Controlling Reaction Paths with Ru–Ni Alloys: C–O Retention for Alcohol Synthesis

Ru-based catalysts are widely used in catalytic reactions, but the electron-deficient nature promotes strong decarbonylation, leading to complete deoxygenation during the conversion of polyhydroxy biomass. Despite extensive research, effectively suppressing this decarbonylation activity remains challenging. Herein, electron-rich Ru and electron-deficient Ni formed due to the electron migration of Ni → Ru have a synergistic catalytic effect, controlling the precise cleavage of CN bonds by Ru⁰ and retaining most of the CO bonds. The amorphous Al₂O₃ is sufficiently bound to the substrate to promote rapid hydrogenation. This modification effectively suppresses the intrinsic decarbonylation activity of Ru and improves selectivity for hydrodeoxygenation. Using carbohydrates as substrates, the Ru-Ni bimetallic catalysts preferentially promote the hydrodeoxygenation pathway, resulting in a significant increase in C3+ monohydric alcohol yields. This work presents a new strategy for modulating reaction pathways via electronic structure engineering, offering valuable insights into the potential of Ru-Ni systems for biomass conversion and sustainable alcohol synthesis.