Substrate engineering of graphene reactivity: towards high-performance graphene-based catalysts

Abstract Graphene-based solid-state catalysis is an emerging direction in research on graphene, which opens new opportunities in graphene applications and thus has attracted enormous interests recently. A central issue in graphene-based catalysis is the lack of an effective yet practical way to activate the chemically inert graphene, which is largely due to the difficulties in the direct treatment of graphene (such as doping transition metal elements and introducing particular type of vacancies). Here we report a way to overcome these difficulties by promoting the reactivity and catalytic activity of graphene via substrate engineering. With thorough first-principles investigations, we demonstrate that when introduce a defect, either a substitutional impurity atom (e.g. Au, Cu, Ag, Zn) or a single vacancy, in the underlying Ru (0001) substrate, the reactivity of the supported graphene can be greatly enhanced, resulting in the chemical adsorption of O₂ molecules on graphene. The origin of the O₂ chemical adsorption is found to be the impurity- or vacancy-induced significant charge transfer from the graphene–Ru (0001) contact region to the 2π* orbital of the O₂ molecule. We then further show that the charge transfer also leads to high catalytic activity of graphene for chemical reaction of CO oxidation. According to our calculations, the catalyzed CO oxidation takes place in Eley-Rideal (ER) mechanism with low reaction barriers (around 0.5 eV), suggesting that the substrate engineering is an effective way to turn the supported graphene into an excellent catalyst that has potential for large-scale industrial applications.