Transforming Metal–Organic Frameworks into Porous Liquids via a Covalent Linkage Strategy for CO₂ Capture

Porous liquids (PLs), an emerging kind of liquid materials with permanent porosity, have attracted increasing attention in gas capture. However, directly turning metal-organic frameworks (MOFs) into PLs via a covalent linkage surface engineering strategy has not been reported. Additionally, challenges including reducing the cost and simplifying the preparation process are daunting. Herein, we proposed a general method to transform Universitetet i Oslo (UiO)-66-OH MOFs into PLs by surface engineering with organosilane (OS) and oligomer species via covalent bonding linkage. The oligomer species endow UiO-66-OH with superior fluidity at room temperature. Meanwhile, the resulting PLs showed great potential in both CO₂ adsorption and CO₂/N₂ selective separation. The residual porosity of PLs was verified by diverse characterizations and molecular simulations. Besides, CO₂ selective capture sites were determined by grand canonical Monte Carlo (GCMC) simulation. Furthermore, the universality of the covalent linkage surface engineering strategy was confirmed using different classes of oligomer species and another MOF (ZIF-8-bearing amino groups). Notably, this strategy can be extended to construct other PLs by taking advantages of the rich library of oligomer species, thus making PLs promising candidates for further applications in energy and environment-related fields, such as gas capture, separation, and catalysis.