Ultra-Selective C-O Hydrogenolysis of Biomass-Based Compounds at Low Temperature and Atmospheric Pressure Driven by Hydrogen Heterolysis over the Pd(2D)-P Interface

The development of highly selective hydrogenolysis catalysts for aromatic alcohols is critical for advancing sustainable biofuel production and high-value fine chemical synthesis. Nevertheless, the intricate reaction networks and intrinsic competing side reactions associated with aromatic alcohol hydrogenolysis pose substantial challenges to mechanistic elucidation and industrial process engineering. Herein, phosphorus-doped carbon supports (Px@AC) were first synthesized via chemical vapor deposition. Subsequently, Pd-based catalysts with well-defined crystal facets, designated as Pd(2D)/Px@AC, were successfully prepared through an in-situ reduction approach. By systematically adjusting the precursor feeding ratios, the structure-activity relationship between phosphorus doping content and the selective C-O bond hydrogenolysis performance was thoroughly investigated. Notably, they demonstrated extraordinary catalytic activity and selectivity for the C-O hydrogenolysis of phenyl alcohols and furan alcohols under mild reaction conditions (14℃, ambient pressure). Mechanistic investigations revealed that hydrogen spillover from Pd nanoparticles to the Pd(2D)-P interfacial sites facilitates the formation of transient P-H+···H–-Pd pairs. These interfacial dual-hydrogen species enable the simultaneous activation of the oxygen and carbon atoms in the C-O bonds of aromatic alcohols via an SN2 reaction pathway, thereby significantly boosting the hydrogenolysis kinetics under mild operating conditions. This work highlights a unique bifunctional catalytic mechanism, wherein in-situ generated transient H⁺-H⁻ pairs mediate efficient C-O bond cleavage under ambient pressure and low temperature, offering valuable insights for the rational design of high-performance catalysts for selective hydrogenolysis reactions.