Boron is a unique element in terms of electron deficiency and Lewis acidity. Incorporation of boron atoms into an aromatic carbon framework offers a wide variety of functionality. However, the intrinsic instability of organoboron compounds against moisture and oxygen has delayed the development. Here, we present boron-doped graphene nanoribbons (B-GNRs) of widths of N=7, 14 and 21 by on-surface chemical reactions with an employed organoboron precursor. The location of the boron dopant is well defined in the centre of the B-GNR, corresponding to 4.8 atom%, as programmed. The chemical reactivity of B-GNRs is probed by the adsorption of nitric oxide (NO), which is most effectively trapped by the boron sites, demonstrating the Lewis acid character. Structural properties and the chemical nature of the NO-reacted B-GNR are determined by a combination of scanning tunnelling microscopy, high-resolution atomic force microscopy with a CO tip, and density functional and classical computations.

When immersed into water, most solids develop a surface charge, which is neutralized by an accumulation of dissolved counterions at the interface. Although the density distribution of counterions perpendicular to the interface obeys well-established theories, little is known about counterions' lateral organization at the surface of the solid. Here we show, by using atomic force microscopy and computer simulations, that single hydrated metal ions can spontaneously form ordered structures at the surface of homogeneous solids in aqueous solutions. The structures are laterally stabilized only by water molecules with no need for specific interactions between the surface and the ions. The mechanism, studied here for several systems, is controlled by the hydration landscape of both the surface and the adsorbed ions. The existence of discrete ion domains could play an important role in interfacial phenomena such as charge transfer, crystal growth, nanoscale self-assembly and colloidal stability.

Calcite is among the most abundant minerals on earth and plays a central role in many environmental and geochemical processes. Here we used amplitude modulation atomic force microscopy (AFM) operated in a particular regime to visualize single ions close to the (1014) surface of calcite in solution. The results were acquired at equilibrium, in aqueous solution containing different concentrations of NaCl, RbCl, and CaCl(2). The AFM images provide a direct and atomic-level picture of the different cations adsorbed preferentially at certain locations of the calcite-water interface. Highly ordered water layers at the calcite surface prevent the hydrated ions from directly interacting with calcite due to the energy penalty incurred by the necessary restructuring of the ions' solvation shells. Controlled removal of the adsorbed ions from the interface by the AFM tip provides indications about the stability of the adsorption site. The AFM results show the familiar "row pairing" of the carbonate oxygen atoms, with the adsorbed monovalent cations located adjacent to the most prominent oxygen atoms. The location of adsorbed cations near the surface appears better defined for monovalent ions than for Ca(2+), consistent with the idea that Ca(2+) ions remain further away from the surface of calcite due to their larger hydration shell. The precise distance between the different hydrated ions and the surface of calcite is quantified using MD simulation. The preferential adsorption sites found by MD as well as the ion residence times close to the surface support the AFM findings, with Na(+) ions dwelling substantially longer and closer to the calcite surface than Ca(2+). The results also bring new insights into the problem of the Stern and electrostatic double layer at the surface of calcite, showing that parameters such as the thickness of the Stern layer can be highly ion dependent.

Here we present both subnanometer imaging of three-dimensional (3D) hydration structures using atomic force microscopy (AFM) and molecular dynamics simulations of the calcite-water interface. In AFM, by scanning the 3D interfacial space in pure water and recording the force on the tip, a 3D force image can be produced, which can then be directly compared to the simulated 3D water density and forces on a model tip. Analyzing in depth the resemblance between experiment and simulation as a function of the tip-sample distance allowed us to clarify the contrast mechanism in the force images and the reason for their agreement with water density distributions. This work aims to form the theoretical basis for AFM imaging of hydration structures and enables its application to future studies on important interfacial processes at the molecular scale.