Selective Hydrogenolysis of Biomass‐Derived Aromatic Alcohols over 2D‐Mo2COx MXene by a Reversible Redox‐Relay Mechanism

Selective CH2–OH hydrogenolysis of biomass‐derived aromatic alcohols to produce methyl aromatics is crucial for synthesizing sustainable fuels and chemicals; yet traditional metal–acid bifunctional catalysis possesses significant challenges owing to its complex reaction network. Herein, a 2D‐Mo2COx MXene was fabricated, demonstrating an efficient hydrogenolysis of 5‐hydroxymethyl furfural into 5‐methyl furfural, achieving an impressive yield (99.5%) at the mild reaction temperature of 90°C. Catalytic mechanism investigations reveal that 2D‐Mo2COx facilitate the activation and cleavage of the CH2–OH bond through a redox mechanism, driven by the strong CH2–OH affinity of the Mo–Mo metallic plane. In the absence of H2, hydrogen from O–H group is the source for methyl formation from CH2–OH. Under a H2 atmosphere, H2 is activated to remove residual oxygen species, boosting selective hydrogenolysis while suppressing furan and CH=O hydrogenation. Furthermore, the catalyst exhibited broad universality for synthesizing methyl aromatics from various furfuryl alcohols, benzyl alcohols, and hydroxycyclopentenones. This study presents a novel redox‐relay mechanism in advanced MXene catalysis, offering a straightforward hydrogenolysis pathway for challenging substrates.