摘要
Hydrophobic DES integrates CO 2 cycloaddition and catalyst recycling. • Polarity evolution drives aqueous extraction of carbonate products. • Water extraction gives 93% recovery and > 97% yield over five cycles. • DFT reveals a water-tolerant decanol-assisted ring-opening pathway. • Catalyst-as-raffinate design enables reaction–separation integration. Homogeneous catalysts offer high activity for CO 2 fixation, yet their separation from polar carbonate products remains a persistent barrier to catalyst recycling. Here, we report an integrated catalysis–separation system based on a catalyst-as-raffinate strategy, exploiting the polarity increase inherent to the CO 2 cycloaddition of epoxides. A hydrophobic deep eutectic solvent composed of trioctylmethylammonium bromide and decanol was constructed as both the catalytic medium and the recyclable low-polarity raffinate phase. During the conversion of glycidol to glycerol carbonate, the reaction-induced polarity shift promotes product partitioning into water during extraction, while retaining the catalyst in the hydrophobic phase. Product extraction reached 93%, and the recovered catalyst maintained glycerol carbonate yields above 97% over five consecutive catalytic–extraction cycles. DFT and energy-decomposition analyses show that residual water is thermodynamically accommodated within the hydrogen-bonding catalytic network, whereas the decanol-assisted ring-opening pathway remains kinetically favored by avoiding excessive exchange repulsion in the rate-determining transition state. These features enable stable catalytic performance during aqueous recycling. Across different epoxides, extraction efficiency correlates with the product–DES polarity difference. This work establishes reaction-induced polarity evolution as a design principle for coupling homogeneous catalysis with product separation and catalyst recycling. Download: Download high-res image (101KB) Download: Download full-size image
危险品化学品经营许可证（带存储）