How Can the PtPd‐Based High‐Entropy Alloy Triumphs Conventional Twc Catalyst During the NO Reduction? A Density Functional Theory Study

Abstract Density functional theory is used to compare the catalytic performance of PtPdRhFeCo(100) high entropy alloy (HEA) three‐way catalyst (TWC) to the conventional Pt(100) in the NO reduction step during NH 3 production that supplies to passive NH 3 ‐SCR. Stronger adsorption of NO on the HEA(100) surface is beneficial to capture NO. During adsorption, the catalyst surface acts as an electron donor while the adsorbate is the acceptor on both HEA(100) and Pt(100) systems. Herein, the reaction mechanism of NO reduction can be classified into two steps: 1) NO activation and 2) product formation. During NO activation, direct NO dissociation is the preferable pathway on both HEA(100) and Pt(100) surfaces with the same E a , whereas HNO and NOH pathways on HEA(100) are suppressed. For NH 3 , N 2 , and N 2 O production on HEA(100) is found to be more difficult than on Pt(100). However, the thermodynamic driving force of all reactions on HEA(100) is more spontaneous than on Pt(100). Also, the rate‐determining step on HEA(100) is found to be NH 3 formation different from the Pt(100), while difficult H diffusion on HEA(100) is the key factor that reduces NH 3 production.