Triggering hydrogenolysis of the lignin model compound benzyl phenyl ether using the intrinsic exothermicity of Pd-hydride formation.

When supported Pd catalysts are exposed to hydrogen, the heat released from the spontaneous and exothermic Pd-hydride formation creates a reaction environment that allows for melting and hydrogenolysis of benzyl phenyl ether (BPE) under nominally ambient conditions. The intrinsic exothermicity of this hydride formation acts as an initiating force for α-O-4 ether cleavage of the BPE dimer, without the need for external heat to be applied to the reaction system. Thermogravimetric analysis with differential scanning calorimetry shows heat flows of 58, 40, and 32 W g-1 for Pd supported on carbon, silica and alumina, respectively. BPE conversion increased with increasing heat flow, which correlated with a higher Pd particle dispersion and lower heat capacity of the support. X-ray absorption spectroscopy at the Pd-K edge confirms Pd-hydride formation. This work shows that the heat released by Pd-H formation can be used as an initiator for α-O-4 ether cleavage in a solid lignin model compound.