Constructing exclusive Pt@WOx interfacial sites enables selective C–O bond activation

Precisely constructing exclusive metal-oxide interfacial active sites while eliminating non-interfacial species represents a longstanding challenge in heterogeneous catalysis. Here we construct catalysts featuring exclusively isolated Pt@WOx interfacial sites via a controlled electrostatic adsorption strategy, thereby eliminating non-interfacial Pt species, enabling controlled reaction pathways. We identify that selective C–O bond activation is governed by the availability of interfacial reactive hydrogen, where isolated Pt sites drive deep hydrogenolysis, while Pt@WOx interfacial sites control reaction pathways by constrained hydrogen availability. This principle is validated in glycerol hydrogenolysis, achieving a high 1,3-PDO selectivity of 73.5% at a low temperature of 130 °C. Experiments reveal that 1,3-PDO selectivity is not enhanced by increasing active site density, but by eliminating intrinsically unselective sites, thereby reshaping the reaction energy landscape to suppress thermodynamically driven over-hydrogenolysis. This architecture provides an ideal platform for disentangling interface effects from contributions arising from non-interfacial metal species. Precisely constructing metal–oxide catalysts with exclusively interfacial active sites remains challenging. Here, glycerol is selectively converted to 1,3-propanediol over catalysts in which Pt exists solely as isolated Pt@WOx interfacial sites.