Exploring the Effects of a Doping Silver Atom on Anionic Gold Clusters’ Reactivity with O 2

作者：Lulu Huang, Wen Liu, Jin Hu, Xiaopeng Xing · 发表于：The Journal of Physical Chemistry A · 年份：2021 · DOI：10.1021/acs.jpca.1c06507 · 被引用次数：11 · 研究领域：Catalytic Processes in Materials Science、Nanocluster Synthesis and Applications、Nanomaterials for catalytic reactions

Reactivities of AgAu n –1 – ( n = 3–10) with O 2 at a low temperature were studied using an instrument combining a magnetron sputter cluster source, a microflow reactor, and a time-of-flight mass spectrometer. Their reaction products as well as size-dependent kinetic rates were nearly identical to those of corresponding Au n – ( n = 3–10). Previous experiments showed that the Ag atom in AgAu n –1 – ( n = 3–10) was fully or partially enclosed by the gold atoms. We studied the adsorption of O 2 on these reported structures using the B3LYP theory with relatively large basis sets. The theoretical results indicate that the adsorption sites as well as the adsorption energies of O 2 on AgAu n –1 – ( n = 3–10) are nearly identical to those on the corresponding Au n – ( n = 3–10). The O 2 adsorption on a series of proposed isomers of AgAu n –1 – (denoted as Au n –1 Ag – ), in which the silver atom was on the protruding site, was explored using the same theoretical methods. The O 2 tends to bond with the protruding Ag atoms, and the binding energies are apparently higher than those on the corresponding Au n – and AgAu n –1 – . The adsorption and activation of O 2 on Au n –, AgAu n –1 –, and Au n –1 Ag – were correlated with their global electron detachment energies (VDEs) as well as the element types of the adsorption sites. Generally, low VDE values and silver sites facilitate the O 2 adsorption, and these two factors separately dominate in various cluster species. The revealed effect...