Epitaxial and Atomically Thin Graphene–Metal Hybrid Catalyst Films—the Dual Role of Graphene As the Support and the Chemically-Transparent Protective Cap

Abstract

Commercialization of polymer electrolyte membrane (PEM) fuel cell materials has been of a great interest over the past decade. At the cathode side, the oxygen reduction reaction (ORR) is the key reaction where sluggish kinetics is present, for which Pt remains the catalyst of choice. In order to leapfrog the current limits to Pt use, three main objectives have to be achieved. First, is a reduction of Pt loading; second, is an enhancement of the mass activity per Pt atom; and third is an increase the catalyst durability. Herein, we demonstrate the dual role of single graphene layer, both as a growth template and as a protective cap for 2D Pt monolayers catalysts, where all three objectives can be achieved.Using iterative under potential deposition (UPD), atomic layers of Pt catalyst are grown on top of a single layer graphene. X-ray absorption spectroscopic (XAS) and scanning transmission electron microscopy (STEM) analyses show that Pt growth is dictated by the graphene-templated epitaxy. Pt/graphene intimacy induces a localized compressive strain on Pt monolayers ranges 3-10%, owing to structural defects, with an overall compressive strain of 3.5% according to extended x-ray absorption fine structure (EXAFS) analysis. In addition, cyclic voltammetry (CV) analysis shows fully-wetted Pt monolayers coverage of graphene under-layer with only a ~1 nm ultra-thin layer of Pt, while ripening was suppressed as shown through STEM images. Atomic Force Microscopy (AFM) analysis demonstrates that Pt monolayers prefer to follow Frank-van der Merwe growth (i.e. layer-by-layer growth mode) rather than Volmer-Weber growth (i.e. island growth mode), where root mean square (rms) of surface roughness remains quite similar while increasing Pt loading is increased.Pt/graphene hybrid catalysts show superior catalytic activity for ORR relative to the graphene-free counterparts or state of the art Pt commercial catalyst. A combination of the graphene-imposed compressive strain and electron transfer, push the Pt d-band center up, lowering the overpotential needed for ORR to occur. Furthermore, the graphene/Pt cap hybrid shows the graphene protecting Pt MLs from both dissolution and from ripening, with no Pt loss after 1000 fuel cell operating cycles. Our demonstration of a graphene-Pt hybrid opens the door for graphene/metal or metal/graphene architectures with potential applications in, and not limited to, energy, thermo-electric and electronics field.