET) between the fluorophore and quencher. These changes in fluorescence intensity allow the selective detection of Pb(2+) and Hg(2+) ions at concentrations as low as 300 pM and 5.0 nM using this TBA probe in the presence of phytic acid and a random DNA/NaCN mixture, respectively. The linear correlation existed between the fluorescence intensity and the concentration of Pb(2+) and Hg(2+) over the range of 0.5-30 nM (R(2) = 0.98) and 10-200 nM (R(2) = 0.98), respectively. To the best of our knowledge, this is the first example of a single DNA-based sensor that allows the detection of both Hg(2+) and Pb(2+) ions. This simple and cost-effective probe was also applied to separately determine Pb(2+) in soil samples and spiked Hg(2+) in pond samples.
TL;DR: A simple derivative of a well-known dye bodipy appears to be a satisfactory sensitizer for singlet oxygen and can be modulated by two cancer-related cellular parameters, sodium ion concentration and acidity.
Abstract: A simple derivative of a well-known dye bodipy appears to be a satisfactory sensitizer for singlet oxygen. Moreover, the rate of singlet oxygen generation can be modulated by two cancer-related cellular parameters, sodium ion concentration and acidity. Singlet oxygen generation rate is maximal when sodium ions and an organic acid were added. The operation of this molecular automaton follows AND logic, which introduces an additional layer of selectivity in the photodynamic action of the reagent. It should also be noted that in this system sensing, computing and actuating functions are realized within a single molecule.
TL;DR: A novel biomimetic nanochannel system which has an ion concentration effect that provides a nonlinear response to potassium ion at the concentration ranging from 0 to 1500 microM and can be further generalized to other more complicated functional molecules for the exploitation of novel bioinspired intelligent nanopore machines.
Abstract: Potassium is especially crucial in modulating the activity of muscles and nerves whose cells have specialized ion channels for transporting potassium. Normal body function extremely depends on the regulation of potassium concentrations inside the ion channels within a certain range. For life science, undoubtedly, it is significant and challenging to study and imitate these processes happening in living organisms with a convenient artificial system. Here we report a novel biomimetic nanochannel system which has an ion concentration effect that provides a nonlinear response to potassium ion at the concentration ranging from 0 to 1500 μM. This new phenomenon is caused by the G-quadruplex DNA conformational change with a positive correlation with ion concentration. In this work, G-quadruplex DNA was immobilized onto a synthetic nanopore, which undergoes a potassium-responsive conformational change and then induces the change in the effective pore size. The responsive ability of this system can be regulated by...
TL;DR: How the DART source can be used to analyze "difficult" or nonpolar compounds such as alkanes and cholesterol is shown and the difference between mass spectra obtained using conditions that favor proton transfer and those that favor molecular ion formation is demonstrated.
Abstract: Positive ions in the direct analysis in real time (DART) ion source are commonly formed by proton transfer However, the DART source is similar to atmospheric pressure photoionization (APPI) in that it can produce molecular ions as well as protonated molecules, although the two sources differ in the initial ion formation process This report discusses some of the factors that influence molecular ion formation in DART and shows how the DART source can be used to analyze “difficult” or nonpolar compounds such as alkanes and cholesterol Trace reagent ions including NO+ and O2+· formed from atmospheric gases are shown to play important roles in DART ionization The use of the DART source as a gas chromatography/mass spectrometry (GC/MS) interface is demonstrated to show the difference between mass spectra obtained using conditions that favor proton transfer and those that favor molecular ion formation
TL;DR: In this paper, a review presents a number of techniques employed in our laboratory and in others for measuring the spectroscopy of cold, gas-phase protonated peptides.
Abstract: While the marriage of mass spectrometry and laser spectroscopy is not new, developments over the last few years in this relationship have opened up new horizons for the spectroscopic study of biological molecules. The combination of electrospray ionisation for producing large biological molecules in the gas phase together with cooled ion traps and multiple-resonance laser schemes are allowing spectroscopic investigation of individual conformations of peptides with more than a dozen amino acids. Highly resolved infrared spectra of single conformations of such species provide important benchmarks for testing the accuracy of theoretical calculations. This review presents a number of techniques employed in our laboratory and in others for measuring the spectroscopy of cold, gas-phase protonated peptides. We show examples that demonstrate the power of these techniques and evaluate their extension to still larger biological molecules.
