Roles of metal and acid sites in the reductive depolymerization of concentrated lignin over supported Pd catalysts

Abstract

Lignin is a natural polymer contained in lignocellulose and is a potential feedstock for the production of phe-nolics or small aromatic molecules. However, lignin depolymerization is typically performed using low lignin concentrations and insufficiently active catalysts, which hinders industrial applications. To address this issue, we herein investigated the depolymerization of concentrated kraft lignin and oak-extracted organosolv lignin pro-moted by supported bifunctional metal (palladium)-acid catalysts and elucidated the roles of acid and metal sites. In addition to acid sites, which are known to be critical for lignin degradation, metal sites were found to be required to initiate lignin depolymerization. Palladium atoms promoted depolymerization even in the absence of acid sites, while acid site-promoted depolymerization required the presence of surface palladium atoms. Cata-lysts with bulk palladium particles were much more active than those with highly dispersed palladium particles, which suggested that efficient depolymerization required the bulky lignin polymer to be adsorbed on the palladium surface in a multidentate fashion. Thus, our work provides valuable insights into the mechanism of catalytic lignin depolymerization and paves the way to the industrial-scale application of this process.