Xu Qiang, Jiang Ling
National Institute of Advanced Industrial Science and Technology, Ikeda, Osaka 563-8577, Japan.
J Phys Chem A. 2006 Mar 2;110(8):2655-62. doi: 10.1021/jp055155d.
Laser-ablated Cu, Ag, and Au atoms react with CO and O2 mixture in solid argon to produce carbonyl metal oxides, (O2)Cu(CO)(n) (n = 1, 2), (eta(1)-OO)MCO (M = Ag, Au), OCAuO2CO, and OAuCO, as well as group 11 metal carbonyls and oxides. These carbonyl metal oxides are characterized using infrared spectroscopy on the basis of the results of the isotopic substitution and the CO concentration change. Density functional theory (DFT) calculations have been performed on these molecules. The identifications of these carbonyl metal oxides are confirmed by the good agreement between the experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts. Carbon dioxide is eliminated from these carbonyl metal oxides upon UV irradiation, providing the evidence for the oxidation of carbon monoxide on group 11 metal atoms. The present experiments also reveal that the reactivity of copper toward CO is prior to O2, and the reactivity of silver toward O2 is prior to CO, whereas the reactivity of gold toward CO is comparable to O2.
激光烧蚀的铜、银和金原子在固态氩气中与一氧化碳和氧气的混合物发生反应，生成羰基金属氧化物，如(O2)Cu(CO)(n)（n = 1, 2）、(η1-OO)MCO（M = 银、金）、OCAuO2CO和OAuCO，以及第11族金属羰基化合物和氧化物。基于同位素取代和一氧化碳浓度变化的结果，利用红外光谱对这些羰基金属氧化物进行了表征。对这些分子进行了密度泛函理论（DFT）计算。实验和计算得到的振动频率、相对吸收强度及同位素位移之间的良好一致性证实了这些羰基金属氧化物的鉴定结果。紫外线照射时，这些羰基金属氧化物会消除二氧化碳，这为一氧化碳在第11族金属原子上的氧化提供了证据。目前的实验还表明，铜对一氧化碳的反应活性高于对氧气的反应活性，银对氧气的反应活性高于对一氧化碳的反应活性，而金对一氧化碳和氧气的反应活性相当。
