Superatomic Layer of Cubic Mo₄S₄ Clusters Connected by Cl Cross-Linking

Area of Science:

• Materials Science
• Nanotechnology
• Solid-State Chemistry

Background:

• Superatomic clusters offer emergent electronic properties in hierarchical architectures.
• Cubic M4X4 clusters are building blocks for 3D structures, but tetrahedral clusters rarely form 2D materials.
• 2D materials offer distinct properties compared to their 3D counterparts.

Purpose of the Study:

• To report the preparation of a novel 2D Mo8S8Cl11 superatomic layer.
• To explore the synthesis and characterization of layered Mo8S8Cl11 structures.
• To investigate the electronic and catalytic properties of 2D Mo8S8Cl11.

Main Methods:

• Vapor-phase reaction within nanotubes for selective nanoribbon growth.
• Transmission electron microscopy for detailed characterization.
• Exfoliation of parent solids to obtain mono- and few-layer Mo8S8Cl11.
• Electronic structure calculations.
• Scanning electrochemical microscopy.

Main Results:

• Successful preparation of 2D Mo8S8Cl11 with a sandwich structure of Mo4S4 clusters linked by Cl.
• Growth of Mo8S8Cl11 nanoribbons and micrometer-scale layered structures.
• Demonstration of mono- and few-layer Mo8S8Cl11 via exfoliation.
• Identification of quasi-flat bands in the 2D monolayer, enabling a strain-induced indirect-to-direct bandgap transition.
• Observation of high catalytic efficiency for the hydrogen-evolution reaction.

Conclusions:

• 2D Mo8S8Cl11 represents a new class of layered superatomic materials.
• The synthesis methodology allows for controlled growth of layered structures.
• The unique electronic and catalytic properties position Mo8S8Cl11 for advanced applications, particularly in catalysis.