Two-dimensional multifunctional metal–organic frameworks with large in-plane negative Poisson ratios and photocatalytic water splitting properties

Abstract

Auxetic materials with multifunctional properties are highly sought after for application in modern nano-devices. However, the majority of reported inorganic auxetic materials exhibit low negative Poisson's ratios (NPR), poor flexibility, and limited functionality. In this study, we employ density-functional-theory (DFT) first-principles simulations to design a series of two-dimensional (2D) metal–organic frameworks (MOFs) M₂C₄X₄ (M = Cu, Ag, Au; X = O, S, NCN) that display intriguing auxetic behavior, superior flexibility and appropriate photocatalytic water-splitting properties. These M₂C₄X₄ MOFs are assembled from carbon tetragon motifs and exist in both cis- and trans-isomer forms, with the NPR ranging from −0.17 to −0.90. Notably, trans-Cu₂C₄(NCN)₄ exhibits a high NPR of −0.90, while cis-Cu₂C₄(NCN)₄ achieves an NPR of −0.67. Both isomers demonstrate excellent flexibility, characterized by ultra-low Young's modulus and high fracture strengths. Furthermore, their direct band gaps, strong light-harvesting capabilities, and long excited-state lifetimes make them promising candidates for the photocatalytic oxygen evolution reaction in water. These results provide a viable strategy for the design and synthesis of novel optoelectronic multifunctional materials.