Synthesis and surface chemistry of high quality wurtzite and kesterite Cu2ZnSnS4 nanocrystals using tin(II) 2-ethylhexanoate as a new tin source.

A novel synthesis method for the preparation of Cu2ZnSnS4 nanocrystals is presented using a liquid precursor of tin, namely tin(II) 2-ethylhexanoate, which yields small and nearly monodisperse NCs either in the kesterite or in the wurtzite phase depending on the sulfur source (elemental sulfur in oleylamine vs. dodecanethiol).

Ion-ion and ion-solvent interactions in lithium imidazolide electrolytes studied by Raman spectroscopy and DFT models.

Molecular level interactions are of crucial importance for the transport properties and overall performance of ion conducting electrolytes. In this work we explore ion-ion and ion-solvent interactions in liquid and solid polymer electrolytes of lithium 4,5-dicyano-(2-trifluoromethyl)imidazolide (LiTDI)-a promising salt for lithium battery applications-using Raman spectroscopy and density functional theory calculations. High concentrations of ion associates are found in LiTDI:acetonitrile electrolytes, the vibrational signatures of which are transferable to PEO-based LiTDI electrolytes. The origins of the spectroscopic changes are interpreted by comparing experimental spectra with simulated Raman spectra of model structures. Simple ion pair models in vacuum identify the imidazole nitrogen atom of the TDI anion to be the most important coordination site for Li(+), however, including implicit or explicit solvent effects lead to qualitative changes in the coordination geometry and improved correlation of experimental and simulated Raman spectra. To model larger aggregates, solvent effects are found to be crucial, and we finally suggest possible triplet and dimer ionic structures in the investigated electrolytes. In addition, the effects of introducing water into the electrolytes-via a hydrate form of LiTDI-are discussed.

Influence of the substituents on the structure and properties of benzoxaboroles.

Benzoxaboroles possessing aryl substituents in the oxaborole ring were synthesized, and their structures were determined by single-crystal X-ray diffraction. Structures in the solid state are centrosymmetric dimers with two intermolecular hydrogen bonds. These compounds were investigated using a combination of the spectroscopic and the computational approach, comparing their properties with the unsubstituted compound. Investigated compounds were characterized by (1)H, (13)C, and (11)B NMR spectroscopy in solution. Assignment of (1)H and (13)C signals was made on the basis of HSQC and HMBC spectra. The molecular structure of 1,3-dihydro-1-hydroxy-3-phenyl-2,1-benzoxaborole was calculated by the density functional (B3LYP) method with the extended 6-311++G(d,p) basis set. The calculated geometrical parameters were compared with experimental X-ray data, and the differences between experimental and calculated values were found to be of the order of experiment standard deviation, confirming a good description by this level of theory. The harmonic frequencies, potential energy distribution (PED), and IR intensities of this compound and its deuterated analogue were calculated with the B3LYP method. The assignment of the experimental spectra was made on the basis of the calculated PED. The consequence of dimer formation is the splitting of the vibrational modes into symmetric and antisymmetric vibrations. The structure modification resulting from the hydrogen bonded dimers formation is presented.

Comparative laser spectroscopy diagnostics for ancient metallic artefacts exposed to environmental pollution.

Metal artworks are subjected to corrosion and oxidation processes due to reactive agents present in the air, water and in the ground that these objects have been in contact with for hundreds of years. This is the case for archaeological metals that are recovered from excavation sites, as well as artefacts exposed to polluted air. Stabilization of the conservation state of these objects needs precise diagnostics of the accrued surface layers and identification of original, historical materials before further protective treatments, including safe laser cleaning of unwanted layers. This paper presents analyses of the chemical composition and stratigraphy of corrosion products with the use of laser induced breakdown spectroscopy (LIBS) and Raman spectroscopy. The discussion of the results is supported by material studies (SEM-EDS, XRF, ion-analyses). The tests were performed on several samples taken from original objects, including copper roofing from Wilanów Palace in Warsaw and Karol Poznanski Palace in LódY, bronze decorative figures from the Wilanów Palace gardens, and four archaeological examples of old jewellery (different copper alloys). Work has been performed as a part of the MATLAS project in the frames of EEA and Norway Grants (www.matlas.eu) and the results enable the comparison of the methodology and to elaborate the joint diagnostic procedures of the three project partner independent laboratories.

Conductive, capacitive, and viscoelastic properties of a new composite of the C60-pd conducting polymer and single-wall carbon nanotubes.

