Capacitive electronic metal-support interactions: Outer surface charging of supported catalyst particles

Electronic metal-support interactions (EMSI) in catalysis are commonly rationalized in terms of an electron transfer between supportmaterial and supportedmetal catalyst particles. This general perspective, however, cannot fully explain experimentally observed EMSI for metallic nanoparticulate catalysts, because the strong charge screening of metals should locally confine effects of direct electronic interaction with the support to the catalystsupport interface (CSI), which, apart from the perimeter, is largely inaccessible for catalysis reactants. The concept of capacitive EMSI is proposed here for catalyst particles at the nanometer scale, where electronic equilibration results in a long-range charging of the catalytically active outer surface (CAOS) bypassing the expected strong metallic charge screening, which is confirmed and quantified by electrostatic and density functional theory simulations revealing a strong dependence on the coverage of the support surface with catalyst particles. This long-range charge transfer leads to a shift of the local work function at the CAOS. In order to describe the catalytic consequences, an amendment of d-band theory in terms of 'd-band + work function' is proposed. Furthermore, the charging of remote catalytic sites at the CAOS scales with the relative dielectric constant of the surrounding medium, and it is concluded that EMSI can have surprisingly strong influence especially in the presence of a strongly polarizable dielectric.