Ultraselective C–O Hydrogenolysis of Biomass-Based Compounds under Ambient Pressure and at Low Temperature via Hydrogen Spillover over the Pd–SO42– Interface

Developing an efficient catalyst for the selective hydrogenolysis of aromatic alcohol and diphenyl ether derivatives is important for synthesizing biofuels and fine chemicals. However, it possesses challenges because of the complex reaction network. Herein, a series of Pd nanoparticle and sulfate ion (SO 4 2– )-supported catalysts were fabricated, catalyzing the hydrogenolysis of benzyl alcohol selectively to methylbenzene with a 99.6% yield at 30 °C under ambient pressure. Furthermore, they showed generality for synthesizing methyl aromatic derivatives from various furfuryl, benzyl, and heterocyclic alcohols under the same reaction conditions. Moreover, the hydrogenolysis of diphenyl ethers was catalyzed at 90 °C under ambient pressure. The catalytic mechanism study revealed that hydrogen spillover from Pd nanoparticles to the Pd–SO 4 2– interface generated the S–O–H + ···H – –Pd pairs, which could simultaneously activate O and C atoms in the C–O bonds of aromatic alcohol and diphenyl ether derivatives based on the S N 2 mechanism, thus accelerating the hydrogenolysis activity. This study presents interesting bifunctional catalysis, offering uncommon hydrogenolysis efficiency under ambient pressure and at low temperature via in situ-generated transient H + –H – pairs.