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 (psit-d, psit-d/u, psit-u, psit-i, psit-d-i, and psit-u-i) derived from merely one parent sit 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.