The growth of single-walled carbon nanotubes (SWCNTs) with predefined structure is of great importance for both fundamental research and their practical applications. Traditionally, SWCNTs are grown from a metal catalyst with a vapor-liquid-solid mechanism, where the catalyst is in liquid state with fluctuating structures, and it is intrinsically unfavorable for the structure control of SWCNTs. Here we report the heteroepitaxial growth of SWCNTs from a platelet boron nitride nanofiber (BNNF), which is composed of stacked (002) planes and is stable at high temperatures. SWCNTs are found to grow epitaxially from the open (002) edges of the BNNFs, and the diameters of the SWCNTs are multiples of the BN (002) interplanar distance. In situ transmission electron microscopy observations coupled with first principles calculations reveal that the growth of SWCNTs from the BNNFs follows a vapor-solid-solid mechanism. Our work opens opportunities for the control over the structure of SWCNTs by hetero-crystallographic epitaxy.

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