Unraveling the Mechanisms of O2 Activation by Size-Selected Gold Clusters: Transition from Superoxo to Peroxo Chemisorption

被引:146
作者
Pal, Rhitankar [2 ]
Wang, Lei-Ming [3 ]
Pei, Yong [4 ]
Wang, Lai-Sheng [1 ]
Zeng, Xiao Cheng [2 ]
机构
[1] Brown Univ, Dept Chem, Providence, RI 02912 USA
[2] Univ Nebraska Lincoln, Dept Chem, Lincoln, NE 68588 USA
[3] Univ Pittsburgh, Dept Phys & Astron, Pittsburgh, PA 15260 USA
[4] Xiangtan Univ, Dept Chem, Key Lab Environmentally Friendly Chem & Applicat, Xiangtan 411105, Hunan, Peoples R China
基金
美国国家科学基金会;
关键词
MOLECULAR-OXYGEN; CARBON-MONOXIDE; ADSORPTION; ANIONS; NANOPARTICLES; CO; OPTIMIZATION; CATALYSIS; OXIDATION; COPPER;
D O I
10.1021/ja302902p
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The activation of dioxygen is a key step in CO oxidation catalyzed by gold nanoparticles. It is known that small gold cluster anions with even-numbered atoms can molecularly chemisorb O-2 via one-electron transfer from Au-n(-) to O-2, whereas clusters with odd-numbered atoms are inert toward O-2. Here we report spectroscopic evidence of two modes of O-2 activation by the small even-sized Au-n(-) clusters: superoxo and peroxo chemisorption. Photoelectron spectroscopy of O2Au8- revealed two distinct isomers, which can be converted from one to the other depending on the reaction time. Ab initio calculations show that there are two close-lying molecular O-2-chemisorbed isomers for O2Au8-: the lower energy isomer involves a peroxo-type binding of O-2 onto Au-8(-), while the superoxo chemisorption is a slightly higher energy isomer. The computed detachment transitions of the superoxo and peroxo species are in good agreement with the experimental observation. The current work shows that there is a superoxo to peroxo chemisorption transition of O-2 on gold clusters at Au-8(-): O2Aun- (n = 2, 4, 6) involves superoxo binding and n = 10, 12, 14, 18 involves peroxo binding, whereas the superoxo binding re-emerges at n = 20 due to the high symmetry tetrahedral structure of Au-20, which has a very low electron affinity. Hence, the two-dimensional (2D) Au8- is the smallest anionic gold nanoparticle that prefers peroxo binding with O-2. At Au-12(-), although both 2D and 3D isomers coexist in the cluster beam, the 3D isomer prefers the peroxo binding with O-2.
引用
收藏
页码:9438 / 9445
页数:8
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