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

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 maximize 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 Co 13 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 Co 13 . Co atoms and clusters can be effectively immobilized 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 μ B ) is significantly reduced due to electron transfer and bonding, resulting in values varying from ≈ 0.9-2.2 μ 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 μ B . The attractive physical properties of these hybrid systems could find applications in catalysis and materials science. • Systematic ab initio calculations of the adsorption of small cobalt clusters on pristine graphene and graphene with a double vacancies. • Co clusters can be effectively immobilized on divacancies with corresponding adsorption energy being significantly enhanced compared to on pristine graphene, by about 5 to 7 eV. • Finite magnetic moments occur for all systems. • For the pristine graphene substrate, the total induced magnetic moments on the carbon atoms are negligible, however on the divacancy system, they are of the order of 0.1–0.3 μ B. • The physical properties of these hybrid systems could hold potential for applications in many areas of physics and high-tech industries. For example, applications in magnetic memory and spin transport. In relation to catalysis, the increased binding strength of cobalt clusters at divacancies will stabilise the system at the operational high temperatures, thus aiding in the development of cheap, resilient graphene-based catalysts with a large surface area for oxygen reduction reactions.