Metal-organic frameworks (MOFs), synthesized by the self-assembly of organic ligands and metal centers, are structurally designable materials. In the current study, first-principles calculation based on density functional theory (DFT) was performed to investigate the intrinsic mechanical and electrical properties and mechanical-electrical coupling behavior of MOF-5. To improve the conductivity of MOF-5, homologous elements of Cu, Ag, and Au were adopted to replace the Zn atom in MOF-5, reducing the band gap and improving its electrical performance. Cu-MOF-5 and Au-MOF-5, with stable structures, exhibit better conductivity. The intrinsic mechanical properties such as independent elastic constants of MOF-5 and M-MOF-5 (M = Cu, Ag, Au) were obtained. MOF-5 and Cu-MOF-5 were experimentally synthesized to demonstrate the reduction in the band gap after metal substitution. The study of the strain effect of MOF-5 and Cu-MOF-5 proves that strain engineering is an effective method to regulate the band gap and this modulation is repeatable. This study clarifies the tunability of the band gap of MOF-5 with metal substituents and provides an efficient strategy for the development of new types of MOFs with desired physical properties using the combination of theoretical prediction and experimental synthesis and validation.
Keywords: electrical property; first-principles calculation; mechanical property; metal substitution; metal−organic frameworks; strain engineering.