Continuous flow (Sulfated) Zirconia Catalysed Cascade Conversion of Levulinic Acid to γ‐Valerolactone

Andrea Merenda, Samantha Alana Orr, Yang Liu, Blanca Hernández Garcia, Amin Osatiashtiani, Gabriel Morales, Marta Paniagua, Juan Antonio Melero, Adam Fraser Lee*, Karen Wilson*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


γ-Valerolactone (GVL) is a renewable and versatile platform chemical derived from sustainable carbon feedstocks. The cascade conversion of levulinic acid into GVL requires Brønsted and Lewis acid catalysed reactions. Here, a dual-catalyst bed configuration is demonstrated that promotes synergy between Brønsted acid sites in sulfated zirconia (SZ) and Lewis acid sites in ZrO 2/SBA-15 for the liquid phase, continuous flow esterification and subsequent catalytic transfer hydrogenation (CTH) of levulinic acid to GVL. A saturated surface sulfate monolayer, possessing a high density of strong Brønsted acid sites, was optimal for levulinic acid esterification to isopropyl levulinate over SZ (>80 % conversion). A conformal ZrO 2 bilayer, deposited over a SBA-15 mesoporous silica and possessing mixed Brønsted:Lewis acidity, catalysed CTH of the levulinate ester and subsequent dealcoholisation/cyclisation to GVL (>60 % selectivity). Maximum stable productivity for the dual-bed was 2.2 mmol GVL.g cat.h −1 at 150 °C, significantly outperforming either catalyst alone or a physical mixture of both. Flow chemistry is a versatile approach to achieve spatial control over cascade transformations involving distinct catalytically active sites.

Original languageEnglish
Early online date19 Dec 2022
Publication statusE-pub ahead of print - 19 Dec 2022

Bibliographical note

Copyright © 2022, The Authors. ChemCatChem published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License [], which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

Funding Information:
The authors thank the Australian Research Council for financial support (DP200100204, DP200100313 and LE210100100), and Luxfer MEL Technologies for providing materials. Open Access publishing facilitated by RMIT University, as part of the Wiley ‐ RMIT University agreement via the Council of Australian University Librarians.


  • catalytic transfer hydrogenation
  • continuous flow reaction
  • dual-bed cascade
  • sulfated zirconia
  • γ-valerolactone


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