Sandwiched Graphene Interdiffusion Barrier for Preserving Au@Pt Atomically Thin Core@Shell Structure and the Resulting Oxygen Reduction Reaction Catalytic Activity.

The concept of a core-shell metallic structures, with a few atomic layers of the "shell" metal delineated from the "core" metal with atomic sharpness opens the door to a multitude of surface-driven materials properties that can be tuned. However, in practice, such architectures are difficult to retain due to the entropic cost of a segregated near-surface architecture, and the core and surface atoms inevitably mix through interdiffusion over time. We present here a systematic study of interdiffusion in a Pt on Au core-shell architecture and the role of an interrupting single layer of graphene sandwiched between them. The physical and chemical structure of the (near)surface is probed via mean-free-path tuned X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy (HRTEM), and electrochemistry (the oxygen reduction reaction, ORR). We find that at operating temperatures above 100 °C, there is potential for interdiffusion to occur between the primary and support metals of the core-shell catalyst system, which can diminish the catalyst activity toward ORR. The introduction of a single-layer graphene, as an interface between the core and shell metal layers, acts as a barrier that prevents unwanted surface alloying between the layered metals. HRTEM imaging shows that fully wetted Pt monolayers can be grown on a graphene template, allowing a high level of surface utilization of the catalyst material. We present how the use of graphene as a barrier to diffusion mitigates the loss of surface catalytic sites, showing much improved retention of Pt monolayer surface at elevated temperatures.