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

• Published in: Advanced materials (Weinheim) 2024-09, Vol.36 (39), p.e2404249-n/a
• Main Authors: Nakanishi, Yusuke, Kanda, Naoyuki, Aizaki, Motoki, Hirata, Kaito, Takahashi, Yasufumi, Endo, Takahiko, Lin, Yung‐Chang, Senga, Ryosuke, Suenaga, Kazu, Aoyagi, Shinobu, Maruyama, Mina, Gao, Yanlin, Okada, Susumu, Miyata, Yasumitsu, Liu, Zheng
• Format: Article
• Language: English
• Subjects: 2D materials; Banded structure; cluster; Clusters; Electronic properties; Electronic structure; Electrons; Functional materials; Hydrogen evolution reactions; Microscopy; Nanoribbons; nanotube; Sandwich structures; Strain; superatomic layer; Transition metals; transmission electron microscopy
• ISSN: 0935-9648; 1521-4095; 1521-4095
• DOI: 10.1002/adma.202404249

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 M4X4 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 M4X4 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 Mo8S8Cl11, a superatomic layer with a sandwich structure consisting of Mo4S4 clusters interconnected through Cl cross‐linking. The vapor‐phase reaction inside nanotubes promotes the selective growth of Mo8S8Cl11 nanoribbons, allowing detailed characterization via transmission electron microscopy. This methodology can be applied to the growth of layered structures containing Mo8S8Cl11 at the micrometer scale. This work has demonstrated that mono‐ and few‐layer Mo8S8Cl11 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. The preparation of Mo8S8Cl11, a superatomic layer with a sandwich structure of cubic Mo4S4 clusters connected by Cl cross‐linking, is reported. This vapor‐phase reaction within nanotubes promotes the selective growth of monolayer Mo8S8Cl11, thereby allowing for comprehensive characterization. This reaction further yields microscopic flakes containing Mo8S8Cl11, which exhibit significant catalytic activity for the hydrogen‐evolution reaction.