A review on machine learning algorithms for the ionic liquid chemical space

There are thousands of papers published every year investigating the properties and possible applications of ionic liquids. Industrial use of these exceptional fluids requires adequate understanding of their physical properties, in order to create the ionic liquid that will optimally suit the application. Computational property prediction arose from the urgent need to minimise the time and cost that would be required to experimentally test different combinations of ions. This review discusses the use of machine learning algorithms as property prediction tools for ionic liquids (either as standalone methods or in conjunction with molecular dynamics simulations), presents common problems of training datasets and proposes ways that could lead to more accurate and efficient models.

In this review article, the authors discuss the use of machine learning algorithms as tools for the prediction of physical and chemical properties of ionic liquids.     

Radioanalytical monitoring of the formation of barium sulfate in aqueous solutions

The formation of barium sulfate in aqueous media causes problems of insoluble scale formation. On the other hand, the coprecipitation of uranium and transuranium elements with barium sulfate has been suggested for the determination of these elements in environmental monitoring processes. Therefore, the study of barium sulfate crystal growth is required. The investigations done so far suffer from the low sensitivity of the analytical methods used. In the present work we have overcome this problem by using¹³¹Ba for the preparation of supersaturated solutions. Thus kinetics parameters such as induction time and precipitation rates were measured. The polynuclear mechanism was found to be operative at high and the spiral growth at low supersaturations.     

Calcium Carbonate Deposition on Cellulose

Cellulose powder was found to be a substrate favoring the deposition of calcite crystals from stable supersaturated solutions at pH 8.50 and at 25 degrees C. Kinetic analysis of the initial rates showed that they were proportional with the relative supersaturation with respect to calcite. Analysis of the dependence of the induction periods on the initial solution conditions showed that the number of ions forming the critical nucleus was 5. The second-order dependence of the rate of precipitation of calcite on cellulose on the solution supersaturation suggested a surface controlled mechanism. The surface energy of the calcite nuclei growing on cellulose was calculated to be 46 mJ m(-2) from the dependence of the induction time on the solution supersaturation. The overgrowth of calcite on cellulose was done selectively on the macromolecules possibly through active sites formation at ionizable functional groups (-OH). The nucleating capability of cellulose was found to be comparable with that of sulfonated polystyrene and significantly lower in comparison with sulfonated polystyrene divinyl benzene copolymer on which vaterite was formed. This fact together with the selective growth of the most stable calcite suggested that stereochemical factors are very important in determining both the kinetics and the nature of the polymorph formed. Copyright 2000 Academic Press.     

Efficiency of tributyltin extraction from rhine river sediment

A Rhine river sediment sample was spiked with tributyltin (TBT), equilibrated for ten days and the tributyltin extraction efficiency was optimised using a simplex algorithm. Analysis was effected using hydride generation gas chromatography-atomic absorption spectroscopy (GC-AAS) apparatus. The results show that, in this sediment sample, different molarities of HCl in methanol extract different species with varying extraction efficiencies. The least polar extraction solution extracted TBT more efficiently, whilst DBT and MBT require molar solution of HCl in methanol for efficient extraction.     

Model Studies on the Interaction of Amino Acids with Biominerals: The Effect of L-Serine at the Hydroxyapatite-Water Interface

The effect of L-serine in supersaturated solutions of calcium phosphate was investigated under plethostatic conditions. The rates of crystal growth measured in the presence of L-serine at relatively high concentrations and in the range between 2x10(-3) and 1x10(-2) mol dm(-3) were appreciably reduced. The inhibitory effect of L-serine was found to be due to blocking of a portion of the active growth sites by adsorption. Kinetics measurements in the presence of L-serine as well as adsorption isotherm analysis suggested Langmuir-type adsorption of L-serine on the surface of hydroxyapatite (HAP) with a relatively low affinity for the substrate. Adsorption experiments showed that at pH 7.4 considerable adsorption of L-serine onto HAP takes place, whereas at pH 10.0 the adsorption was negligible, suggesting that electrostatic interactions are dominant. Attraction between the positively charged protonated amino group of the L-serine molecule and the negatively charged HAP surface contributed largely to the adsorption. This was corroborated by the fact that, in the presence of L-serine in the solution, a significant shift of zeta-potential of the HAP particles to less negative values was found at pH values close to 7.4. At pH values higher than 10.0 essentially no shift of zeta-potential takes place. On the basis of the experimental results, a model was proposed according to which L-serine absorbs on the surface of HAP through electrostatic attractions exerted between one negative site of the HAP surface, i.e., phosphate or hydroxyl ion, and the positively charged protonated amino group of one L-serine molecule, forming a surface ion pair. Copyright 2001 Academic Press.     

