Selective Hydrogenolysis of Biomass‐Derived Aromatic Alcohols over 2D‐Mo₂CO_x MXene by a Reversible Redox‐Relay Mechanism

Abstract Selective CH 2 −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‐Mo 2 CO x 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‐Mo 2 CO x facilitate the activation and cleavage of the CH 2 −OH bond through a redox mechanism, driven by the strong CH 2 −OH affinity of the Mo–Mo metallic plane. In the absence of H 2 , hydrogen from O−H group is the source for methyl formation from CH 2 −OH. Under a H 2 atmosphere, H 2 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.