TL;DR: Unexpected temperature-induced valence changes at the A and B sites in the A-site-ordered double perovskite LaCu3Fe4O12 are reported; the underlying intersite charge transfer is accompanied by considerable changes in the material’s structural, magnetic and transport properties.
Abstract: The introduction of 'foreign' elements into transition-metal oxides (called chemical doping) can change the valence state of the metal's cations and hence modify the physical properties of the material as a whole. These changes can be dramatic, for example causing high-temperature superconductivity in copper oxides and colossal magnetoresistance in manganese oxides. Youwen Long et al. have identified an oxide system, the perovskite LaCu3Fe4O12, in which changes in valence state occur when charge is shuffled between different cations (iron and copper) in the host structure, rather than via doping. As a result, the material can be reversibly transformed from one possessing iron in an unusually high Fe3.75+ state (partnered with fairly common Cu2+ ions) to one possessing rare Cu3+ ions. These changes are reflected in the magnetic and electronic properties of the material and, intriguingly, the material contracts slightly on being warmed through the transition. The temperature sensitivity of this effect makes it a strong candidate for technological applications. This paper identifies an oxide system where changes in valence state occur as a result of charge being shuffled between different cations in the host structure, rather than via doping, this charge transfer being sensitive to temperature. As a result, the material can be reversibly transformed from one possessing iron in an unusually high Fe3.75+ state to one possessing rare Cu3+ ions. These changes are reflected in the magnetic and electronic properties of the material and, intriguingly, are accompanied by negative thermal expansion. Changes of valence states in transition-metal oxides often cause significant changes in their structural and physical properties1,2. Chemical doping is the conventional way of modulating these valence states. In ABO3 perovskite and/or perovskite-like oxides, chemical doping at the A site can introduce holes or electrons at the B site, giving rise to exotic physical properties like high-transition-temperature superconductivity and colossal magnetoresistance3,4. When valence-variable transition metals at two different atomic sites are involved simultaneously, we expect to be able to induce charge transfer—and, hence, valence changes—by using a small external stimulus rather than by introducing a doping element. Materials showing this type of charge transfer are very rare, however, and such externally induced valence changes have been observed only under extreme conditions like high pressure5,6. Here we report unusual temperature-induced valence changes at the A and B sites in the A-site-ordered double perovskite LaCu3Fe4O12; the underlying intersite charge transfer is accompanied by considerable changes in the material’s structural, magnetic and transport properties. When cooled, the compound shows a first-order, reversible transition at 393 K from LaCu2+3Fe3.75+4O12 with Fe3.75+ ions at the B site to LaCu3+3Fe3+4O12 with rare Cu3+ ions at the A site. Intersite charge transfer between the A-site Cu and B-site Fe ions leads to paramagnetism-to-antiferromagnetism and metal-to-insulator isostructural phase transitions. What is more interesting in relation to technological applications is that this above-room-temperature transition is associated with a large negative thermal expansion.
TL;DR: The results suggest that the kinetics of the interfacial lithium ion transfer at graphite is influenced by the compositions of SEI films as well as the desolvation of lithium ion from solvent molecules.
Abstract: The kinetics of lithium ion transfer at an interface between graphite and liquid electrolyte was studied by ac impedance spectroscopy. Using highly oriented pyrolytic graphite (HOPG) as a model electrode, we evaluated the activation energies of the interfacial lithium ion transfer from the temperature dependences of the interfacial conductivities. When a binary electrolyte consisting of LiClO4 dissolved in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) (1:1 by volume) was used, the activation energy of the interfacial lithium ion transfer was 58 kJ mol−1, while an electrolyte consisting of LiClO4 dissolved in DMC gave an activation energy of 40 kJ mol−1. A calculation with the density functional theory clarified that the solvation ability of EC is higher than that of DMC. Therefore, we concluded that the activation energies of the interfacial lithium ion transfer at graphite reflected the energies for the desolvation of lithium ion from the solvent molecule. Furthermore, the activation ...
TL;DR: A new theory is proposed which allows us to explicitly calculate the ionic density profiles, the surface tension, and the electrostatic potential difference across the solution-air interface.