Study of copper sulfide crystallization in PEO-SDS solutions

The crystallization of copper sulfide in aqueous supersaturated solutions in the presence of the polymer poly(ethylene oxide), PEO, and the surfactant sodium dodecyl sulfate, SDS, was investigated. In these systems, copper sulfide precipitation competes with the reaction between copper cations and dodecyl sulfate anions. The competition of the two reactions may affect the reaction products significantly; therefore it is important to study the properties of the surfactant salt, copper dodecyl sulfate (Cu(DS)2), in detail. The thermodynamic solubility constant of Cu(DS)2 was measured at 8 degrees C and was equal to (2.4 +/- 0.4) x 10(-10) M3. The Krafft point of Cu(DS)2 and its solubility curve (precipitation temperature for a range of concentrations) were also measured. The latter was found to be very close to room temperature. Temperature is thus a very significant parameter in these systems and must be carefully controlled in all experiments. The crystallization of copper sulfide in PEO-SDS solutions was investigated in solutions with compositions above and below the solubility curve. Copper sulfide nanoparticles predominate and are stabilized at temperatures above the solubility curve. Surprisingly, at temperatures below the solubility curve CuxS coexists with Cu(DS)2, which appears in the form of lamellar crystals. The system is further complicated by the presence of at least two different types of copper sulfides corresponding to different oxidation states of copper. Our results suggest that the predominance of Cu(DS)2 at lower temperatures is due to its limited solubility and is modified by the CuI/CuII redox equilibrium in combination with the solution pH.     

Oxygen evolution reaction: a perspective on a decade of atomic scale simulations

Multiple strategies to overcome the intrinsic limitations of the oxygen evolution reaction (OER) have been proposed by numerous research groups. Despite the substantial efforts, the driving force required for water oxidation is largely making the reaction inefficient. In the present work, we collected published studies involving DFT calculations for the OER, with the purpose to understand why the progress made so far, for lowering the overpotential of the reaction, is relatively small. The data revealed that the universal scaling relationship between HO* and HOO* intermediates is still present and robust, despite the variety in methods and structures used for calculating the binding energies of the intermediates. On the other hand, the data did not show a clear trend line regarding the O* binding. Our analysis suggested that trends in doped semiconducting oxides behave very differently from those in other oxides. This points towards a computational challenge in describing doped oxides in a realistic manner. We propose a way to overcome these computational challenges, which can be applied to simulations corresponding to doped semiconductors in general.

Multiple strategies to overcome the intrinsic limitations of the oxygen evolution reaction (OER) have been proposed by numerous research groups.     

Uniform estimates for the X-ray transform restricted to polynomial curves

We establish near-optimal mixed norm estimates for the X-ray transform restricted to polynomial curves with a weight that is a power of the affine arclength. The bounds that we establish depend only on the spatial dimension and the degree of the polynomial. Some of our results are new even in the well-curved case.     

Electrochemical behavior of silver thin films interfaced with yttria-stabilized zirconia

Thin silver films (100–800 nm) were deposited by physical vapor deposition (PVD) on yttria-stabilized zirconia solid electrolyte. The electric percolation as a function of the film thickness was studied during deposition and annealing using a two-electrode in-situ resistance measurement technique. Electrical percolation was achieved in as-deposited films greater than 5.4?±?0.4 nm; however, thermal treatment (550 °C in air) resulted in film dewetting for Ag films as thick as 500 nm and formation of electronically isolated Ag nanoparticles, as was confirmed by SEM and XPS. In thermally treated samples, stable electronic conductivity associated with a continuous percolated network was only observed in samples greater than 600 nm in thickness. The effect of polarization on the electrochemical reactions at the three-phase (electrode-gas-electrolyte) and two-phase (electrode-electrolyte) boundaries of the electrode was investigated by solid electrolyte cyclic voltammetry (SECV) at 350 °C and P _O2?=?6 kPa. With the application of positive potential, silver oxide (Ag₂O) was found to form along the three-phase boundary and then extends within the bulk of the electrode with increasing anodic potentials. By changing the hold time at positive potential, passivating oxide layers are formed which results in a shift in favor of the oxygen evolution reaction at the working electrode. This oxide forms according to a logarithmic rate expression with thick oxides being associated with decrease in current efficiency for subsequent oxide formation.