When van der Waals Met Kagome: A 2D Antimonide with a Vanadium-Kagome Network.

Abstract

2D materials showcase unconventional properties emerging from quantum confinement effects. In this work, a "soft chemical" route allows for the deintercalation of K+ from the layered antimonide KV6Sb6, resulting in the discovery of a new metastable 2D-Kagome antimonide K0.1(1)V6Sb6 with a van der Waals gap of 3.2 Å. The structure of K0.1(1)V6Sb6 was determined via the synergistic techniques, including X-ray pair distribution function analysis, advanced transmission electron microscopy, and density functional theory calculations. The K0.1(1)V6Sb6 compound crystallizes in the monoclinic space group C2/m (a = 9.57(2) Å, b = 5.502(8) Å, c = 10.23(2) Å, β = 97.6(2)°, Z = 2). The [V6Sb6] layers in K0.1(1)V6Sb6 are retained upon deintercalation and closely resemble the layers in the parent compound, yet deintercalation results in a relative shift of the adjacent [V6Sb6] layers. The magnetic properties of the K0.1(1)V6Sb6 phase in the 2-300 K range are comparable to those of KV6Sb6 and another Kagome antimonide KV3Sb5, consistent with nearly temperature-independent paramagnetism. Electronic band structure calculation suggests a nontrivial band topology with flat bands and opening of band crossing afforded by deintercalation. Transport property measurements reveal a metallic nature for K0.1(1)V6Sb6 and a low thermal conductivity of 0.6 W K-1 m-1 at 300 K. Additionally, ion exchange in KV6Sb6 via a solvothermal route leads to a successful partial exchange of K+ with A+ (A = Na, Rb, and Cs). This study highlights the tunability of the layered structure of the KV6Sb6 compound, providing a rich playground for the realization of new 2D materials.