Adsorption and dissociation of hydrogen molecules on bare and functionalized carbon nanotubes

Abstract

We investigated interaction between hydrogen molecules and bare as well as functionalized single-wall carbon nanotubes (SWNT) using first-principles plane wave method. We found that the binding energy of the H$_{2}$ physisorbed on the bare SWNT is very weak, and can be enhanced neither by increasing the curvature of the surface through radial deformation, nor by the coadsorption of Li atom that makes the semiconducting tube metallic. Though the bonding is strengthened upon adsorption directly to Li atom, yet its nature continues to be physisorption. However, the character of the bonding changes dramatically when SWNT is functionalized by the adsorption of Pt atom. Single H$_{2}$ is chemisorbed to Pt atom on the SWNT either dissociatively or molecularly. If Pt-SWNT bond is weakened either by displacing Pt from bridge site to a specific position or by increasing number of the adsorbed H$_{2}$, the dissociative adsorption of H$_{2}$ is favored. For example, out of two adsorbed H$_{2}$, first one can be adsorbed dissociatively, second one is chemisorbed molecularly. The nature of bonding is weak physisorption for the third adsorbed H$_{2}$. Palladium also promotes the chemisorption of H$_{2}$ with relatively smaller binding energy. Present results reveal the important effect of transition metal atom adsorbed on SWNT and advance our understanding of the molecular and dissociative adsorption of hydrogen for efficient hydrogen storage.