Interaction of Gallium with a Copper Surface: Surface Alloying and Formation of Ordered Structures.

Alloys of gallium with transition metals have recently received considerable attention for their applications in microelectronics and catalysis. Here, we investigated the initial stages of the Ga-Cu alloy formation on Cu(111) and Cu(001) surfaces using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and low energy electron diffraction (LEED). The results show that Ga atoms deposited using physical vapor deposition readily intermix with the Cu surface, leading to a random distribution of the Ga and Cu atoms within the surface layer, on both terraces and monolayer-thick islands formed thereon. However, as the Ga coverage increases, several ordered structures are formed. The (√3×√3)R30° structure is found to be thermodynamically most stable on Cu(111). This structure remains after vacuum annealing at 600 K, independent of the initial Ga coverage (varied between 0.5 and 3 monolayers), indicating a self-limited growth of the Ga-Cu alloy layer, with the rest of the Ga atoms migrating into the Cu crystal. For Ga deposited on Cu(001), we observed a (1 × 5)-reconstructed surface, which has never been observed for surface alloys on Cu(001). The experimental findings were rationalized on the basis of density functional theory (DFT) calculations, which provided structural models for the most stable surface Ga-Cu alloys on Cu(111) and Cu(001). The study sheds light on the complex interaction of Ga with transition metal surfaces and the interfaces formed thereon that will aid in a better understanding of surface alloying and chemical reactions on the Ga-based alloys.

Diversity of platinum-sites at platinum/fullerene interface accelerates alkaline hydrogen evolution.

Membrane-based alkaline water electrolyser is promising for cost-effective green hydrogen production. One of its key technological obstacles is the development of active catalyst-materials for alkaline hydrogen-evolution-reaction (HER). Here, we show that the activity of platinum towards alkaline HER can be significantly enhanced by anchoring platinum-clusters onto two-dimensional fullerene nanosheets. The unusually large lattice distance (~0.8 nm) of the fullerene nanosheets and the ultra-small size of the platinum-clusters (~2 nm) leads to strong confinement of platinum clusters accompanied by pronounced charge redistributions at the intimate platinum/fullerene interface. As a result, the platinum-fullerene composite exhibits 12 times higher intrinsic activity for alkaline HER than the state-of-the-art platinum/carbon black catalyst. Detailed kinetic and computational investigations revealed the origin of the enhanced activity to be the diverse binding properties of the platinum-sites at the interface of platinum/fullerene, which generates highly active sites for all elementary steps in alkaline HER, particularly the sluggish Volmer step. Furthermore, encouraging energy efficiency of 74% and stability were achieved for alkaline water electrolyser assembled using platinum-fullerene composite under industrially relevant testing conditions.