Anisotropic Growth of One-Dimensional Carbides in Single-Walled Carbon Nanotubes with Strong Interaction for Catalysis

Tungsten and molybdenum carbides have shown great potential in catalysis and superconductivity. However, the synthesis of ultrathin W/Mo carbides with a controlled dimension and unique structure is still difficult. Here, inspired by the host-guest assembly strategy with single-walled carbon nanotubes (SWCNTs) as a transparent template, we reported the synthesis of ultrathin (0.8-2.0 nm) W₂C and Mo₂C nanowires confined in SWCNTs deriving from the encapsulated W/Mo polyoxometalate clusters. The atom-resolved electron microscope combined with spectroscopy and theoretical calculations revealed that the strong interaction between the highly carbophilic W/Mo and SWCNT resulted in the anisotropic growth of carbide nanowires along a specific crystal direction, accompanied by lattice strain and electron donation to the SWCNTs. The SWCNT template endowed carbides with resistance to H₂O corrosion. Different from normal modification on the outer surface of SWCNTs, such M₂C@SWCNTs (M = W, Mo) provided a delocalized and electron-enriched SWCNT surface to uniformly construct the negatively charged Pd catalyst, which was demonstrated to inhibit the formation of active PdH_x hydride and thus achieve highly selective semihydrogenation of a series of alkynes. This work could provide a nondestructive way to design the electron-delocalized SWCNT surface and expand the methodology in synthesizing unusual 1D ultrathin carbophilic-metal nanowires (e.g., TaC, NbC, β-W) with precise control of the anisotropy in SWCNT arrays.