Local-Global Synergistic Pore Space Partition in Metal-Organic Frameworks for Boosting CO2 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.