Hydrogen-Transfer Reductive Catalytic Fractionation of Lignocellulose: High Monomeric Yield with Switchable Selectivity

Angew Chem Int Ed Engl. 2023 Aug 7;62(32):e202307116. doi: 10.1002/anie.202307116. Epub 2023 Jul 3.

Abstract

Lignin solubilization and in situ hydrogenolysis are crucial for reductive catalytic fractionation (RCF) of lignocellulose to aromatic monomers. In this study, we reported a typical hydrogen bond acceptor of choline chloride (ChCl) to tailor the hydrogen-donating environment of the Ru/C-catalyzed hydrogen-transfer RCF of lignocellulose. The ChCl-tailored hydrogen-transfer RCF of lignocellulose was conducted under mild temperature and low-pressure (<1 bar) conditions, which was applicable to other lignocellulosic biomass sources. We obtained an approximate theoretical yield of propylphenol monomer of 59.2 wt % and selectivity of 97.3 % using an optimal content of ChCl (10 wt %) in ethylene glycol at 190 °C for 8 h. When the content of ChCl in ethylene glycol was increased to 110 wt %, the selectivity of propylphenol switched toward propylenephenol (yield of 36.2 wt % and selectivity of 87.6 %). The findings in this work provide valuable information for transforming lignin from lignocellulose into value-added products.

Keywords: Aromatic Monomer; Biomass Refinery; Hydrogen Transfer; Lignin; Reductive Catalytic Fractionation.