The Reactivity of Ptn+ Clusters With N2O Facilitated by Dual Lewis‐Acid Sites

Abstract

AbstractThe size dependence of metal cluster reactions frequently reveals valuable information on the mechanism of nanometal catalysis. Here, the reactivity of the Ptn+ (n = 1−40) clusters with N2O is studied and a significant dependence on the size of these clusters is noticed. Interestingly, the small Ptn+ clusters like Pt3+ and Pt4+ are inclined to form N2O complexes; some larger clusters, such as Pt19+, Pt21+, and Pt23+, appear to be unreactive; however, the others such as Pt3,9,15+ and Pt18+ are capable of decomposing N2O. While Pt9+ rapidly reacts with N2O to form a stable quasitetrahedron Pt9O+ product, Pt18+ experiences a series of N2O decompositions to produce Pt18O1‐7+. Utilizing high‐precision theoretical calculations, it is shown how the atomic structures and active sites of Ptn+ clusters play a vital role in determining their reactivity. Cooperative dual Lewis‐acid sites (CDLAS) can be achieved on specific metal clusters like Pt18+, rendering accelerated N2O decomposition via both N‐ and O‐bonding on the neighboring Pt atoms. The influence of CDLAS on the size‐dependent reaction of Pt clusters with N2O is illustrated, offering insights into cluster catalysis in reactions that include the donation of electron pairs.