The distribution of ions and charge at solid-water interfaces plays an essential role in a wide range of processes in biology, geology and technology. While theoretical models of the solid-electrolyte interface date back to the early 20th century, a detailed picture of the structure of the electric double layer has remained elusive, largely because of experimental techniques have not allowed direct observation of the behaviour of ions, i.e. with subnanometer resolution. We have made use of recent advances in high-resolution Atomic Force Microscopy to reveal, with atomic level precision, the ordered adsorption of the mono- and divalent ions that are common in natural environments to heterogeneous gibbsite/silica surfaces in contact with aqueous electrolytes. Complemented by density functional theory, our experiments produce a detailed picture of the formation of surface phases by templated adsorption of cations, anions and water, stabilized by hydrogen bonding.
Various two-dimensional (2D) carbon allotropes with nonalternant topologies, such as pentaheptites and phagraphene, have been proposed. Predictions indicate that these metastable carbon polymorphs, which contain odd-numbered rings, possess unusual (opto)electronic properties. However, none of these materials has been achieved experimentally due to synthetic challenges. In this work, by using on-surface synthesis, nanoribbons of the nonalternant graphene allotropes, phagraphene and tetrapenta-hepta(TPH)-graphene, have been obtained by dehydrogenative C−C coupling of 2,6-polyazulene chains. These chains were formed in a preceding reaction step via on-surface Ullmann coupling of 2,6-dibromoazulene. Low-temperature scanning probe microscopies with CO-functionalized tips and density functional theory calculations have been used to elucidate their structural properties. The proposed synthesis of nonalternant carbon nanoribbons from the fusion of synthetic line-defects may pave the way for large-area preparation of novel 2D carbon allotropes.
Characterization of subsurface morphology and mechanical properties with nanoscale resolution and depth control is of significant interest in soft matter fields like biology, polymer science, and even in future applications like nanomanufacturing, where buried structural and compositional features are important to the functionality of the system. However, controllably "feeling" the subsurface is a challenging task for which the available imaging tools are relatively limited. In this paper, we propose a trimodal atomic force microscopy (AFM) imaging scheme, whereby three eigenmodes of the microcantilever probe are used as separate control "knobs" to simultaneously measure the topography, modulate sample indentation by the tip during tip-sample impact, and map compositional contrast, respectively. We illustrate this multifrequency imaging approach through computational simulation and experiments conducted on ultrathin polymer films with embedded glass nanoparticles in ambient air. By actively increasing the tip-sample indentation using a higher eigenmode of the cantilever, we are able to gradually and controllably reveal glass nanoparticles which are buried tens of nanometers deep under the surface, while still being able to refocus on the surface.
We present a method to determine the local surface charge of solid-liquid interfaces from Atomic Force Microscopy (AFM) measurements that takes into account shifts of the adsorption/desorption equilibria of protons and ions as the cantilever tip approaches the sample. We recorded AFM force distance curves in dynamic mode with sharp tips on heterogeneous silica surfaces partially covered by gibbsite nano-particles immersed in an aqueous electrolyte with variable concentrations of dissolved NaCl and KCl at pH 5.8. Forces are analyzed in the framework of Derjaguin-Landau-Verwey-Overbeek (DLVO) theory in combination with a charge regulation boundary that describes adsorption and desorption reactions of protons and ions. A systematic method to extract the equilibrium constants of these reactions by simultaneous least-squared fitting to experimental data for various salt concentrations is developed and is shown to yield highly consistent results for silica-electrolyte interfaces. For gibbsite-electrolyte interfaces, the surface charge can be determined, yet, an unambiguous identification of the relevant surface speciation reactions is not possible, presumably due to a combination of intrinsic chemical complexity and heterogeneity of the nano-particle surfaces.
The synthesis of cycloarenes in solution is challenging
because
of their low solubility and the often hindered cyclodehydrogenation
reaction of their nonplanar precursors. Using an alternative on-surface
synthesis protocol, we achieved an unprecedented double-stranded hexagonal
cycloarene containing 108 sp2 carbon atoms. Its synthesis
is based on hierarchical Ullmann coupling and cyclodehydrogenation
of a specially designed precursor on a Au(111) surface. The structure
and other properties of the cycloarene are investigated by scanning
tunneling microscopy/spectroscopy, atomic force microscopy, and density
functional theory calculations.
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