Unpromoted copper supported mesoporous silica nanocatalysts for the selective hydrogenation of biomass-derived levulinic acid to γ-valerolactone

Levulinic acid (LA), derived from lignocellulosic biomass, is an important platform molecule for the production of renewable fuels and value-added chemicals. Its catalytic hydrogenation to γ-valerolactone (GVL), a bio-based compound with applications as a fuel additive, solvent, and precursor to valeric biofuels, represents a promising route for upgrading biomass-derived feedstocks. In this work, we investigate the structure–activity–stability relationships of unpromoted, high-loading (10 wt%) Cu/SBA-15 catalysts prepared by incipient wetness impregnation, glycine-assisted auto-combustion, and deposition–precipitation, respectively. Quantitative N 2 O chemisorption shows that the preparation method strongly affects copper dispersion (9.3–56.5%) and active Cu surface area (5.9–32.5 m 2 Cu g cat −1 ), which correlate with LA-to-GVL hydrogenation productivity (0.26–5.93 h −1 at 150 °C and 30 bar H 2 ). XRD, XPS, and Cu LMM Auger spectroscopy reveal differences in copper reduction and surface speciation, indicating that the Cu 0 /Cu + balance is a contributing factor to the observed GVL selectivity. HAADF-STEM confirms that the deposition–precipitation method produces finely dispersed Cu nanoparticles with sizes below 5 nm within the SBA-15 mesopores. The optimized unpromoted catalyst achieves a GVL productivity of 25.60 h −1 at 175 °C and 30 bar H 2 , which, to the best of our knowledge, is the highest reported for Cu-based catalysts in liquid-phase LA hydrogenation. The catalysts also exhibit good structural and catalytic stability upon recycling, with low Cu leaching (<2 ppm), limited particle growth, and no evidence of severe surface deactivation. Overall, the results demonstrate the potential of unpromoted Cu/SBA-15 catalysts for the efficient conversion of levulinic acid to γ-valerolactone and provide practical guidelines for developing stable, earth-abundant catalysts for biomass valorization.

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Journal
Biomass and Bioenergy
Published
2026-10-14
DOI
https://doi.org/10.1016/j.biombioe.2026.110185
Primary Topic
Catalysis for Biomass Conversion
Type
article
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article

Unpromoted copper supported mesoporous silica nanocatalysts for the selective hydrogenation of biomass-derived levulinic acid to γ-valerolactone

Cédric Gennequin, Cezar Catrinescu, Adrian Ungureanu, Sébastien Royer et al.
Biomass and Bioenergy
Catalysis for Biomass Conversion
article

Unpromoted copper supported mesoporous silica nanocatalysts for the selective hydrogenation of biomass-derived levulinic acid to γ-valerolactone

Cédric Gennequin, Cezar Catrinescu, Adrian Ungureanu, Sébastien Royer, Carmen Ciotonea, Mihaela Bectoraș
article en

Abstract

Levulinic acid (LA), derived from lignocellulosic biomass, is an important platform molecule for the production of renewable fuels and value-added chemicals. Its catalytic hydrogenation to γ-valerolactone (GVL), a bio-based compound with applications as a fuel additive, solvent, and precursor to valeric biofuels, represents a promising route for upgrading biomass-derived feedstocks. In this work, we investigate the structure–activity–stability relationships of unpromoted, high-loading (10 wt%) Cu/SBA-15 catalysts prepared by incipient wetness impregnation, glycine-assisted auto-combustion, and deposition–precipitation, respectively. Quantitative N 2 O chemisorption shows that the preparation method strongly affects copper dispersion (9.3–56.5%) and active Cu surface area (5.9–32.5 m 2 Cu g cat −1 ), which correlate with LA-to-GVL hydrogenation productivity (0.26–5.93 h −1 at 150 °C and 30 bar H 2 ). XRD, XPS, and Cu LMM Auger spectroscopy reveal differences in copper reduction and surface speciation, indicating that the Cu 0 /Cu + balance is a contributing factor to the observed GVL selectivity. HAADF-STEM confirms that the deposition–precipitation method produces finely dispersed Cu nanoparticles with sizes below 5 nm within the SBA-15 mesopores. The optimized unpromoted catalyst achieves a GVL productivity of 25.60 h −1 at 175 °C and 30 bar H 2 , which, to the best of our knowledge, is the highest reported for Cu-based catalysts in liquid-phase LA hydrogenation. The catalysts also exhibit good structural and catalytic stability upon recycling, with low Cu leaching (<2 ppm), limited particle growth, and no evidence of severe surface deactivation. Overall, the results demonstrate the potential of unpromoted Cu/SBA-15 catalysts for the efficient conversion of levulinic acid to γ-valerolactone and provide practical guidelines for developing stable, earth-abundant catalysts for biomass valorization.

Biomass and BioenergyVol. 217
Université du littoral côte d'opale (FR), Gheorghe Asachi Technical University of Iași (RO)
Ministry of Education and Research, Romania
Affordable and clean energy
Openalex Percentile: Top 25%
Catalysis for Biomass Conversion
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