What Atomic Positions Determines Reactivity of a Surface? Long‐Range, Directional Ligand Effects in Metallic Alloys. Issue 9 (14th February 2021)

• Record Type: Journal Article
• Authors: Clausen, Christian M.; Batchelor, Thomas A. A.; Pedersen, Jack K.; Rossmeisl, Jan
• Is Part Of: Advanced science. Volume 8:Issue 9(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-02-14
• Subjects: adsorption energy predictions -- electrocatalysis -- high‐entropy alloys -- ligand effects -- oxygen reduction reaction; Science -- Periodicals; 505
• DOI: 10.1002/advs.202003357
• Languages: English
• ISSNs: 2198-3844

Abstract

Abstract: Ligand and strain effects can tune the adsorption energy of key reaction intermediates on a catalyst surface to speed up rate‐limiting steps of the reaction. As novel fields like high‐entropy alloys emerge, understanding these effects on the atomic structure level is paramount: What atoms near the binding site determine the reactivity of the alloy surface? By statistical analysis of 2000 density functional theory calculations and subsequent host/guest calculations, it is shown that three atomic positions in the third layer of an fcc(111) metallic structure fourth‐nearest to the adsorption site display significantly increased influence on reactivity over any second or third nearest atomic positions. Subsequently observed in multiple facets and host metals, the effect cannot be explained simply through the d‐band model or a valence configuration model but rather by favorable directions of interaction determined by lattice geometry and the valence difference between host and guest elements. These results advance the general understanding of how the electronic interaction of different elements affect adsorbate–surface interactions and will contribute to design principles for rational catalyst discovery of better, more stable and energy efficient catalysts to be employed in energy conversion, fuel cell technologies, and industrial processes. Abstract : A statistical analysis uncovers what atomic positions, near the binding site on the surface of an alloy, exert an electronic effect on the adsorbate–surface bond. It is found that a specific position in the third layer has a significantly larger effect on the binding energy than similar or closer positions due to a favorable direction of interaction.