Fine‐Tuned Charge Density of Pt Single‐Atom Sites for Controllable Hydrodeoxygenation of Lignin

Abstract Achieving high‐selectivity conversion of lignin to value‐added chemicals and biofuels remains a desirable but challenging target due to its complex structure with multiple reaction paths. Herein, we designed the robust Pt single‐atom sites supported on NiAl layered double hydroxide (Pt 1 /NiAl‐LDH) and intermetallic compound (Pt 1 /NiAl‐IMC) with distinct local charge density for selectivity‐controllable hydrodeoxygenation of lignin. The Pt 1 /NiAl‐LDH with electron‐deficient Pt sites hydrogenated 4‐propylguaiacol into 4‐propylcyclohexanol with 100% conversion and over 90% selectivity, while Pt 1 /NiAl‐IMC with electron‐rich Pt sites favored complete deoxygenation, yielding almost equivalent of propylcyclohexane. Similar results were achieved using lignin samples. Density functional theory calculations revealed that the deoxygenation capacity of Pt 1 /NiAl‐IMC stems from the high electronic density of Pt single atoms, which injects electrons into the C─O bond and weakens its bonding energy. This study demonstrates that the catalytic performance of single‐atom catalysts in biopolymers hydrodeoxygenation can be optimized toward different products by well‐controlled electronic structures.