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Synthesis of γ-Valerolactone from Levulinic Acid with Co/NC, and from Furfural via Cascade Reaction Using Co/NC and H-Beta
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    Synthesis of γ-Valerolactone from Levulinic Acid with Co/NC, and from Furfural via Cascade Reaction Using Co/NC and H-Beta
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    Energy & Fuels

    Cite this: Energy Fuels 2024, 38, 7, 5998–6011
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    https://doi.org/10.1021/acs.energyfuels.3c04228
    Published January 25, 2024
    Copyright © 2024 American Chemical Society

    Abstract

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    γ-Valerolactone (GVL) has transpired as an ecofriendly solvent, a promising fuel additive, and a precursor to valuable chemicals. The study explores an approach to GVL synthesis by employing non-noble metals in contrast to conventional methods involving noble metals. The selective hydrogenation of levulinic acid (LA) and levulinate esters offers a pathway to GVL production, while the direct transformation from furfural (FA) enhances its potential. The study focuses on 3d transition metal-based N-doped carbon catalysts, highlighting Co/NC as the most effective catalyst for LA to GVL hydrogenation, yielding ∼100% GVL. The catalyst was also employed in a one-pot, three-step cascade reaction: FA hydrogenation to furfuryl alcohol (FOL) was performed using 10% Co/NC, ethanolysis of FOL to ethyl levulinate (EL) was facilitated by H-β, and EL hydrogenation to GVL was performed using 10% Co/NC. Each step was optimized independently. The cascade reaction was executed at 140 °C for 12 h through a comprehensive approach, achieving a noteworthy 92.1% GVL yield from FA, which was further upcycled to the gram scale, offering 86% of the final GVL yield. The catalyst characterization, catalytic activity data, and control experiments culminate in the proposed LA to GVL transformation mechanisms and the one-pot, three-step cascade FA to GVL conversion. The research significantly contributes to advancing sustainable GVL production and its multifaceted applications.

    Copyright © 2024 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.energyfuels.3c04228.

    • Electronic Supporting Information (ESI) contains all the detailed experimental procedures, detailed synthesis, and characterization of catalysts, the procedure of the catalytic reactions, N2 adsorption profiles, H2, and CO2 temperature-programmed desorption profiles of x% Co/NC catalysts, NH3-TPD of H-beta, TGA, solvent studies, optimization and kinetics, recyclability, and complete characterizations of the recycled catalyst. (PDF)

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    Energy & Fuels

    Cite this: Energy Fuels 2024, 38, 7, 5998–6011
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.energyfuels.3c04228
    Published January 25, 2024
    Copyright © 2024 American Chemical Society

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