Crystal‐Plane‐Controlled Selectivity of Cu₂O Catalysts in Propylene Oxidation with Molecular Oxygen

Abstract

Abstract The selective oxidation of propylene with O 2 to propylene oxide and acrolein is of great interest and importance. We report the crystal‐plane‐controlled selectivity of uniform capping‐ligand‐free Cu 2 O octahedra, cubes, and rhombic dodecahedra in catalyzing propylene oxidation with O 2 : Cu 2 O octahedra exposing {111} crystal planes are most selective for acrolein; Cu 2 O cubes exposing {100} crystal planes are most selective for CO 2 ; Cu 2 O rhombic dodecahedra exposing {110} crystal planes are most selective for propylene oxide. One‐coordinated Cu on Cu 2 O(111), three‐coordinated O on Cu 2 O(110), and two‐coordinated O on Cu 2 O(100) were identified as the catalytically active sites for the production of acrolein, propylene oxide, and CO 2 , respectively. These results reveal that crystal‐plane engineering of oxide catalysts could be a useful strategy for developing selective catalysts and for gaining fundamental understanding of complex heterogeneous catalytic reactions at the molecular level.