Superatomic Layer of Cubic Mo 4 S 4 Clusters Connected by Cl Cross-Linking.

Superatomic clusters - assemblies of atoms with various sizes, shapes, and compositions - can form hierarchical architectures that exhibit emergent electronic properties not found in their individual units. In particular, cubic M 4 X 4 clusters of chalcogenides (M = transition metal; X = chalcogen) are recognized as versatile building blocks for 3D structures with tunable morphologies and electronic properties. However, tetrahedral M 4 X 4 clusters rarely assemble into 2D architectures, which could offer a distinct class of functional materials from their 3D analogues. Here, this work reports the preparation of 2D Mo 8 S 8 Cl 11 , a superatomic layer with a sandwich structure consisting of Mo 4 S 4 clusters interconnected through Cl cross-linking. The vapor-phase reaction inside nanotubes promotes the selective growth of Mo 8 S 8 Cl 11 nanoribbons, allowing detailed characterization via transmission electron microscopy. This methodology can be applied to the growth of layered structures containing Mo 8 S 8 Cl 11 at the micrometer scale. This work has demonstrated that mono- and few-layer Mo 8 S 8 Cl 11 can be prepared by exfoliation of parent solids. Electronic structure calculations indicate that the 2D monolayer has quasi-flat bands, giving rise to an indirect-to-direct bandgap transition under mechanical strain. Furthermore, scanning electrochemical microscopy reveals the potential of the layered structures as highly efficient catalysts for the hydrogen-evolution reaction.