Selective Hydrodeoxygenation of Esters to Unsymmetrical Ethers over a Zirconium Oxide-Supported Pt-Mo Catalyst.

The catalytic hydrodeoxygenation (HDO) of carbonyl oxygen in esters using H 2 is an attractive method for synthesizing unsymmetrical ethers because water is theoretically the sole coproduct. Herein, we report a heterogeneous catalytic system for the selective HDO of esters to unsymmetrical ethers over a zirconium oxide-supported platinum-molybdenum catalyst (Pt-Mo/ZrO 2 ). A wide range of esters were transformed into the corresponding unsymmetrical ethers under mild reaction conditions (0.5 MPa H 2 at 100 °C). The Pt-Mo/ZrO 2 catalyst was also successfully applied to the conversion of a biomass-derived triglyceride into the corresponding triether. Physicochemical characterization and control experiments revealed that cooperative catalysis between Pt nanoparticles and neighboring molybdenum oxide species on the ZrO 2 surface plays a key role in the highly selective HDO of esters. This Pt-Mo/ZrO 2 catalyst system offers a highly efficient strategy for synthesizing unsymmetrical ethers and broadens the scope of sustainable reaction processes.