Tuning the Functionalities of Porous Liquids for Emergent Gas-Capture Properties

Type 3 Porous Liquids (PLs) are a class of materials with the potential to revolutionize gas capture, storage, and utilization. These PLs are formed by suspending sorbent nanoparticles (e.g., metal-organic frameworks) in sterically excluded solvents, creating permanent porosity for gas capture in a processable, low-viscosity phase. Herein, a computational study revealed sorbent surface functionalization strategies to enhance CO₂ sorption, and the molecular structural signatures underpinning the enhancements in gas uptake. PLs composed of a ZIF-8 surface functionalized with 3-amino-1,2,4-triazole (Atz) in glyceryl triacetate were targeted for emergent CO₂ capture, exceeding that of the unfunctionalized ZIF-8 PL. ZIF-8 was surface functionalized with Atz at various surface coverage fractions (<i>f</i>), and classical molecular dynamics simulations predicted an increase in CO₂ sorption capacity with increasing <i>f</i>, up to <i>f</i> = 0.75. Detailed structural analyses revealed that solvent orientational order, derived from the solvent triplet-angle distribution, can identify the gas-capture potential of a PL without requiring computationally expensive direct modeling of the CO₂ sorption. Combined with experimental validation, initial computational screening of PL compositions promises to accelerate the discovery of PL compositions for novel gas separation materials platforms.