Reactivity Screening of Single Atoms on Modified Graphene Surface: From Formation and Scaling Relations to Catalytic Activity

Abstract Single atom catalysts (SACs) present the ultimate level of catalyst utilization, which puts them in the focus of current research. Using density functional theory calculations, model SACs consisting of nine metals (Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) on four different supports (pristine graphene, N‐ and B‐doped graphene and graphene with single vacancy) are analyzed. Only graphene with a single vacancy enables the formation of SACs, which are stable in terms of aggregation and dissolution under electrochemical conditions. Reactivity of models SACs is probed using atomic (hydrogen and A = C, N, O, and S) and molecular adsorbates (AH x , x = 1, 2, 3, or 4, depending on A). Scaling relations between adsorption energies of A and AH x on model SACs are confirmed. However, the scaling is broken for CH 3 . There is also an evident scaling between adsorption energies of atomic and molecular adsorbates on metals SAs supported by pristine, N‐doped and B‐doped graphene, which originates from similar electronic structures of SAs on these supports. Using the obtained data, the authors analyze the hydrogen evolution on the model SACs. Only M@graphene vacancy systems (excluding Ag and Au) are stable under hydrogen evolution conditions in highly acidic solutions.