Metal–Organic-Framework-Derived Copper Catalysts for the Hydrogenolysis of Lignin into Monomeric Phenols

Reductive catalytic fractionation (RCF) of lignocellulosic biomass has emerged as a leading biorefinery strategy. Herein, we present a copper-based catalyst (CuO/C) derived from a metal–organic backbone (HKUST-1) with enhanced catalytic performance for RCF of woody sawdust, which affords high yields of propyl and propanol end-chain monomeric phenols (15.5 wt % in softwoods and 46.7 wt % in hardwoods) via the C–O bond scission. A series of conifer β-O-4 models and their deuterated analogues revealed that the synergistic action of CuO/C and hydrogen could effectively cleave aryl ether linkages. It was deduced that lignin alcoholysis led to partial α-OH etherification of the β-O-4′ units, which promoted the C–O bond breakage of Cα-OMe and Cβ-O, thus giving propanol phenolic compounds through the hydrogenation of coniferyl alcohol over the CuO/C catalyst. When both α- and γ-OH of β-O-4′ motifs were meoxylated, the para-propyl phenolics were obtained through the scission of C–O linkages (Cα-OMe and Cβ-O), followed by the Cγ-OMe cleavage of propenyl ethers and hydrogenation of propenyl phenols. We envision that this work may pave the way for the development of non-noble catalysts with high reactivity and selectively for lignin valorization.