Boosting POM-ionosolv biorefining of lignocellulosic biomass by using redox-balanced polyoxometalate catalysts in methanolic ionic liquid reaction media
Author(s)
Type
Journal Article
Abstract
This article presents an advanced iteration of the polyoxometalate (POM)-Ionosolv concept to generate biobased methyl formate in high yield and a bleached cellulose pulp from lignocellulosic biomass in a single-step operation by using redox-balanced POM catalysts and molecular oxygen in alcoholic ionic liquid (IL) mixtures. The performance of the three Ionosolv-ILs triethylammonium hydrogen sulfate ([TEA][HSO4]), N,N-dimethylbutylammonium hydrogen sulfate ([DMBA][HSO4]), and tributylmethylphosphonium methyl sulfate ([TBMP][MeSO4]), mixed with methanol (MeOH) (30/70 wt%), is evaluated by methyl formate yield from extracted hemicellulose and lignin as well as purity of the bleached cellulose pulp in the presence of various Keggin-type POMs. The redox-balanced H8PVMnMo10O40 POM catalyst in [TBMP][MeSO4]/MeOH emerge as the most effective combination, achieving 20% methyl formate yield from commercial beech wood. The glucan content in the bleached cellulose-enriched solid consisted is over 90%, demonstrating that the use of MeOH drastically improved lignin extraction in parallel with full hemicellulose extraction. The cellulose is highly susceptible to enzymatic hydrolysis, generating a pure and concentrated cellulosic glucose stream. The formed solid catalyst complex is examined in detail to reveal its chemical nature as POM-IL-complex. The approach is applicable to disparate types of lignocellulosic biomass, including hardwood, softwood, and grass.
Date Issued
2025-10-23
Date Acceptance
2025-09-01
Citation
ChemSusChem, 2025, 18 (20)
ISSN
1864-5631
Publisher
Wiley
Journal / Book Title
ChemSusChem
Volume
18
Issue
20
Copyright Statement
© 2025 The Author(s). ChemSusChem published by Wiley-VCH GmbH This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
License URL
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/40928152
Subjects
cellulose pulp
Chemistry
Chemistry, Multidisciplinary
FORMIC-ACID
FRACTIONATION
Green & Sustainable Science & Technology
green chemistry
LIGNIN
lignocellulosic biomass
methyl formate
OXIDATION
Physical Sciences
polyoxometalate
polyoxometalate-ionosolv biorefining
PRETREATMENT
Science & Technology
Science & Technology - Other Topics
Publication Status
Published
Coverage Spatial
Germany
Article Number
e202501034
Date Publish Online
2025-09-10