Facile Synthesis of Ru Nanoboxes with a Hexagonal Close‐Packed Structure by Templating with Ag Nanocubes and Their Catalytic Properties

Noble-metal nanoboxes offer an attractive form of nanomaterials for catalytic applications owing to their open structure and highly efficient use of atoms. Herein, we report the facile synthesis of Ag-Ru core-shell nanocubes and then Ru nanoboxes with a hexagonal close-packed (hcp) structure, as well as evaluation of their catalytic activity toward a model hydrogenation reaction. By adding a solution of Ru(acac)3 in ethylene glycol (EG) dropwise to a suspension of silver nanocubes in EG at 170 °C, Ru atoms are generated and deposited onto the entire surface of a nanocube. As the volume of the RuIII precursor is increased, Ru atoms are also produced through a galvanic replacement reaction, generating Ag-Ru nanocubes with a hollow interior. The released Ag+ ions are then reduced by EG and deposited back onto the nanocubes. By selectively etching away the remaining Ag with aqueous HNO3 , the as-obtained Ag-Ru nanocubes are transformed into Ru nanoboxes, whose walls are characterized by an hcp structure and an ultrathin thickness of a few nanometers. Finally, we evaluated the catalytic properties of the Ru nanoboxes with two different wall thicknesses by using a model hydrogenation reaction; both samples showed excellent performance.