Isoreticular Tolerance and Phase Selection in the Synthesis of Multi-Module Metal–Organic Frameworks for Gas Separation and Electrocatalytic OER

Abstract

Although metal–organic frameworks are coordination-driven assemblies, the structural prediction and design using metal-ligand interactions can be unreliable due to other competing interactions. Leveraging non-coordination interactions to develop porous assemblies could enable new materials and applications. Here, we use a multi-module MOF system to explore important and pervasive impact of ligand-ligand interactions on metal-ligand as well as ligand-ligand co-assembly process. It is found that ligand-ligand interactions play critical roles on the scope or breakdown of isoreticular chemistry. With cooperative di- and tri-topic ligands, a family of Ni-MOFs has been synthesized in various structure types including partitioned MIL-88-acs (pacs), interrupted pacs (i-pacs), and UMCM-1-muo. A new type of isoreticular chemistry on the muo platform is established between two drastically different chemical systems. The gas sorption and electrocatalytic studies were performed that reveal excellent performance such as high C₂H₂/CO₂ selectivity of 21.8 and high C₂H₂ uptake capacity of 114.5 cm³/g at 298 K and 1 bar.