It is challenging but desirable to synthesize hierarchically porous MOFs (HP-MOFs) with well-defined topology. Herein, a series of HP-Zr-MOFs (H-UiO-66-X) with different topologies were synthesized through an in situ self-assembly template strategy. Further, H₃PMo₁₂O₄₀ (PMA) was dispersed within H-UiO-66-X to illustrate the confinement effect of HP-MOFs on PMA as ultra-efficient ODS catalysts. Potentiometric acid–base titration is used to evaluate three typical types of Brønsted acid protons (μ₃–OH, Zr-OH₂, and Zr-OH) presented in the nodes of defect HP-MOFs according to their different pKa values (∼3, ∼6 and ∼8). By quantifying the amount of defect sites (Zr-OH₂ and Zr-OH) resulting from either missing Zr₆O₈ clusters or missing linkers in the HP-MOFs, the information about the true topology of HP-MOFs is provided. The Zr-OH₂ defects are correlated to missing Zr₆O₈ cluster and the Zr-OH defects are related to missing linkers. The loaded PMA molecules mainly occupy the Zr-OH₂ defect sites by the substitution of H₂O molecules and still maintain the Keggin structure. The results give deep insight on the structure-activity relationship for PMA confined in HP-Zr-MOFs with clear topologies.

合成具有明确定义的拓扑结构的分层多孔 MOF (HP-MOF) 具有挑战性，但也是可取的。在此，通过原位自组装模板策略合成了一系列具有不同拓扑结构的 HP-Zr-MOFs (H-UiO-66-X) 。此外，H ₃ PMo ₁₂ O ₄₀ (PMA) 分散在 H-UiO-66-X 中，以说明 HP-MOF 作为超高效 ODS 催化剂对 PMA 的限制作用。_电位酸碱滴定用于根据不同的 pKa 值₍ ∼3 , ~6 和 ~8). 通过量化缺陷位点的数量（Zr-OH ₂和 Zr-OH) 由于 HP-MOF 中缺少 Zr ₆ O ₈簇或缺少连接基而导致，提供了有关 HP-MOF 真实拓扑结构的信息。Zr-OH _{2缺陷与缺失的Zr 6} O ₈簇相关，而Zr-OH 缺陷与缺失的接头相关。_{负载的PMA分子主要通过H 2} O分子的取代占据Zr-OH ₂缺陷位点，仍然保持Keggin结构。该结果对限制在具有清晰拓扑结构的 HP-Zr-MOF 中的 PMA 的构效关系提供了深入的了解。