Best practices of modeling complex materials in electrocatalysis, exemplified by oxygen evolution reaction on...

Pentlandites are natural ores with structural properties comparable to that of [FeNi] hydrogenases. While this class of transition-metal sulfide materials - (Fe,Ni)₉S₈ - with a variable Fe : Ni ratio has been proven to be an active electrode material for the hydrogen evolution reaction, it is also discussed as electrocatalyst for the alkaline oxygen evolution reaction (OER), corresponding to the bottleneck of anion exchange membrane electrolyzers for green hydrogen production. Despite the experimental evidence for the use of (Fe,Ni)₉S₈ as an OER catalyst, a detailed investigation of the elementary reaction steps, including consideration of adsorbate coverages and limiting steps under anodic polarizing conditions, is still missing. We address this gap in the present manuscript by gaining atomistic insights into the OER on an Fe_4.5Ni_4.5S₈(111) surface through density functional theory calculations combined with a descriptor-based analysis. We use this system to introduce best practices for modeling this rather complex material by pointing out hidden pitfalls that can arise when using the popular computational hydrogen electrode approach to describe electrocatalytic processes at the electrified solid/liquid interface for energy conversion and storage.