A comparative study of secondary Ion emission from water ice under Ion bombardment by Au+, Au3+, and C60+

Secondary ion emission from water ice has been studied using Au⁺, Au₃⁺, and C₆₀⁺ primary ions. In contrast to the gas phase in which the spectra are dominated by the (H₂O)_nH⁺ series of ions, the spectra from ice using all three primary ions are principally composed of two series of cluster ions (H₂O)_nH⁺ and (H₂O)_n⁺. Dependent on the conditions, the unprotonated series can dominate the spectra. Since in the gas phase (H₂O)_n⁺ is unstable with respect to the formation of the protonated ion series, the presence of the solid must provide a means to stabilize their formation. The cluster ion yields under Au⁺ bombardment are very low and can be understood in terms of sputtering on the borderline between linear cascade and thermal spike behavior. There is a 10⁴ increase in yield across the whole spectrum compared to Au⁺ when Au₃⁺ and C₆₀⁺ species are used as primary ions. The character of the spectra differed between these two primary ions, but insights into the mechanism of secondary ion emission for both is discussed within an energy deposition framework provided by the fluid flow-based mesoscale energy deposition footprint (MEDF) model that predicts a cone-shaped zone of activation and emission. C₆₀⁺ differs from Au^₃+ in that it delivers its energy closer to the surface, and it is argued this has consequences for the cluster ion distribution and yield. Increasing the ion dose by sputtering suppresses the yield of (H₂O)_n⁺ and increases the yield of the protonated ions in the small cluster region, whereas the yield in the large cluster regime is suppressed significantly. The three primary ions show rather different behavior, and this is discussed in the light of the sputtering models. Finally, negative ion spectra including cluster ions have been observed for the first time. C₆₀⁺ delivers the highest yields, but these are less than 10 times the positive ion yields, probably because the O and OH fragment ions on which the clusters are based are easily neutralized by protons.

A simple method for measuring carbon-13 fatty acid enrichment in the major lipid classes of microalgae using GC-MS

A simple method for tracing carbon fixation and lipid synthesis in microalgae was developed using a combination of solid-phase extraction (SPE) and negative ion chemical ionisation gas chromatography mass spectrometry (NCI-GC-MS). NCI-GC-MS is an extremely sensitive technique that can produce an unfragmented molecular ion making this technique particularly useful for stable isotope enrichment studies. Derivatisation of fatty acids using pentafluorobenzyl bromide (PFBBr) allows the coupling of the high separation efficiency of GC and the measurement of unfragmented molecular ions for each of the fatty acids by single quadrupole MS. The key is that isotope spectra can be measured without interference from co-eluting fatty acids or other molecules. Pre-fractionation of lipid extracts by SPE allows the measurement of13C isotope incorporation into the three main lipid classes (phospholipids, glycolipids, neutral lipids) in microalgae thus allowing the study of complex lipid biochemistry using relatively straightforward analytical technology. The high selectivity of GC is necessary as it allows the collection of mass spectra for individual fatty acids, including cis/trans isomers, of the PFB-derivatised fatty acids. The combination of solid-phase extraction and GC-MS enables the accurate determination of13C incorporation into each lipid pool. Three solvent extraction protocols that are commonly used in lipidomics were also evaluated and are described here with regard to extraction efficiencies for lipid analysis in microalgae.

Investigation of the postcure reaction and surface energy of epoxy resins using time-of-flight secondary ion mass spectrometry and contact-angle measurements

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to investigate correlations between the molecular changes and postcuring reaction on the surface of a diglycidyl ether of bisphenol A and diglycidylether of bisphenol F based epoxy resin cured with two different amine-based hardeners. The aim of this work was to present a proof of concept that ToF-SIMS has the ability to provide information regarding the reaction steps, path, and mechanism for organic reactions in general and for epoxy resin curing and postcuring reactions in particular. Contact-angle measurements were taken for the cured and postcured epoxy resins to correlate changes in the surface energy with the molecular structure of the surface. Principal components analysis (PCA) of the ToFSIMS positive spectra explained the variance in the molecular information, which was related to the resin curing and postcuring reactions with different hardeners and to the surface energy values. The first principal component captured information related to the chemical phenomena of the curing reaction path, branching, and network density based on changes in the relative ion density of the aliphatic hydrocarbon and the C₇H₇O⁺ positive ions. The second principal component captured information related to the difference in the surface energy, which was correlated to the difference in the relative intensity of the C_xH_yN_z⁺ ions of the samples. PCA of the negative spectra provided insight into the extent of consumption of the hardener molecules in the curing and postcuring reactions of both systems based on the relative ion intensity of the nitrogen-containing negative ions and showed molecular correlations with the sample surface energy.

