Hydrogen-induced formation of surface acid sites on Pt/Al(PO3)3 enables remarkably efficient hydrogenolysis of C−O bonds in alcohols and ethers

The hydrogenolysis of oxygenates such as alcohols and ethers is central to the biomass valorization and also a valuable transformation in organic synthesis. However, there is lack of a mild and efficient catalyst system that is applicable to a wide range of alcohols and ethers. Here, we report an aluminum metaphosphate-supported Pt nanoparticles for the hydrogenolysis of a wide variety of primary, secondary, and tertiary alkyl and benzylic alcohols, and dialkyl, aryl alkyl, and diaryl ethers, including biomass-derived furanic compounds, under mild conditions (0.1–1 atm of H2, as low as 70 °C). Mechanistic studies suggested that H2 induces formation of the surface Brønsted acid sites via its cleavage by supported Pt nanoparticles. Accordingly, the high efficiency and the wide applicability of the catalyst system can be attributed to the cooperative activation and cleavage of C–O bonds of alcohols and ethers by the hydrogen-induced Brønsted acid sites and Lewis acidic Al sites on Al(PO3)3 surface. The high efficiency of the catalyst imply its potential application in energy efficient biomass valorization or fine chemical synthesis.