Abstract: Availability of highly reactive halogen ions at the surface of aerosols has tremendous implications for the atmospheric chemistry. Yet neither simulations, experiments, nor existing theories are able to provide a fully consistent description of the electrolyte-air interface. In this Letter a new theory is proposed which allows us to explicitly calculate the ionic density profiles, the surface tension, and the electrostatic potential difference across the solution-air interface. Predictions of the theory are compared to experiments and are found to be in excellent agreement. The theory also sheds new light on one of the oldest puzzles of physical chemistry---the Hofmeister effect.
TL;DR: From observations on the relative depths of the free energies of the contact ion pair and the solvent-shared ion pair, along with related solvent structure analyses, a good correlation is found with this proposition: small-small and large- Large should associate in water, and small-large should be more dissociated.
Abstract: Using classical molecular dynamics simulations, we study ion−ion interactions in water. We study the potentials of mean force (PMF) for the full set of alkali halide ion pairs, and in each case, we test different parameter sets for modeling both the water and the ions. Altogether, we compared 300 different PMFs. We also calculate association equilibrium constants (KA) and compare them to two types of experiments. Of additional interest here was the proposition of Collins called the “law of matching water affinities”, where the relative affinity of ions in solution depends on the matching of cation and anion sizes. From observations on the relative depths of the free energies of the contact ion pair (CIP) and the solvent-shared ion pair (SIP), along with related solvent structure analyses, we find a good correlation with this proposition: small−small and large−large should associate in water, and small−large should be more dissociated.
TL;DR: In this article, an asymmetric supercapacitor activated carbon/0.5-mol/l K2SO4/V2O5·0.6H2O was successfully assembled, which could be cycled reversibly in the voltage region of 0.8-1.8
TL;DR: It is found that the hydrogen bonds are weaker than expected, as indicated by their short lifetimes, which is due to the fast rotational motion of anions, and this deviation results from the correlated motion of cations and anions over time scales up to nanoseconds.
Abstract: Molecular dynamics simulations with an all-atom model were carried out to study the ionic liquid 1-n-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6]. Analysis was carried out to characterize a number of structural and dynamic properties. It is found that the hydrogen bonds are weaker than expected, as indicated by their short lifetimes, which is due to the fast rotational motion of anions. Transport properties such as ion diffusion coefficients and ionic conductivity were also measured on the basis of long trajectories, and good agreement was obtained with experimental results. The phenomenon that electrical conductivity of ionic liquids deviates from the Nernst−Einstein relation was well reproduced in our work. On the basis of our analysis, we suggest that this deviation results from the correlated motion of cations and anions over time scales up to nanoseconds. In contrast, we find no evidence for long-lived ion-pairs migrating together.
TL;DR: In this paper, a state-of-the-art understanding on the physics of homogeneous dielectric barrier discharge at atmospheric pressure is presented. But it is based on the analysis of present and previous work about the behavior of these discharges and the conditions to get them.
Abstract: This paper is a state of the art of the understanding on the physics of homogeneous dielectric barrier discharge at atmospheric pressure. It is based on the analysis of present and previous work about the behavior of these discharges and the conditions to get them. Mechanisms controlling the homogeneity during gas breakdown and discharge development are successively discussed. The breakdown has to be a Townsend one, the ionization has to be slow enough to avoid a large avalanche development. During the breakdown, the discharge homogeneity is related to the ratio of the secondary emission at the cathode (γ coefficient) on the ionization in the gas bulk (α coefficient). Higher is this ratio, higher is the pressure × gas gap product (P.d.) value for which a Townsend breakdown is obtained. Among the phenomena enhancing the secondary emission there is the negative charge of the dielectric on the cathode surface, the trapping of ions in the gas and the existence of excited state having a long lifetime compared to the time between two consecutive discharges. The first phenomenon is always present when the electrodes are covered by a solid dielectric, the second one is related to the formation of a positive column and the third one is specific of the gas. During the discharge development, the homogeneity is mainly controlled by the voltage or the current imposed by the electrical circuit /electrode configuration and to the gas ability to be slowly ionized. Larger is the contribution of a multiple step ionization process like Penning ionization, higher will be the working domain of the discharge. A decrease of the gas voltage during the discharge development is a solution to enhance the contribution of this process. After 20 years of research a lot of mechanisms have been understood however there is still open questions like the nature of the Inhibited homogeneous DBD, surface energy transfers, role of attachment and detachment…