Self-assembly of atomically thin and unusual face-centered cubic re nanowires within carbon nanotubes

Rhenium (Re), a high-performance engineering material with a hexagonal close-packed (hcp) structure, remains stable even under pressures of up to 250 GPa and at temperatures up to its melting point (3453 K). We observed here that Re atoms self-assembled, within the confined space of carbon nanotubes (CNTs) with a diameter of <1.5 nm, into ultrathin nanowires stacking with an unusual face-centered cubic (fcc) structure along the CNTs. In contrast, only Re nanoparticles of hcp structure formed on an open surface of graphite and carbon black. Aberration-corrected electron microscopy unambiguously showed the atomic arrangements of the Re nanowires and their confinement within the CNTs, ∼80% exhibiting a four-atom and 15% a nine-atom configuration. Density functional theory calculations confirmed that the formation of unusual fcc-stacking Re nanowires is largely facilitated by the strong interaction between Re atoms and CNTs and the spatial restriction within the CNTs. The use of CNTs as nanoscale reactors to create novel structures not only is fundamentally interesting but also may find unique applications in catalysis, sensing, and nanoelectronics.