Pt‐Loaded Nb─W Metal Composite Oxide for Selective Cleavage of Secondary C─O Bonds

Abstract Selective hydrogenolysis of glycerol to 1,3‐propanediol (1,3‐PDO) is recognized as one of the most promising reactions for the valorization of biomass. Precise activation of C─O bonds of glycerol molecule is the key step to realize the high yield of catalytic conversion. Here, a Pt‐loaded Nb–W composite oxides with crystallographic shear phase for the precise activation and cleavage of secondary C─O (C(2)─O) bonds are first reported. The developed Nb₁₄W₃O₄₄ with uniform structure possesses arrays of W–O–Nb active sites that totally distinct from individual WO_x or NbO_x species, which is superior to the adsorption and activation of C(2)─O bonds. The Nb₁₄W₃O₄₄ support with rich reversible redox couples also promotes the electron feedback ability of Pt and enhances its interaction with Pt nanoparticles, resulting in high activity for H₂ dissociation and hydrogenation. All these favorable factors confer the Pt/Nb₁₄W₃O₄₄ excellent performance for selective hydrogenolysis of glycerol to 1,3‐PDO with the yield of 75.2% exceeding the record of 66%, paying the way for the commercial development of biomass conversion. The reported catalysts or approach can also be adopted to create a family of Nb–W metal composite oxides for other catalytic reactions requiring selective C─O bond activation and cleavage.