Ruthenium Nanoframes in the Face-Centered Cubic Phase: Facile Synthesis and Their Enhanced Catalytic Performance

Owing to their highly open structure and a large number of low-coordination sites on the surface, noble-metal nanoframes are intriguing for catalytic applications. Here, we demonstrate the rational synthesis of Ru cuboctahedral nanoframes with enhanced catalytic performance toward hydrazine decomposition. The synthesis starts from Pd nanocubes, which quickly undergo truncation at the corners as a consequence of oxidative etching caused by Br^- ions. Afterward, the galvanic replacement reaction between Pd and Ru(III) ions dominates, leading to the selective deposition of Ru atoms on the corners and edges and thereby the fabrication of Pd@Ru core-frame cuboctahedra. Significantly, the deposited Ru atoms are crystallized in a face-centered cubic (fcc) phase instead of the hexagonal close-packed (hcp) structure typical of bulk Ru. Upon the removal of Pd remaining in the core via chemical etching, we obtain Ru cuboctahedral nanoframes. By varying the amount of the Ru(III) precursor, the ridge thickness of the nanoframes can be tuned from a few atomic layers up to 10. Both the frame structure and fcc crystal phase of the Ru cuboctahedral nanoframes can be well preserved up to 300 °C. When compared with hcp-Ru nanoparticles, the fcc-Ru nanoframes displayed substantial enhancement in terms of H₂ selectivity toward hydrazine decomposition. This work offers the opportunity to engineer both the morphology and crystal phase of Ru nanocrystals for catalytic applications.