Thin films of a new composite of an electroactive fullerene-based (C60-Pd) polymer and HiPCO single-wall carbon nanotubes, which were noncovalently modified by 1-pyrenebutiric acid (pyr-SWCNTs), were electrochemically prepared under multiscan cyclic voltammetry conditions. With respect to blank polymer, superior conductive, capacitive, and viscoelasitic properties of the composite were demonstrated. Composition of pyr-SWCNTs was determined by thermogravimetric analyses, which showed one molecule of 1-pyrenebutiric acid per approximately 20 carbon atoms of SWCNT. Atomic force microscopy imaging revealed that pyr-SWCNTs form tangles of pyr-SWCNTs bundles surrounded by globular clusters of the C60-Pd polymer. Peaks characteristic of both pyr-SWCNTs (radial breathing modes at approximately 200 to 300 cm(-1)) and C60-Pd polymer in the Raman spectra recorded for the composite confirmed the presence of pyr-SWCNTs in the composite film. The mass of the deposited film was in situ measured by piezoelectric microgravimetry with the use of an electrochemical quartz crystal microbalance (EQCM). Then, curves of the current, resonant frequency change, and dynamic resistance change versus the potential in different potential ranges were simultaneously recorded in a blank acetonitrile solution of tetrabutylammonium perchlorate. Specific capacitance, determined at -1.20 V for the composite as 90 F g(-1), was twice as high as that for the polymer. Electrochemical impedance spectroscopy was used to determine impedance parameters of both the C60-Pd polymer and C60-Pd/pyr-SWCNTs composite film. This data analysis indicated increased capacitance and decreased resistance for the new composite film.

Structural and spectroscopic properties of an aliphatic boronic acid studied by combination of experimental and theoretical methods.

Boronic acids have emerged as one of the most useful class of organoboron molecules, with application in synthesis, catalysis, analytical chemistry, supramolecular chemistry, biology, and medicine. In this study, the structural and spectroscopic properties of n-butylboronic acid were investigated using experimental and theoretical approaches. X-ray crystallography method provided structural information on the studied compound in the solid state. Infrared and Raman spectroscopy served as tools for the data collection on vibrational modes of the analyzed system. Car-Parrinello molecular dynamics simulations in solid state were carried out at 100 and 293 K to investigate an environmental and temperature influence on molecular properties of the n-butylboronic acid. Analysis of interatomic distances of atoms involved in the intermolecular hydrogen bond was performed to study the proton motion in the crystal. Subsequently, Fourier transform of autocorrelation functions of atomic velocities and dipole moment was applied to study the vibrational properties of the compound. In addition, the inclusion of quantum nature of proton motion was performed for O-H stretching vibrational mode by application of the envelope method for intermolecular hydrogen-bonded system. The second part of the computational study consists of simulations performed in vacuo. Monomeric and dimeric forms of the n-butylboronic acid were investigated using density functional theory and Moller-Plesset second-order perturbation method. The basis set superposition error was estimated. Finally, atoms in molecules (AIM) theory was applied to study electron density topology and properties of the intermolecular hydrogen bond. Successful reproduction of the molecular properties of the n-butylboronic acid by computational methodologies, presented in the manuscript, indicates the way for future studies of large boron-containing organic systems of importance in biology or materials science.

Analysis of charge transport in gels containing polyoxometallates using methods of different sensitivity to migration.

Two methods have been used for examination of transport of charge in gels soaked with DMF and containing dissolved polyoxometallates. The first method is based on the analysis of both Cottrellian and steady-state currents and therefore is capable of giving the concentration of the electroactive redox centres and their transport (diffusion-type) coefficient. The second method provides the real diffusion coefficients, i.e. transport coefficients free of migrational influence, for both the substrate and the product of the electrode reaction. Several gels based on poly(methyl methacrylate), with charged (addition of 1-acrylamido-2-methyl-2-propanesulphonic acid to the polymerization mixture) and uncharged chains, have been used in the investigation. The ratio obtained for the diffusion coefficient (second method) and transport coefficient (first method) was smaller for the gels containing charged polymer chains than for the gels with uncharged chains. In part these changes could be explained by the contribution of migration to the transport of polyoxomatallates in the gels. However, the impact of the changes in the polymer-channel capacity at the electrode surface while the electrode process proceeds was also considered. These structural changes should affect differently the methods based on different time domains.