Lattice distortion releasing local surface strain on high-entropy alloys

Saturday 29 May 21
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High-entropy alloys (HEAs) have the potential to be a paradigm-shift for rational catalyst discovery but this new type of alloy requires a completely new approach to predict the surface reactivity. In addition to the ligand effect perturbing the surface-adsorbate bond, the random configuration of elements in the surface will also induce local strain effects due to the varying radii of neighboring atoms. Accurate modelling of HEA surface reactivity requires an estimate of this effect: To what degree is the adsorption of intermediates on these lattice distorted atomic environments affected by local strain?

In this study, more than 3,500 density functional theory (DFT) calculated adsorption energies of *OH and *O adsorbed on the HEAs IrPdPtRhRu and AgAuCuPdPt are statistically analyzed with respect to the lattice constants of the alloys and the surfaces of each individual binding site. It is found that the inherent distortion of the lattice structure in HEAs releases the local strain effect on the adsorption energy as the atomic environment surrounding the binding atom(s) settles into a relaxed structure. This is even observed to be true for clusters of atoms of which the sizes deviate significantly from the atomic environment in which they are embedded. This elucidates an important aspect of binding site interaction with the neighboring atoms and thus constitutes a step towards a more accurate theoretical model of estimating the reactivity of HEA surfaces.

Christian M. Clausen, Jack K. Pedersen, Thomas A. A. Batchelor & Jan Rossmeisl

Nano Research (2021)164 

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