Measurement of surface forces between mica sheets immersed in aqueous quaternary ammonium ion solutions

Forces between mica surfaces immersed in Me4NBr, Pr4NBr, and Pe4NBr solutions over a wide concentration range are reported (Me = methyl, Pr = propyl, Pe = pentyl). In each case the cation adsorbs quite strongly onto the negatively charged mica surface and determines the double-layer potential. However, this strong adsorption does not cause complete neutralization of the negative lattice charge apparently because of packing constraints due to the large size of these ions. Adsorption of Me4N+ ions gives rise to a short-range (<2 nm) repulsive force similar to that previously observed between bilayers of CTAB and may be due to the residual hydration of these ions. The large rations also, unexpectedly, give rise to short-range repulsive forces but of a somewhat different nature. In this case, the repulsive forces can be explained by assuming that the large adsorbed ions shift the plane of charge a distance of one ion diameter from the mica surface. At all but very high concentrations these larger ions could be displaced from the mica surfaces on forcing them together. No evidence of any “hydrophobic attraction” was observed between surfaces containing these adsorbed ions. Previous studies on coagulation are discussed in the light of our results.

Ex situ electrochemical sodiation/desodiation observation of Co₃O₄ anchored carbon nanotubes: a high performance sodium-ion battery anode produced by pulsed plasma in a liquid

Liquid plasma, produced by nanosecond pulses, provides an efficient and simple way to fabricate a nanocomposite architecture of Co3O4/CNTs from carbon nanotubes (CNTs) and clusters of Co3O4 nanoparticles in deionized water. The crucial feature of the composite's structure is that Co3O4 nanoparticle clusters are uniformly dispersed and anchored to CNT networks in which Co3O4 guarantees high electrochemical reactivity towards sodium, and CNTs provide conductivity and stabilize the anode structure. We demonstrated that the Co3O4/CNT nanocomposite is capable of delivering a stable and high capacity of 403 mA h g(-1) at 50 mA g(-1) after 100 cycles where the sodium uptake/extract is confirmed in the way of reversible conversion reaction by adopting ex situ techniques. The rate capability of the composite is significantly improved and its reversible capacity is measured to be 212 mA h g(-1) at 1.6 A g(-1) and 190 mA h g(-1) at 3.2 A g(-1), respectively. Due to the simple synthesis technique with high electrochemical performance, Co3O4/CNT nanocomposites have great potential as anode materials for sodium-ion batteries.

Improvement of charge/discharge properties of oligoether electrolytes by zwitterions with an attached cyano group for use in lithium-ion secondary batteries

Zwitterions with a cyano group on the side chain (CZ) were synthesized. Although the addition of CZ caused a slightly negative effect on viscosity, ionic conductivity, limiting current density, and lithium transference number, the oxidation limit of PEGDME/lithium bis(trifluoromethylsulfonyl)amide (LiTFSA) composites was improved to over 5 V. For charge/discharge testing using Li|electrolyte|LiCoO2 cells, the cycle stability of PEGDME/LiTFSA with CZ in the voltage range of 3.0-4.6 V was much higher than that of PEGDME/LiTFSA. Incorporating a small mole fraction of CZ into PEGDME-based electrolytes prevented an increase in the interface resistance between the electrolyte and cathode with increasing numbers of the cycle.

Lithium-ion capacitors with 2D Nb2CTx (MXene) - carbon nanotube electrodes

There is a growing interest to hybrid energy storage devices, such as lithium-ion capacitors, in which battery-type electrodes are combined with capacitor-type ones. It is anticipated that the energy density (either gravimetric or volumetric) of lithium-ion capacitors is improved if pseudocapacitive or fast insertion materials are used instead of conventional activated carbon (AC) in the capacitor-type electrode. MXenes, a new family of two-dimensional transition metal carbides, demonstrate metallic conductivity and fast charge-discharge behavior that make them suitable for this application. In this study, we move beyond single electrodes, half-cell studies and demonstrate three types of hybrid cells using Nb2CTx-carbon nanotube (CNT) films. It is shown that lithiated graphite/Nb2CTx-CNT, Nb2CTx-CNT/LiFePO4 and lithiated Nb2CTx-CNT/Nb2CTx-CNT cells are all able to operate within 3 V voltage windows and deliver capacities of 43, 24 and 36 mAh/g (per total weight of two electrodes), respectively. Moreover, the polarity of the electrodes can be reversed in the symmetric Nb2CTx-CNT cells from providing a positive potential between 0 and 3 V to a negative one from -3 to 0 V. It is shown that the volumetric energy density (50-70 Wh/L) of our first-generation devices with MXene electrodes exceeds that of a lithium titanate/AC capacitor.