Abstract
Citrus oils are widely used in the pharmaceutical and food industries, accounting for 30% of the global essential oils market. Deterpenation, separation between high-value oxyterpenes (5 wt%) and terpenes, is crucial for obtaining higher quality citrus oils and high-purity limonene, a major terpene pharmaceutical intermediate. Despite various treatments, achieving sustainable, mild, yet efficient deterpenation remains challenging because of their structural and property similarities. We designed a hybrid porous aromatic framework (PAF) by integrating lactic acid-based deep eutectic solvents (LaDESs) as functionalized sites. Compared to available adsorbents, PAF functionalized by LaDES (LaDES@PAF) can realize oxyterpenes adsorption gently without citrus oils dilution by volatile solution. Moreover, it exhibited 91.20% citral adsorption efficiency and 13.60 citral selectivity over limonene, an 11-fold selectivity improvement. Finally, 96.38 wt% pure limonene and high-value citrus oil containing 80 wt% oxyterpenes were achieved. Modeling studies revealed the strong induction effect of LaDESs improved H-bonds between citral and the framework, facilitating citral adsorption. Our findings highlight that LaDES@PAF can serve as a competitive deterpenation medium, establishing PAFs as promising platforms for addressing complex separations in the natural essential oil industry.
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