Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Republic of China.
J Am Chem Soc. 2014 Mar 5;136(9):3617-23. doi: 10.1021/ja412608b. Epub 2014 Feb 21.
Laser ablation generated Au(x)(TiO2)(y)O(z)(-) (x = 0, 1; y = 2, 3; z = 1, 2) oxide cluster anions have been mass-selected using a quadrupole mass filter and reacted with CO in a hexapole collision cell. The reactions have been characterized by time-of-flight mass spectrometry and density functional theory calculations. Gold-titanium bimetallic oxide clusters Au(TiO2)(y)O(z)(-) are more reactive in CO oxidation than pure titanium oxide clusters (TiO2)(y)O(z)(-). The computational studies identify the dual roles that the gold atom plays in CO oxidation: functioning as a CO trapper and electron acceptor. Both factors are important for the high reactivity of Au(TiO2)(y)O(z)(-) clusters. To the best of our knowledge, this is the first example of CO oxidation by gold-containing heteronuclear oxide clusters, which provides molecular-level insights into the roles of gold in CO oxidation over oxide supports.
激光烧蚀产生的 Au(x)(TiO2)(y)O(z)(-)（x = 0, 1；y = 2, 3；z = 1, 2）氧化物团簇阴离子已使用四极质量过滤器进行质量选择，并在六极碰撞室中与 CO 反应。反应已通过飞行时间质谱法和密度泛函理论计算进行了表征。与纯氧化钛团簇（TiO2）（y）O（z）（-）相比，金-钛双金属氧化物团簇 Au（TiO2）（y）O（z）（-）在 CO 氧化中具有更高的反应性。计算研究确定了金原子在 CO 氧化中起的双重作用：作为 CO 捕获剂和电子受体。这两个因素对于 Au（TiO2）（y）O（z）（-）团簇的高反应性都很重要。据我们所知，这是首例含金异核氧化物团簇促进 CO 氧化的例子，它为金在氧化物载体上促进 CO 氧化中的作用提供了分子水平的见解。
