Synergistic Cu-Pd Nanocatalysts on MOF-Derived N-Doped Carbon for Selective Hydrogenolysis of Lignin to Aromatic Monomers

Catalytic hydrogenolysis of lignin to produce high-value monophenols has emerged as a pivotal strategy in modern biorefineries. In this study, we synthesized spherical nitrogen-doped porous carbon (SNCB) materials by using Al/Co-BTC as a precursor, introducing melamine as a supplementary carbon and nitrogen source, and activating the material with NaOH solution. The SNCB framework was decorated with Cu-Pd bimetallic nanoparticles, exhibiting outstanding catalytic activity in the hydrogenolytic depolymerization of organosolv lignin. The Cu-Pd@SNCB catalyst exhibited remarkable activity, attributed to the hierarchical porous structure of SNCB that facilitated metal nanoparticle dispersion and reactant accessibility. The synergistic effect between Cu as the reactive site for reactant adsorption and Pd as the reactive site for H2adsorption enhanced the catalytic activity of the catalyst. Systematically optimized conditions (2 MPa H2, 270 °C, 3 h) yielded 43.02 wt% phenolic monomers, with 4-(3-hydroxypropyl)-2,6-dimethoxyphenol dominating the product profile at 46.3% selectivity. The catalyst and its reaction products were analyzed using advanced characterization techniques, including XPS, XRD, TEM, SEM, BET, GC-MS, GPC, 2D HSQC NMR, and FT-IR, to elucidate the reaction mechanism. The mechanism proceeds through: (1) nucleophilic substitution of the β-O-4 hydroxyl group by MeOH, followed by (2) simultaneous hydrogenolytic cleavage of Cβ-O and Cα-O bonds mediated by Cu-Pd@SNCB under H2atmosphere, which selectively produces 4-(3-hydroxypropyl)-2,6-dimethoxyphenol and 4-propyl-2,6-dimethoxyphenol. This study proposes a bimetallic synergistic mechanism, offering a general blueprint for developing selective lignin valorization catalysts.