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Decoding Solvent Effects in Electrocatalytic Biomass Valorization: Levulinic Acid to γ‑Valerolactone.

Pol Vilariño1,2, Queralt Bautista1,2, Elvira Gómez1,2

  • 1Grup d'Electrodeposició de Capes Primes i Nanoestructures (GE-CPN), Departament de Ciència de Materials i Química Física, Universitat de Barcelona, Martí i Franquès, 1, E-08028 Barcelona, Catalonia, Spain.

ACS Sustainable Chemistry & Engineering
|June 1, 2026
PubMed
Summary

Solvent choice and temperature are key for efficiently converting levulinic acid (LA) to gamma-valerolactone (GVL) via electrocatalytic hydrogenation (ECH). Higher temperatures and methanol unlock high GVL yields, crucial for green chemistry applications.

Keywords:
Biomass valorizationCopper−nickel catalystsElectrocatalytic hydrogenationGreen chemistrySolvent effects

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Published on: January 7, 2019

Area of Science:

  • Green Chemistry and Catalysis
  • Electrochemical Engineering
  • Biomass Conversion

Background:

  • Electrocatalytic hydrogenation (ECH) of levulinic acid (LA) is a sustainable pathway to gamma-valerolactone (GVL), a valuable green solvent and fuel additive.
  • Existing research often overlooks the critical influence of solvent choice on reaction outcomes, conflating substrate conversion with actual product yield.

Purpose of the Study:

  • To systematically investigate the role of different solvent environments and temperatures in the ECH of LA to GVL.
  • To decouple the effects of solvent properties and temperature on LA conversion and GVL selectivity.
  • To establish design principles for optimizing GVL production via ECH.

Main Methods:

  • Electrocatalytic hydrogenation of LA using various metal cathodes (GC, Cu, Ni, CuNi).
  • Experiments conducted in three distinct solvents (methanol, DMSO, IPA) at two temperatures (15 °C and 35 °C).
  • Analysis of solvent properties (viscosity, dielectric constant, ionic conductivity) and computational modeling (DFT).

Main Results:

  • Solvent choice significantly impacts the maximum achievable LA conversion, while temperature governs selectivity towards GVL.
  • At 15 °C, LA conversion occurs, but lactonization to GVL is suppressed. At 35 °C, GVL selectivity exceeds 90% in methanol, particularly with Ni-based catalysts.
  • Methanol proved most effective due to low viscosity and high ionic conductivity, minimizing diffusion and ohmic losses. DMSO showed intermediate performance, while IPA yielded the lowest conversions.

Conclusions:

  • Efficient LA-to-GVL ECH requires a synergistic interplay between catalyst, solvent properties, and temperature.
  • Optimizing GVL production necessitates careful consideration of solvent effects on mass transport and reaction kinetics, alongside temperature control for thermally assisted lactonization.
  • This study provides a clear design rule for maximizing GVL yield in ECH processes, emphasizing solvent and temperature optimization over mere conversion.