Synergy of heterogeneous Co/Ni dual atoms enabling selective C–O bond scission of lignin coupling with in-situ N-functionalization

Selective cleavage of Csp2–OCH3 bond in lignin without breaking other types of C–O bonds followed by N-functionalization is fascinating for on-purpose valorization of biomass. Here, a Co/Ni-based dual-atom catalyst CoNiDA@NC prepared by in-situ evaporation and acid-etching of metal species from tailor-made metal-organic frameworks was efficient for reductive upgrading of various lignin-derived phenols to cyclohexanols (88.5%–99.9% yields), which had ca. 4 times higher reaction rate than the single-atom catalyst and was superior to state-of-the-art heterogeneous catalysts. The synergistic catalysis of Co/Ni dual atoms facilitated both hydrogen dissociation and hydrogenolysis steps, and could optimize adsorption configuration of lignin-derived methoxylated phenols to further favor the Csp2–OCH3 cleavage, as elaborated by theoretical calculations. Notably, the CoNiDA@NC catalyst was highly recyclable, and exhibited excellent demethoxylation performance (77.1% yield) in real lignin monomer mixtures. Via in-situ cascade conversion processes assisted by dual-atom catalysis, various high-value N-containing chemicals, including caprolactams and cyclohexylamines, could be produced from lignin.