RESUMEN
While intensive studies have focused on the synthesis and characterization of new metal-organic nanotube (MONT) structures, the lack of size and morphology control remains an obstacle in broadening applications for this class of materials. Herein, we demonstrate control of MONT crystallite size and morphology by tuning polarity and the protic/aprotic nature of solvents, including dimethylformamide, N-methyl-2-pyrrolidone, ethanol, and 2-methyltetrahydrofuran, for the isostructural syntheses of two MONTs. Through a combination of transmission electron microscopy, powder X-ray diffraction, and selected area electron diffraction, we find that MONT crystallite sizes can be tuned while maintaining control over the relative dispersity without significantly altering the underlying crystal structure.
RESUMEN
Premelting of ice, a quasi-liquid layer (QLL) at the surface below the melting temperature, was first postulated by Michael Faraday 160 y ago. Since then, it has been extensively studied theoretically and experimentally through many techniques. Existing work has been performed predominantly on hexagonal ice, at conditions close to the triple point. Whether the same phenomenon can persist at much lower pressure and temperature, where stacking disordered ice sublimates directly into water vapor, remains unclear. Herein, we report direct observations of surface premelting on ice nanocrystals below the sublimation temperature using transmission electron microscopy (TEM). Similar to what has been reported on hexagonal ice, a QLL is found at the solid-vapor interface. It preferentially decorates certain facets, and its thickness increases as the phase transition temperature is approached. In situ TEM reveals strong diffusion of the QLL, while electron energy loss spectroscopy confirms its amorphous nature. More significantly, the premelting observed in this work is thought to be related to the metastable low-density ultraviscous water, instead of ambient liquid water as in the case of hexagonal ice. This opens a route to understand premelting and grassy liquid state, far away from the normal water triple point.
RESUMEN
Herein, we present the direct observation via liquid-phase transmission electron microscopy (LPTEM) of the nucleation and growth pathways of structures formed by the so-called "ouzo effect", which is a classic example of surfactant-free, spontaneous emulsification. Such liquid-liquid phase separation occurs in ternary systems with an appropriate cosolvent such that the addition of the third component extracts the cosolvent and makes the other component insoluble. Such droplets are homogeneously sized, stable, and require minimal energy to disperse compared to conventional emulsification methods. Thus, ouzo precipitation processes are an attractive, straightforward, and energy-efficient technique for preparing dispersions, especially those made on an industrial scale. While this process and the resulting emulsions have been studied by numerous indirect techniques (e.g., X-ray and light scattering), direct observation of such structures and their formation at the nanoscale has remained elusive. Here, we employed the nascent technique of LPTEM to simultaneously evaluate droplet growth and nanostructure. Observation of such emulsification and its rate dependence is a promising indication that similar LPTEM methodologies may be used to investigate emulsion formation and kinetics.
RESUMEN
Metal-organic nanotubes (MONTs) are 1-dimensional crystalline porous materials that are formed from ligands and metals in a manner identical to more typical 3-dimensional metal-organic frameworks (MOFs). MONTs form anisotropically in one dimension making them excellent candidates for linker engineering for control of chemical composition and spacing. A novel series of MONTs was synthesized utilizing a mixture of 1,2,4-ditriazole ligands containing both a fully protonated aryl moiety and its tetrafluorinated analog in ratios of, 0 : 1, 1 : 4, 1 : 1, 4 : 1, and 1 : 0, respectively. All MONTs were characterized by both bulk and nanoscale measurements, including SCXRD, PXRD, ssNMR and TEM, to determine the resulting co-polymer architecture (alternating, block, or statistical) and the ligand ratios in the solid materials. All characterization methods point towards statistical copolymerization of the materials in a manner analogous to 3D MOFs, all of which notably could be achieved without destructive analytical methods.
