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Efficient synthesis of γ-valerolactone from ethyl levulinate via catalytic transfer hydrogenation in supercritical isopropanol over nickel aluminum oxide nanosheets

JOURNAL OF SUPERCRITICAL FLUIDS [2024]
Dongjie Zhang, Yue Zhang, Yifei Li, Zanhong Wang, Yin Zhang, Haitao Li
ABSTRACT

This study reports a novel method for γ-valerolactone (GVL) production from ethyl levulinate (EL) utilizing non-noble metal catalysts within a supercritical isopropanol (IPA) system. Nickel-loaded nickel–aluminum oxide nanosheets (Ni X Al-R) were fabricated via hydrothermal treatment of Ni–Al layered double hydroxide precursors, followed by hydrogen reduction at 550 °C for 1.5 h. Using Ni X Al-R as the catalyst and IPA as the hydrogen donor , we achieved notable results: 82.7% EL conversion, 73.6% GVL yield, and 1.178 mol GVL g −1 h −1 reaction efficiency after 1.5 h in supercritical IPA. The catalytic activity of Ni X Al-R remained stable over five catalytic cycles. The surface of Ni X Al-R exhibits abundant oxygen vacancies and unsaturated Al species (Al x+ ), which promote the initial transfer hydrogenation of EL to form the ethyl 4-hydroxypentanoate (4-HPE) intermediate. Simultaneously, the supercritical IPA environment overcomes mass transfer limitations at the solid–liquid interface between 4-HPE and the catalyst, thereby facilitating the Al x+ -catalyzed intramolecular esterification of 4-HPE into GVL.

MATERIALS

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