No abstract

To optimize the performance of catalytic materials, it is paramount to elucidate the dependence of the chemical reactivity on the atomic arrangement of the catalyst surface. Therefore, identifying the nature...

Surfaces are at the frontier of every known solid. They provide versatile supports for functional nanostructures and mediate essential physicochemical processes. Intimately related to two-dimensional materials, interfaces and atomically thin films often feature distinct electronic states with respect to the bulk, which is key to many relevant properties, such as catalytic activity, interfacial charge-transfer, and crystal growth mechanisms. To induce novel quantum properties via lateral scattering and confinement, reducing the surface electrons' dimensionality and spread with atomic precision is of particular interest. Both atomic manipulation and supramolecular principles provide access to custom-designed molecular assemblies and superlattices, which tailor the surface electronic landscape and influence fundamental chemical and physical properties at the nanoscale. Here the confinement of surface-state electrons is reviewed, with a focus on their interaction with molecular scaffolds created by molecular manipulation and self-assembly protocols under ultrahigh vacuum conditions. Starting with the quasifree twodimensional electron gas present at the ð111Þ-oriented surface planes of noble metals, the intriguing molecule-based structural complexity and versatility is illustrated. Surveyed are low-dimensional confining structures in the form of artificial lattices, molecular nanogratings, or quantum dot arrays, which are constructed upon an appropriate choice of their building constituents. Whenever the realized (metal-)organic networks exhibit long-range order, modified surface band structures with characteristic features emerge, inducing noteworthy physical phenomena such as discretization, quantum coupling or energy, and effective mass renormalization. Such collective electronic states can be additionally modified by positioning guest species at the voids of open nanoarchitectures. The designed scattering potential landscapes can be described with semiempirical models, bringing thus the prospect of total control over surface electron confinement and novel quantum states within reach.

Silicene, the two-dimensional (2D) allotrope of silicon, is a promising material for electronics. So far, the most direct synthesis strategy has been to grow it epitaxially on metal surfaces; however, the effect of the strong silicon-metal interaction on the structure and electronic properties of the metal-supported silicene is generally poorly understood. In this work, we consider the 4×4-silicene monolayer grown on Ag(111), probably the most illustrious representative of the 2D silicon family, and show that our experimental results refute the common interpretation of this system as a simple buckled, honeycomb monolayer with a sharp interface to the Ag substrate. Instead, the presented analysis demonstrates the pervasive presence of a second silicon species, which we conclude to be a Si‑Ag alloy stacked between the 2D silicene and the silver substrate and scaffolding the 2D silicene layer. These findings question the current structural understanding of the silicene/Ag(111) interface and may raise expectations of analogous alloy systems in the stabilization of other 2D materials grown epitaxially on metal surfaces.