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

doi:10.1002/cctc.202201224

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 journal › Article › peer-review

Abstract

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 language	English
Journal	ChemCatChem
Early online date	19 Dec 2022
DOIs	https://doi.org/10.1002/cctc.202201224
Publication status	E-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 [https://creativecommons.org/licenses/by-nc/4.0/], 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.

Keywords

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

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10.1002/cctc.202201224

Merenda et al ChemCatChem VOR - Continuous flow Sulfated Zirconia Catalysed Cascade Conversion of Levulinic Acid
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 [https://creativecommons.org/licenses/by-nc/4.0/], which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
Final published version, 1.83 MBLicence: CC BY-NC 4.0

Cite this

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

abstract = "γ-Valerolactone (GVL) is a renewable and versatile platform chemical derived from sustainable carbon feedstocks. The cascade conversion of levulinic acid into GVL requires Br{\o}nsted and Lewis acid catalysed reactions. Here, a dual-catalyst bed configuration is demonstrated that promotes synergy between Br{\o}nsted 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 Br{\o}nsted 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 Br{\o}nsted: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.",

keywords = "catalytic transfer hydrogenation, continuous flow reaction, dual-bed cascade, sulfated zirconia, γ-valerolactone",

author = "Andrea Merenda and Orr, {Samantha Alana} and Yang Liu and {Hern{\'a}ndez Garcia}, Blanca and Amin Osatiashtiani and Gabriel Morales and Marta Paniagua and Melero, {Juan Antonio} and Lee, {Adam Fraser} and Karen Wilson",

note = "Copyright {\textcopyright} 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 [https://creativecommons.org/licenses/by-nc/4.0/], 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. ",

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T1 - Continuous flow (Sulfated) Zirconia Catalysed Cascade Conversion of Levulinic Acid to γ‐Valerolactone

AU - Merenda, Andrea

AU - Orr, Samantha Alana

AU - Liu, Yang

AU - Hernández Garcia, Blanca

AU - Osatiashtiani, Amin

AU - Morales, Gabriel

AU - Paniagua, Marta

AU - Melero, Juan Antonio

AU - Lee, Adam Fraser

AU - Wilson, Karen

N1 - 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 [https://creativecommons.org/licenses/by-nc/4.0/], 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.

PY - 2022/12/19

Y1 - 2022/12/19

N2 - 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.

AB - 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.

KW - catalytic transfer hydrogenation

KW - continuous flow reaction

KW - dual-bed cascade

KW - sulfated zirconia

KW - γ-valerolactone

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DO - 10.1002/cctc.202201224

M3 - Article

SN - 1867-3880

JO - ChemCatChem

JF - ChemCatChem

ER -

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

Abstract

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Keywords

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