Simultaneous size and defect control of metal-organic framework by deep eutectic solvent for efficient perfluoroalkyl substances adsorption: Delving into mechanism

This study reports an environment-friendly protocol to prepare a metal-organic framework (MOF) with simultaneously controlled particle size and open metal site for adsorption removal of perfluoroalkyl substances (PFASs). The successful preparation of UiO-66 with defect and crystal size modulation was achieved using a green and straightforward method, adjusting the components and molar ratios of ammonium salt/glycolic acid deep eutectic solvents (DESs). The corresponding modulation mechanism primarily relied on the combined regulation of the deprotonation and competitive coordination abilities of the eutectic solvent components. The adsorption process was thoroughly examined using spectral analyses, adsorption behavior profiling, and ab initio molecular dynamics simulations. The results revealed that PFAS adsorption is driven by combined capturing effects, such as CF-π, acid/base coordination, C-F···Zr, hydrogen bonding, and hydrophobic interactions. Our findings were not thus that the smaller the crystal size of MOF and the higher the defect concentration in the material, the better the PFAS adsorption performance. The result demonstrated the combined effect of these adsorbent features on PFAS mixtures. Furthermore, they revealed unique differences in sorption properties between these targets with different carbon chain lengths. Extensive defects in DES-based UiO-66 led to larger pores, increasing the availability of many adsorption sites and aiding in PFAS adsorption and diffusion. Nevertheless, the surplus of larger pores in the substance increased the competitive adsorption, reducing the total quantity of PFASs absorbed. Furthermore, various interactions and a less restrictive configuration increased the contact of functional groups with adsorbates, substantially enhancing the adsorption. This study investigates the basic questions about how PFAS molecules are adsorbed on DES-based MOFs and the relationship among the structure, properties, and performance to improve the efficiency of this novel adsorbent.