A novel heterostructured hexagonal-boron nitride (h-BN) flake-coating on multi-wall carbon nanotubes (MWCNT/BN) is reported and synthesized by chemical vapor deposition (CVD). Comprehensive characterization using X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM), combined with electron energy loss spectroscopy (EELS), revealed the atomic structure and growth mechanism, which is further validated by molecular dynamics simulations. The resulting MWCNT/BN structure comprises three distinct layers: an inner carbon nanotube (CNT) core, coaxial BN nanotubes (BNNTs) surrounding the CNT core, and outer BN flakes extending from the BNNTs. We propose that BN layers first form coaxial BNNTs on the CNT surface; as deposition proceeds, BN accumulation generate in-plane and out-of-plane compressive stresses in the h-BN layers. When these stresses exceed a critical threshold, local buckling or cracking occurs, BN flakes emerge and grow further. This work elucidates, for the first time, the formation mechanism of BN nanoflakes on MWCNTs and confirms that the structure is a van der Waals heterostructure. The approach also offers a new route for synthesizing coaxial MWCNT@BN with only a few h-BN layers. Notably, the BN flake coatings provide efficient phonon transport pathways and a large surface area, making this heterostructure highly promising for applications in thermal dissipation.
