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

Abstract The size dependence of metal cluster reactions frequently reveals valuable information on the mechanism of nanometal catalysis. Here, the reactivity of the Pt n + ( n = 1−40) clusters with N 2 O is studied and a significant dependence on the size of these clusters is noticed. Interestingly, the small Pt n + clusters like Pt 3 + and Pt 4 + are inclined to form N 2 O complexes; some larger clusters, such as Pt 19 + , Pt 21 + , and Pt 23 + , appear to be unreactive; however, the others such as Pt 3 , 9,15 + and Pt 18 + are capable of decomposing N 2 O. While Pt 9 + rapidly reacts with N 2 O to form a stable quasitetrahedron Pt 9 O + product, Pt 18 + experiences a series of N 2 O decompositions to produce Pt 18 O 1‐7 + . Utilizing high‐precision theoretical calculations, it is shown how the atomic structures and active sites of Pt n + clusters play a vital role in determining their reactivity. Cooperative dual Lewis‐acid sites (CDLAS) can be achieved on specific metal clusters like Pt 18 + , rendering accelerated N 2 O 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 N 2 O is illustrated, offering insights into cluster catalysis in reactions that include the donation of electron pairs.