Pd6O4+: an oxidation resistant yet highly catalytically active nano-oxide cluster.
Pd6O4+: an oxidation resistant yet highly catalytically active nano-oxide cluster.
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DOI：
10.1021/ja308189w
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发表时间：
2012-12
影响因子：
15
通讯作者：
S. M. Lang;I. Fleischer;T. Bernhardt;R. Barnett;U. Landman
中科院分区：
文献类型：
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作者：
S. M. Lang;I. Fleischer;T. Bernhardt;R. Barnett;U. Landman
钯氧化物团簇Pd(6)O(4)（+）是裸钯团簇Pd(6)（+）在多碰撞条件下与分子氧在八爪离子阱中反应形成的唯一产物。这种氧化团簇在很大的温度范围内可以抵抗进一步的氧化，并且在低温下O(2)分子仅在其上物理吸附。Pd(6)O(4)（+）的特殊稳定性通过观察Pd(7)（+）与O(2)反应导致碎裂形成Pd(6)O(4)（+）得到证实。然而，在富氧O(2)/CO混合物中，Pd(6)O(4)（+）被认为是有效促进CO低温氧化的催化活性物质。气相反应动力学测量与第一级原理计算相结合，为纳米氧化物簇化学提供了详细的分子水平洞察，并能够揭示完整的催化燃烧反应循环。
The palladium oxide cluster Pd(6)O(4)(+) is formed as the sole product upon reaction of a bare palladium cluster Pd(6)(+) with molecular oxygen in an octopole ion trap under multicollision conditions. This oxide cluster is found to be resistant to further oxidation over a large temperature range, and further O(2) molecules merely physisorb on it at cryogenic temperatures. The particular stability of Pd(6)O(4)(+) is confirmed by the observation that the reaction of Pd(7)(+) with O(2) leads to fragmentation resulting in the formation of Pd(6)O(4)(+). However, in an oxygen-rich O(2)/CO mixture, Pd(6)O(4)(+) is identified as the catalytically active species that effectively facilitates the low-temperature oxidation of CO. Gas-phase reaction kinetics measurements in conjunction with first-principles calculations provide detailed molecular level insight into the nano-oxide cluster chemistry and are able to reveal the full catalytic combustion reaction cycle.