Lignin hydrogenolysis: Tuning the reaction by lignin chemistry

Replacing fossil resource with biomass is one of the promising approaches to reduce our carbon footprint. Lignin is one of the three major components of lignocellulosic biomass, accounting for 10-35 wt% of dried weight of the biomass. Hydrogenolytic depolymerization of lignin is attracting increasing attention because of its capacity of utilizing lignin in its uncondensed form and compatibility with the biomass fractionation processes. Lignin is a natural aromatic polymer composed of a variety of monolignols associated with a series of lignin linkage motifs. Hydrogenolysis cleaves various ether bonds in lignin and releases phenolic monomers which can be further upgraded into valuable products, i.e., drugs, terephthalic acid, phenol. This review provides an overview of the state-of-the-art advances of the reagent (lignin), products (hydrol lignin), mass balance, and mechanism of the lignin hydrogenolysis reaction. The chemical structure of lignin is reviewed associated with the free radical coupling of monolignols and the chemical reactions of lignin upon isolation processes. The reactions of lignin linkages upon hydrogenolysis are discussed. The components of hydrol lignin and the selectivity production of phenolic monomers are reviewed. Future challenges on hydrogenolysis of lignin are proposed. This article provides an overview of lignin hydrogenolysis reaction which shows light on the generation of optimized lignin ready for hydrogenolytic depolymerization.