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【Frontiers in HaiChuan Chemical Technology】Researchers achieved the hydroxycarboxylation of γ-valerolactone with CO₂ and H₂ via cascade catalysis to produce adipic acid

2025-10-22View Original

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Researchers achieved the hydroxycarboxylation of γ-valerolactone with CO₂ and H₂ through tandem catalysis to produce adipic acid. 2025-10-22 15:51:45 Adipic acid is an important industrial chemical, and its production currently relies on fossil resources. Academician Han Buxing and Researcher Qian Qingli from the Institute of Chemistry, Chinese Academy of Sciences, first reported a method for preparing adipic acid by reacting biomass-derived γ-valerolactone (GVL) with CO₂ and H₂. Studies have found that in an acetic acid/water (AcOH/H₂O) binary solvent system, a rhodium (Rh) catalyst promoted by iodine (I₂) can efficiently catalyze this reaction at industrially relevant temperatures (140°C). Through experiments and density functional theory (DFT) calculations, the study conducted a systematic and detailed analysis of the reaction pathways. This tandem one-pot method achieves thermodynamic control by coupling the thermodynamically unfavorable GVL ring-opening reaction with the thermodynamically favorable hydroxycarboxylation reaction, thereby driving the overall reaction toward diacid products. The reaction involves three key steps: first, H₂ reduces CO₂ to carbon monoxide (CO) and water (H₂O) ; Second is the GVL open-loop formation of reaction intermediates ; Third, the intermediate undergoes hydroxycarbonylation with CO and H₂O. A stable GVL can maintain a low concentration of highly reactive intermediates, preventing hydrogenation side reactions and thus facilitating high selectivity in the formation of diacid products. Furthermore, this strategy allows for the preparation of various diacids from different lactones with high yields, the yield of the diacid products reaching up to 89%. This method opens up a new pathway for the sustainable synthesis of adipic acid by utilizing two renewable carbon sources and a green reducing agent (H₂). This research work, titled “Tandem Catalysis Enables the Hydrocarboxylation of γ-Valerolactone with CO2 and H2 to Produce Adipic Acid,” was published in the Journal of the American Chemical Society.
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