Synchronous Construction of the Hierarchical Pores and High Hydrophobicity of Stable Metal-Organic Frameworks through a Dual Coordination-Competitive Strategy

Hierarchical-pore construction and functionalities are critical to further extend the applications of some stable MOFs, such as water remediation, fuel purification, oil/water separation, and self-cleaning, which are rarely achieved simultaneously. Herein, we demonstrate a method of synchronously constructing high-hydrophobicity Zr-based metal-organic frameworks with hierarchical pores (HP-UiO-66) through a dual coordination-competitive strategy. The addition of alkanoic acids and Zn²⁺ ions as coordination-competitors could reduce the coordinative degree between the ligand and Zr⁴⁺ ions to effectively induce defect formation. The resulting unsaturated Zr⁴⁺ ions could fully combine with the existing alkanoic acid with a long chain to afford HP-UiO-66 with high-hydrophobicity characteristics. In addition, the particle size of pristine UiO-66 could be adjusted effectively from around 280 to 120 nm using different alkanoic acids when Zn²⁺ ions are not added. This study provided a simple way for effectively controlling the morphology and structure of UiO-66 at the same time. Moreover, this kind of high-hydrophobicity HP-UiO-66 showed potential applications in oil/water separation and selective adsorption of organic mixtures.