Noncovalent chemistry of xenon opens the door for anesthetic xenon recovery using Bio-MOFs

Abstract

Designing an inexpensive and highly efficient recovery process for xenon (Xe) is gaining importance in the development of sustainable applications. Using metal organic frameworks (MOFs) for separating Xe from anesthetic gas mixtures has been a recent topic studied rarely and superficially in the literature. We theoretically investigated Xe recovery performances of 43 biological MOFs (Bio-MOFs) formed by biocompatible metal cations and biological endogenous linkers. Xe uptakes and Xe permeabilities in its binary mixtures with CO₂, O₂, and N₂ were investigated by applying Grand Canonical Monte Carlo and Molecular Dynamics simulations. Materials with metalloporphyrin, hexacarboxylate, triazine, or pyrazole ligands, dimetallic paddlewheel units, relatively large pore sizes (PLD > 5 Å and LCD > 10 Å), large void fractions (≈0.8), and large surface areas (>2900 m² g⁻¹) have been determined as top performing Bio-MOFs for Xe recovery. By applying Density Functional Theory simulations and generating electron density difference maps, we determined that Xe-host interactions in the top performing Bio-MOFs are maximized mainly due to noncovalent interactions of Xe, such as charge-induced dipole and aerogen–π interactions. Polarized Xe atoms in the vicinity of cations/anions as well as π systems are fingerprints of enhanced guest–host interactions. Our results show examples of rarely studied aerogen interactions that play a critical role in selective adsorption of Xe in nanoporous materials.