Adsorption of perfluoroalkyl substances on deep eutectic solvent-based amorphous metal-organic framework: Structure and mechanism

Abstract

Perfluoroalkyl substances (PFASs) are a class of emerging organic pollutants characterized by high toxicity, environmental persistence, and widespread detection in water sources. The removal of PFASs from water is a matter of global concern, given their detrimental impact on both the environment and public health. Many commonly used PFAS adsorbents demonstrate limited adsorption capacities and/or slow adsorption kinetics. Therefore, there is an urgent need for the development of efficient adsorbents. For the first time, this work systematically investigated the performance of a deep eutectic solvent (DES)-based amorphous metal-organic framework (MOF) for the adsorption of PFASs with different carbon-chain lengths under the state of the mixture in aquatic environments. The adsorption mechanism was probed by a suite of adsorption kinetics studies, adsorption isotherm profiling, spectral characterization, and ab initio molecular dynamics (AIMD) simulations, revealing that PFAS adsorption is driven by synergistic capturing effects including acid/base coordination, CF-π (carbon-fluorine-π), hydrogen bonding, and hydrophobic interactions. Furthermore, the adsorption processes of short-chain and long-chain targets were found to involve different rate-controlling steps and interaction sites. Hydrophobic interactions facilitated the swift arrival of long-chain PFASs at the coordinatively interacting sites between carboxyl termini and Lewis acid Zr unsaturated sites, thanks to their lower reaction barriers. On the other hand, the adsorption of short-chain PFASs primarily relied on a Zr hydroxyl-based ligand exchange force, which would take place at Brønsted acid sites. The existence of massive structural disorder in amorphous UiO-66 led to the development of larger pores, thus improving the accessibility of abundant adsorption sites and facilitating adsorption and diffusion. The presence of multiple types of interactions and flexible structure in defect-rich amorphous UiO-66 significantly increased the exposure of functional groups to the adsorbates. Additionally, this material possessed outstanding regeneration efficiency and outperformed other MOF-based adsorbents with high affinity for targets. It enhances our understanding of the adsorption performances and mechanisms of amorphous materials toward PFASs, thereby paving the way for designing more efficient PFAS adsorbents.