Local-Global Synergistic Pore Space Partition in Metal–Organic Frameworks for Boosting CO ₂ Capture and Conversion

How to rationally maximize host-guest interactions or the density of binding sites within metal-organic framework (MOF) pores is critical to their promising adsorption and catalysis performance but still challenging. In this work, a local-global synergistic pore space partition (LGS-PSP) strategy is proposed to integrate ligand-mediated local partition with interpenetration-driven global partition, enabling precise design and efficient utilization of MOF pore space. Forty-four MOF examples featuring six types of pore-space partitioned modes (<i><b>psit-d</b></i>, <i><b>psit-d/u</b></i>, <i><b>psit-u</b></i>, <i><b>psit-i</b></i>, <i><b>psit-d-i</b></i>, and <i><b>psit-u-i</b></i>) derived from merely one parent <i><b>sit</b></i> framework, along with their tunable and boosting CO₂ adsorption and photocatalytic ability, clearly demonstrate the power of the LGS-PSP strategy. Detailed single-crystal structure analysis indicates that the translation/rotation of ligands and frameworks can dynamically regulate the microenvironment of the local pores and the interpenetration mode of the global network, realizing a dynamic and controllable alignment of local and global pore engineering with the pore environment. Remarkably, the dual-partitioned SNNU-196-Ni MOF with ultramicropores and uniformly dispersed Lewis-basic and acidic sites promoted the CO₂ adsorption capacity by 206%, and the photocatalytic conversion efficiency in the carboxylation cyclization of propargylic amines and CO₂ was nearly 100% under visible light irradiation.