Electrocatalytic properties of scandium metallofullerenes for the hydrogen evolution reaction

Endohedral metallofullerenes (M n @C m ) with single metal atom or metal clusters encapsulated have been studied extensively due to their unique hybrid structures and novel properties in physics and chemistry. In this manuscript, we use density functional theory (DFT) to investigate the potential of scandium metallofullerenes as potential catalysts for the hydrogen evolution reaction (HER). By comparing a series of monometallofullernes, we found that scandium metallofullerenes are structurally stable, but possess inferior HER catalytic activity. We therefore propose using an endohedral scandium clusterfullerene (Sc n @C m ) to tune HER catalytic activity by optimizing van der Waals (VDW) interactions between the cluster and the carbon cage wall. Strikingly, two clusterfullerenes, Sc 6 @C 80 and Sc 10 @C 100 , exhibit excellent HER activity with Gibbs free energies of adsorbed hydrogen close to 0. Based on the analysis of charge density difference and the density of states, we explain the mechanism influencing the HER catalytic properties at the electronic level. • The Sc clusterfullerene has been explored as HER catalyst. • The structural stability and the HER activity are theoretically studied. • The high HER activity can be achieved by tuning the VDW interactions. • The high HER activity can be well explained by d-band center theory.