N2 dissociation on AuCoFeMoRu high-entropy alloys: Circumventing scaling relations and step dependencies

Finding a better catalyst for the reduction of nitrogen to ammonia would be of considerable use to the chemical industry, allowing for cheaper and possibly decentralized ammonia production. One approach to find a better catalyst is to explore the element component space continuously via the use of high-entropy alloys, uncovering as of yet untested multi-element catalysts and reaction sites to optimize reaction activity. Utilizing DFT calculations and microkinetic modeling, we use the AuCoFeMoRu high-entropy alloy as a discovery platform for \ch{N2} reduction catalysts. Testing both terrace and step sites, we find that high-entropy alloy terraces can reach as high activities as steps for the \ch{N2} reduction reaction, due to their heterogeneous surface structure. We also find that high-entropy alloys are able to circumvent the scaling relations to an extent, due to the decoupling of the transition state and final state structure of the reaction. We discover several promising high-entropy alloy reaction sites, with a roughly twofold improvement in activity over the best monometallic surface. However, significantly larger gains in activity seem to still be fundamentally limited by the scaling relations.