Independent Multiple-Atom-Site Functionality in Composition Adjustable Immiscible Ru-Rh-Pd-Pt Solid-Solution High-Entropy Alloys for NOx Reduction Outperforming Rh.

Abstract

The high-entropy-alloy (HEA) nanoparticles with four, five or more metals significantly can yield the developments of functional materials with excellent performances in various reactions. However, the underlying reaction mechanisms of heterogeneous catalysis for HEA have been rarely investigated, due to their diverse elements and complex compositions. In this study, we successfully synthesized the homogeneously dispersed Ru-Rh-Pd-Pt HEA with adjustable compositions, as the multiple-atom-site catalysts (MASC). In the NOx reduction performance tests, Ru0.4 (Rh0.33Pd0.33Pt0.33)0.6 MASC showed the highest activity, which was significantly improved compared to that of the best monometal Rh, with the light-off temperature decreasing by ca. 50 °C. The Fourier transform infrared measurements revealed that the outstanding activity of Ru-Rh-Pd-Pt MASC was attributable to the well-coupled elementary steps of the CO adsorption, NO adsorption, NO dissociation and O spillover on the Ru, Rh, Rh-Pd and Pt sites, respectively, which explained the first clear reaction mechanism in heterogeneous catalysis for HEA.