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Water hydrogen bonding is extremely versatile; approximately 20 ice structures and several types of clathrate hydrate structures have been identified. These crystalline water structures form at temperatures below room temperature and/or at high pressure. We used transmission electron microscopy to study a new crystalline water structure in a clathrate state that is prepared by sandwiching gas-supersaturated water between graphene layers under ambient conditions. In this clathrate state, water molecules form a three-dimensional hydrogen bonding network that encloses gas-filled cages 2-4 nm in size. We derived the crystalline water structure by recording and analyzing electron diffraction patterns and performing first-principles calculations. The structure consists purely of pentagonal rings and has a topology similar to that of water ice XVII. The study proposed a mechanism for the formation of the clathrate state. The present results improve the understanding of interactions among water and small nonpolar molecules and offer novel insights into the local structures of ambient liquid water.

Surfaces (interfaces) dictate many physical and chemical properties of solid materials and adsorbates considerably affect these properties. Nitrogen molecules, which are the most abundant constituent in ambient air, are considered to be inert. Our study combining atomic force microscopy (AFM), X-ray photoemission spectroscopy (XPS), and thermal desorption spectroscopy (TDS) revealed that nitrogen and water molecules can self-assemble into two-dimensional domains, forming ordered stripe structures on graphitic surfaces in both water and ambient air. The stripe structures of this study were composed of approximately 90% and 10% water and nitrogen molecules, respectively, and survived in ultra-high vacuum (UHV) conditions at temperatures up to approximately 350 K. Because pure water molecules completely desorb from graphitic surfaces in a UHV at temperatures lower than 200 K, our results indicate that the incorporation of nitrogen molecules substantially enhanced the stability of the crystalline water hydrogen bonding network. Additional studies on interfacial gas hydrates can provide deeper insight into the mechanisms underlying formation of gas hydrates.

Water-alcohol mixtures exhibit many abnormal physicochemical properties, the origins of which remain controversial. Here we use transmission electron microscopy (TEM), nanoparticle tracking analysis (NTA), and atomic force microscopy (AFM) to study ethanol-water mixtures. TEM reveals mesoscopic clathrate structures with water molecules forming a crystalline matrix hosting a high density of tiny cells. The presence of these mesoscopic clathrate structures is further supported by a refractive index of 1.27+-0.02 at 405 nm measured via NTA and the hydrophilic nature of the mesoscopic structures implied by AFM observations, explaining many long-standing puzzles related to water-alcohol mixtures.

There is only a handful of scanning techniques that can provide surface topography at nanometre resolution. At the same time, there are no methods that are capable of non-invasive imaging of the three-dimensional surface topography of a thin free-standing crystalline material. Here we propose a new technique - the divergent beam electron diffraction (DBED) and show that it can directly image the inhomogeneity in the atomic positions in a crystal. Such inhomogeneities are directly transformed into the intensity contrast in the first order diffraction spots of DBED patterns and the intensity contrast linearly depends on the wavelength of the employed probing electrons. Three-dimensional displacement of atoms as small as 1 angstrom can be detected when imaged with low-energy electrons (50 - 250 eV). The main advantage of DBED is that it allows visualisation of the three-dimensional surface topography and strain distribution at the nanometre scale in non-scanning mode, from a single shot diffraction experiment.

The contact of water with graphene is of fundamental importance and of great interest for numerous promising applications, but how graphene interacts with water remains unclear. Here we used atomic force microscopy to investigate hydrophilic mica substrates with some regions covered by mechanically exfoliated graphene layers in water. In water containing air gas close to the saturation concentration (within ~40%), cap-shaped nanostructures and ordered stripe domains were observed on graphene-covered regions, but not on pure mica regions. These structures did not appear on graphene when samples were immersed in highly degassed water, indicating that their formation was caused by adsorption of gas dissolved in water. Thus, atomically thin graphene, even at a narrow width of 20 nm, changes the local surface chemistry of a highly hydrophilic substrate. Further, surface hydrophobicity significantly affects gas adsorption, which has broad implications for diverse phenomena in water.

It has been a general trend to develop low-voltage electron microscopes due to their high imaging contrast of the sample and low radiation damage. Atom-resolved transmission electron microscopes with voltages as low as 15-40 kV have been demonstrated. However, achieving atomic resolution at voltages lower than 10 kV is extremely difficult. An alternative approach is coherent imaging or phase retrieval imaging, which requires a sufficiently coherent source and an adequately small detection area on the sample as well as the detection of high-angle diffracted patterns with a sufficient resolution. In this work, we propose several transmission-type schemes to achieve coherent imaging of thin materials (less than 5 nm thick) with atomic resolution at voltages lower than 10 kV. Experimental schemes of both lens-less and lens-containing designs are presented and the advantages and challenges of these schemes are discussed. Preliminary results based on a highly coherent single-atom electron source are presented. The image plate is designed to be retractable to record the transmission patterns at different positions along the beam propagation direction. In addition, reflection-type coherent electron imaging schemes are also proposed as novel methods for characterizing surface atomic and electronic structures of materials.