Temperature dependence of the hydrogen bond network in Trimethylamine N-oxide and guanidine hydrochloride - water solutions

We present an X-ray Compton scattering study on aqueous Trimethylamine N-oxide (TMAO) and guanidine hydrochloride solutions (GdnHCl) as a function of temperature. Independent from the concentration of the solvent, Compton profiles almost resemble results for liquid water as a function of temperature. However, The number of hydrogen bonds per water molecule extracted from the Compton profiles suggests a decrease of hydrogen bonds with rising temperatures for all studied samples, the differences between water and the solutions are weak. Nevertheless, the data indicate a reduced bond weakening with rising TMAO concentration up to 5M of 7.2% compared to 8 % for pure water. In contrast, the addition of GdnHCl appears to behave differently for concentrations up to 3.1 M with a weaker impact on the temperature response of the hydrogen bond structure

Breathing porous liquids based on responsive metal-organic framework particles

Responsive metal-organic frameworks (MOFs) that display sigmoidal gas sorption isotherms triggered by discrete gas pressure-induced structural transformations are highly promising materials for energy related applications. However, their lack of transportability via continuous flow hinders their application in systems and designs that rely on liquid agents. We herein present examples of responsive liquid systems which exhibit a breathing behaviour and show step-shaped gas sorption isotherms, akin to the distinct oxygen saturation curve of haemoglobin in blood. Dispersions of flexible MOF nanocrystals in a size-excluded silicone oil form stable porous liquids exhibiting gated uptake for CO2, propane and propylene, as characterized by sigmoidal gas sorption isotherms with distinct transition steps. In situ X-ray diffraction studies show that the sigmoidal gas sorption curve is caused by a narrow pore to large pore phase transformation of the flexible MOF nanocrystals, which respond to gas pressure despite being dispersed in silicone oil. Given the established flexible nature and tunability of a range of MOFs, these results herald the advent of breathing porous liquids whose sorption properties can be tuned rationally for a variety of technological applications

Transition from elastic to plastic strain release in core−shell nanowires revealed by in-plane x-ray diffraction

We investigate the strain evolution and relaxation process as function of increasing lattice mismatch between the GaAs core and surrounding InxGa$_{1-x}$As shell in core–shell nanowire heterostructures grown on Si(111) substrates. The dimensions of the core and shell are kept constant whereas the indium concentration inside the shell is varied. Measuring the $22\bar{4}$ and $2\bar{2}0$ in-plane Bragg reflections normal to the nanowire side edges and side facets, we observe a transition from elastic to plastic strain release for a shell indium content x > 0.5. Above the onset of plastic strain relaxation, indium rich mounds and an indium poor coherent shell grow simultaneously around the GaAs core. Mound formation was observed for indium contents x = 0.5 and 0.6 by scanning electron microscopy. Considering both the measured radial reflections and the axial 111 Bragg reflection, the 3D strain variation was extracted separately for the core and the InxGa$_{1-x}$As shell

Towards in-line real-time characterization of roll-to-roll produced ZTO/Ag/ITO thin films by hyperspectral imaging

Large area manufacturing processes of thin films such as large-area vacuum roll-to-roll coating of dielectric and gas permeation barrier layers in industry require a precise control of e.g. film thickness, homogeneity, chemical compositions, crystallinity and surface roughness. In order to determine these properties in real time, hyperspectral imaging is a novel, cost-efficient, and fast tool as in-line technology for large-area quality control. We demonstrate the application of hyperspectral imaging to characterize the thickness of thin films of the multilayer system ZTO/Ag/ITO produced by roll-to-roll magnetron sputtering on 220 mm wide polyethylene terephthalate substrate. X-ray reflectivity measurements are used to determine the thickness gradients of roll-to-roll produced foils with sub nanometer accuracy that serve as ground truth data to train a machine learning model for the interpretation of the hyperspectral imaging spectra. Based on the model, the sub-layer thicknesses on the complete substrate foil area were predicted which demonstrates the capabilities of this approach for large-scale in-line real-time quality control for industrial applications

