Electronic Modulation of CoNi Nanoparticles by N‐Doped Carbon for Efficient Lignin Hydrogenolysis to Aromatic Monomers

ABSTRACT Cost‐effective and efficient non‐noble‐metal catalysts for selective lignin hydrogenolysis remain elusive, representing a significant challenge in biorefinery. Here, we prepared a nitrogen‐doped carbon supported CoNi bimetallic catalyst, which was successfully derived from zeolitic imidazolate framework (ZIF) via high‐temperature pyrolysis. The incorporation of Ni facilitates the formation of highly dispersed CoNi alloy nanoparticles, effectively preventing their agglomeration, and simultaneously induces substantial electronic modulation that enriches Co sites through charge transfer from Ni. Acting in concert, these structural and electronic effects accelerate C–O bond cleavage while limiting over‐hydrogenation of aromatic rings. Under mild conditions, the optimized 3Co1Ni/NC‐800 catalyst delivers nearly complete conversion of the lignin model substrate 2‐phenylethyl phenyl ether and furnishes a 26.5 wt% phenolic monomer yield from birch lignin, outperforming Co/NC‐800 and Ni/NC‐800 (17.1 and 19.4 wt%, respectively). The catalyst also demonstrates excellent stability and recyclability, credited to the robust N‐doped carbon framework and strong metal‐support interaction. Collectively, the study outlines outline a rational route for designing advanced bimetallic catalysts for lignin valorization.