Work

Boosting POM‐Ionosolv Biorefining of Lignocellulosic Biomass by Using Redox‐Balanced Polyoxometalate Catalysts in Methanolic Ionic Liquid Reaction Media

Year: 2025

Type: 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][HSO 4 ]), N , N ‐dimethylbutylammonium hydrogen sulfate ([DMBA][HSO4]), and tributylmethylphosphonium methyl sulfate ([TBMP][MeSO 4 ]), 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 H 8 PVMnMo 10 O 40 POM catalyst in [TBMP][MeSO 4 ]/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.

Source: ChemSusChem

DOI: 10.1002/cssc.202501034