Electronic and magnetic properties of cobalt clusters on pristine and divacancy graphene

Abstract

Using ab initio calculations we investigate the adsorption of Co atoms, dimers and small cobalt clusters of 5 and 13 atoms on pristine graphene and graphene with a double vacancy. We report the atomic, electronic, magnetic and energetic properties of these systems. Stable adsorption configurations tend to maximise the number of cobalt-carbon bonds. On graphene, the adsorption energy of the clusters is only about 0.4 to 1 eV, and the clusters are relatively mobile on graphene. Interestingly, for different adsorbed Co₁₃ isomers on graphene it is found that they converge to the same atomic structure. On graphene with a divacancy, the Co clusters bind in the divacancy site and isomerisation also occurs for the Co${}_5$ cluster system as well as for Co₁₃. Co atoms and clusters can be effectively immobilised on the divacancy with corresponding adsorption energy being significantly enhanced by about 5 to 7 eV. All clusters act as electron donors in the interaction with the graphene/divacancy systems, and the amount of electron charge transfer increases with cluster size. Finite magnetic moments occur for all systems, where upon adsorption, the magnetic moment of the isolated Co atom (3${\mu }_B$) is significantly reduced due to electron transfer and bonding, resulting in values varying from $\approx$0.9-2.2 ${\mu }_B$ per Co atom. For the pristine graphene substrate, the total induced magnetic moments on the carbon atoms are negligible, while on the divacancy system, they are of the order of 0.1-0.3 ${\mu }_B$. The attractive physical properties of these hybrid systems could find applications in catalysis and materials science.