Coordination‐Engineered Ni‐Pd on Lignin‐Derived Carbon for the Upgrading of Technical Lignin Toward Aromatic‐Rich Aviation Fuel Precursors

ABSTRACT Technical lignin valorization is fundamentally limited by the scarcity and kinetic inertia of cleavable C─O linkages in a condensed C─C/C─O network, constraining the production of aromatic monomers and other fuel‐relevant intermediates. Here, we report a coordination‐engineered Ni‐Pd on lignin‐derived Carbon (NiPd 0.1 /C) constructed via solvent/antisolvent assembly to enable trace Pd incorporation that electronically modulates Ni. Structural analyses suggest a uniform solid solution with interfacial charge redistribution (Ni δ+ ‐Pd δ− ), which generates polarized interfacial sites and strengthens C─O bond activation. The NiPd 0.1 /C boosts aromatic monomer yield from enzymatic hydrolysis lignin to 23 wt.%, outperforming commercial Pd/C (∼16 wt.%). Product analysis shows syringyl/guaiacyl/p‐hydroxyphenyl (S/G/H)phenolics dominated by G‐type units, and the catalyst remains effective for more condensed alkali lignin (∼16 wt.% monomers), underscoring feedstock tolerance. Model‐compound and kinetic studies indicate that Ni‐Pd alloying accelerates the turnover of phenoxy intermediates by lowering the apparent barrier for dehydrogenation and subsequent ether C─O bond cleavage, thereby enabling the selective cleavage of C─O bonds. This work establishes solid‐solution electronic engineering as a broadly generalizable strategy to unlock cost‐effective C─O activation and accelerate lignin valorization toward scalable, low‐carbon aviation fuel precursors.