Tetrahydrofuran Clathrate Hydrate Formation

We report on the formation of tetrahydrofuran clathrate hydrate studied by x-ray Raman scattering measurements at the oxygen K edge. A comparison of x-ray Raman spectra measured from water-tetrahydrofuran mixtures and tetrahydrofuran hydrate at different temperatures supports stochastic hydrate formation models rather than models assuming hydrate precursors. This is confirmed by molecular dynamics simulations and density functional theory calculations of x-ray Raman spectra. In addition, changes in the spectra of tetrahydrofuran hydrate with temperatures close to the hydrate's dissociation temperature were observed and may be connected to changes in hydrate's local structure due to the formation of hydrogen bonds between guest and water molecules.We report on the formation of tetrahydrofuran clathrate hydrate studied by x-ray Raman scattering measurements at the oxygen K edge. A comparison of x-ray Raman spectra measured from water-tetrahydrofuran mixtures and tetrahydrofuran hydrate at different temperatures supports stochastic hydrate formation models rather than models assuming hydrate precursors. This is confirmed by molecular dynamics simulations and density functional theory calculations of x-ray Raman spectra. In addition, changes in the spectra of tetrahydrofuran hydrate with temperatures close to the hydrate's dissociation temperature were observed and may be connected to changes in hydrate's local structure due to the formation of hydrogen bonds between guest and water molecules.We report on the formation of tetrahydrofuran clathrate hydrate studied by x-ray Raman scattering measurements at the oxygen K edge. A comparison of x-ray Raman spectra measured from water-tetrahydrofuran mixtures and tetrahydrofuran hydrate at different temperatures supports stochastic hydrate formation models rather than models assuming hydrate precursors. This is confirmed by molecular dynamics simulations and density functional theory calculations of x-ray Raman spectra. In addition, changes in the spectra of tetrahydrofuran hydrate with temperatures close to the hydrate's dissociation temperature were observed and may be connected to changes in hydrate's local structure due to the formation of hydrogen bonds between guest and water molecules.Peer reviewe

Intramolecular structure and energetics in supercooled water down to 255 K

We studied the structure and energetics of supercooled water by means of X-ray Raman and Compton scattering. Under supercooled conditions down to 255 K, the oxygen K-edge measured by X-ray Raman scattering suggests an increase of tetrahedral order similar to the conventional temperature effect observed in non-supercooled water. Compton profile differences indicate contributions beyond the theoretically predicted temperature effect and provide a deeper insight into local structural changes. These contributions suggest a decrease of the electron mean kinetic energy by 3.3 +/- 0.7 kJ (mol K)(-1) that cannot be modeled within established water models. Our surprising results emphasize the need for water models that capture in detail the intramolecular structural changes and quantum effects to explain this complex liquid.Peer reviewe

In situ characterization of the decomposition behavior of Mg(BH4)(2) by X-ray Raman scattering spectroscopy

We present an in situ study of the thermal decomposition of Mg(BH4)(2) in a hydrogen atmosphere of up to 4 bar and up to 500 degrees C using X-ray Raman scattering spectroscopy at the boron K-edge and the magnesium L2,3-edges. The combination of the fingerprinting analysis of both edges yields detailed quantitative information on the reaction products during decomposition, an issue of crucial importance in determining whether Mg(BH4)(2) can be used as a next-generation hydrogen storage material. This work reveals the formation of reaction intermediate(s) at 300 degrees C, accompanied by a significant hydrogen release without the occurrence of stable boron compounds such as amorphous boron or MgB12H12. At temperatures between 300 degrees C and 400 degrees C, further hydrogen release proceeds via the formation of higher boranes and crystalline MgH2. Above 400 degrees C, decomposition into the constituting elements takes place. Therefore, at moderate temperatures, Mg(BH4)(2) is shown to be a promising high-density hydrogen storage material with great potential for reversible energy storage applications.Peer reviewe

Ultrathin films of 2D Hofmann-type coordination polymers: influence of pillaring linkers on structural flexibility and vertical charge transport

Searching for novel materials and controlling their nanostructuration into electronic devices is a challenging task ahead of chemists and chemical engineers. Even more so when this new application requires an exquisite control over the morphology, crystallinity, roughness and orientation of the films produced. In this context, it is of critical importance to analyze the influence of the chemical composition of perspective materials on their properties at the nanoscale. We report the fabrication of ultrathin films (thickness < 30 nm) of a family of FeII Hofmann-like coordination polymers by using an optimized liquid phase epitaxy (LPE) set-up. The series [Fe(L)2{Pt(CN)4}] (L = pyridine, pyrimidine and isoquinoline) conform an ideal platform for correlating the effect of the axial nitrogenated ligand with changes to their structural response to guests or electrical resistance. All film properties relevant to device integration have been thoroughly analyzed with complementary surface techniques for a meaningful comparison. Our results reveal that changes to this ligand can hinder the structural transformation triggered by the absorption of guest molecules previously reported for the pyridine phase. Also important, it can substantially hinder vertical charge transport across the layers, even at the ultrathin film limit