Abstract:
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Electrocatalytic properties of materials are
governed by the electronic structure, stability, and reactivity
of the surface layer which is exposed to the electrolyte. Over
the years, different strategies have been developed to tailor
electrocatalyst surfaces but also to reduce the cost of these
materials, which is the bottleneck for any practical application.
When a very thin metallic layer, intended to serve as an
electrocatalyst, is placed over a substrate, its configuration is
influenced by the structure of the substrate due to lattice
mismatch, while the electronic structure is affected due to the
strain and the electronic effects of the support. This results in
altered bonding within the electrocatalyst layer and the
modification of its electronic properties when compared to the
pure phase. In this contribution, we address the possibilities of theoretical prediction of surface properties of atomically thin
electrocatalyst films formed over different substrates, focusing on the metal side of the electrified interface. While all these
properties can be calculated quite easily using modern computational techniques (but used with care), most often based on
density functional theory, we also address an attractive, fast screening possibility to estimate the properties of monometallic and
multimetallic overlayers using small sets of calculations on model systems. We discuss how lattice mismatch between a substrate
and an overlayer can be used to predict the properties of electrocatalytic films, limitations of such approach, and a possibility of
deploying of large databases which enable rapid prescreening of different support/overlayer systems for various electrocatalytic
applications. |