Clusters of transition metals, W, Re, and Os, upon encapsulation within a single-walled carbon nanotube (SWNT) exhibit marked differences in their affinity and reactivity with the SWNT, as revealed by low-voltage aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM). Activated by an 80 keV electron beam, W reacts only weakly with the SWNT, Re creates localized defects on the sidewall, and Os reacts readily causing extensive defect formation and constriction of the SWNT sidewall followed by total rupture of the tubular structure. AC-HRTEM imaging at the atomic level of structural transformations caused by metal-carbon bonding of π- and σ-character demonstrates what a crucial role these types of bonds have in governing the interactions between the transition metal clusters and the SWNT. The observed order of reactivity W < Re < Os is independent of the metal cluster size, shape, or orientation, and is related to the metal to nanotube bonding energy and the amount of electronic density transferred between metal and SWNT, both of which increase along the triad W, Re, Os, as predicted by first-principles density functional theory calculations. By selecting the appropriate energy of the electron beam, the metal-nanotube interactions can be controlled (activated or precluded). At an electron energy as low as 20 keV, no visible transformations in the nanotube in the vicinity of Os-clusters are observed.
ASJC Scopus subject areas
- Colloid and Surface Chemistry