Multicriteria design of novel natural hydrophobic deep eutectic solvents for the extraction of perfluoroalkyl acids using COSMO-RS

[Display omitted] •COSMO-RS screening of 129 HDES constituents for PFOA/PFOS extraction.•Identification of 55 novel constituents from essential oils and plants.•Top constituents found to be primarily from terpene and terpenoid family.•Toxicity analysis and multicriteria evaluation for sustainable LLE process.•Reported framework can be considered as a robust selection tool. In this study, a molecular modeling approach was used to identify the most effective natural hydrophobic deep eutectic solvents (HDESs) for extracting the emerging pollutants, perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) from synthetic wastewater. The use of HDESs for this purpose has not been reported in the literature, making this a pioneering contribution to the field. First, an extensive literature search was conducted to generate a list of 74 non-ionic HDES constituents. In the second step, a systematic screening of natural components was conducted to identify 55 new compounds that can be used for the synthesis of HDESs. The Conductor-like Screening Model for Real Solvents (COSMO-RS) was then used to screen the 129 potential HDES constituents based on three key performance indicators: distribution ratio, selectivity, and performance index at infinite dilution compared to the predicted performance of toluene as a benchmark, as the use of molecular solvents or DESs for this purpose has never been reported in the literature. The top 20 HDES constituents with the highest extraction performance were predominantly from the terpene and terpenoid families. The median lethal dose was also used to analyze toxicity. A multicriteria evaluation approach was adopted to evaluate several properties important to liquid–liquid extraction (LLE) processes, including the extraction performance, density, vapor pressure, water solubility, and leachability of DESs. Three HDESs, namely, trioctylphosphine oxide: 2-methylbenzothiazole (1:9), trioctylphosphine oxide: menthyl acetate (1:4), and 1,8-cineole: menthyl acetate (2.5:1), showed promising results. This study provides molecular insights on extracting PFOA/PFOS from wastewater using HDESs and emphasizes the need to evaluate LLE units using multicriteria. In addition, the results may serve as a starting point for further research, including the synthesis and characterization of novel HDES constituents and the development of optimized HDESs for the extraction of PFOA/PFOS from wastewater.