Ultrasmall (<2 nm) Au@Pt Nanostructures: Tuning the Surface Electronic States for Electrocatalysis.

The ability to tune the electronic properties of nanomaterials have played a major role in the development of sustainable energy technologies. The metallic nanocatalysts are at the forefront of these advances. Their unique properties become even more interesting when we can control the distribution of the electronic states in the nanostructure. Here, we provide a comprehensive evaluation of the electronic surface states in ultrasmall metallic nanostructures by combining experimental and theoretical methods. The developed strategy allows the controlled synthesis of bimetallic nanostructures in the core-shell configuration, dispensing the use of any surfactant or stabilizing agents, which usually inactivate important surface phenomena. The synthesized ultrasmall Au@Pt nanoarchitecture (~1.8 nm) presents an enhanced performance catalyzing the hydrogen evolution reaction. First principles calculations of projected and space-resolved local density of states of Au55@Pt92 (core-shell), Au55Pt92 (alloy) and Pt147 nanoparticles show a prominent increase in the surface electronic states for the core-shell bimetallic nanomaterial. It arises from a more effective charge transfer from gold to the surface platinum atoms in the core-shell configuration. In pure Pt147 or Au55Pt92 alloy nanoparticles, great part of the electronic states near the Fermi level are buried in the core atoms, disabling these states for catalytic applications. The proposed experimental-theoretical approach may be useful for the design of other systems comprising metallic nanoparticles supported on distinct substrates, such as two-dimensional materials and porous matrices. These nanomaterials find several applications not only in heterogeneous catalysis, but also in sensing and optoelectronic devices.