Ma Jia-Bi, Meng Jing-Heng, He Sheng-Gui
Key Laboratory of Cluster Science, The Institute for Chemical Physics, School of Chemistry, Beijing Institute of Technology, 100081, Beijing, People's Republic of China.
Dalton Trans. 2015 Feb 21;44(7):3128-35. doi: 10.1039/c4dt03398a.
Cerium-vanadium oxide cluster cations CeVO5(+) were generated by laser ablation, mass-selected using a quadrupole mass filter, thermalized through collisions with helium atoms, and then reacted with ethene molecules in a linear ion trap reactor. The cluster reactions have been characterized by time-of-flight mass spectrometry and density functional theory calculations. The CeVO5(+) cluster has a closed-shell electronic structure and contains a peroxide (O2(2-)) unit. The cluster bonded O2(2-) species is reactive enough to oxidize a C2H4 molecule to generate C2H4O2 that can be an acetic acid molecule. Atomic oxygen radicals (O(-)˙), superoxide radicals (O2(-)˙), and peroxides are the three common reactive oxygen species. The reactivity of cluster bonded O(-)˙ and O2(-)˙ radicals has been widely studied while the O2(2-) species were generally thought to be much less reactive or inert toward small molecules under thermal collision conditions. This work is among the first to report the reactivity of the peroxide unit on transition metal oxide clusters with hydrocarbon molecules, to the best of our knowledge.
通过激光烧蚀产生铈 - 钒氧化物簇阳离子CeVO5(+)，使用四极杆质量过滤器进行质量选择，通过与氦原子碰撞使其热化，然后在线性离子阱反应器中与乙烯分子反应。通过飞行时间质谱和密度泛函理论计算对簇反应进行了表征。CeVO5(+)簇具有闭壳层电子结构，并包含一个过氧化物（O2(2-)）单元。与簇结合的O2(2-)物种具有足够的反应活性，能够将C2H4分子氧化生成C2H4O2，后者可能是一个乙酸分子。原子氧自由基（O(-)˙）、超氧自由基（O2(-)˙）和过氧化物是三种常见的活性氧物种。与簇结合的O(-)˙和O2(-)˙自由基的反应活性已得到广泛研究，而在热碰撞条件下，O2(2-)物种通常被认为对小分子的反应活性要低得多或呈惰性。据我们所知，这项工作是最早报道过渡金属氧化物簇上过氧化物单元与烃分子反应活性的研究之一。
