Experimental and theoretical study of the reactions between vanadium oxide cluster cations and water.
Experimental and theoretical study of the reactions between vanadium oxide cluster cations and water.
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DOI：
10.1021/jp300279u
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发表时间：
2012-02
期刊：
影响因子：
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通讯作者：
Jiabi Ma;Yan-xia Zhao;Sheng‐Gui He;Xunlei Ding
中科院分区：
文献类型：
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作者：
Jiabi Ma;Yan-xia Zhao;Sheng‐Gui He;Xunlei Ding
采用激光烧蚀法制备了钒簇阳离子V(x)O(y)(+) (x = 2-6)，并与D(2)O在室温快流反应器中反应。用飞行时间质谱仪检测了反应前后的团簇分布。观察产物(V(2)O(5))(1-3)D（+）表明是氘原子萃取反应(V(2)O(5))(1-3)(+) + D(2)O→(V(2)O(5))(1-3)D(+) + OD。此外，实验中还观察到显著的缔合产物(V(2)O(5))(1-3)D(2)O（+）。采用密度泛函理论计算研究了V(4)O(10)（+）与H(2)O的反应机理。计算结果与实验结果一致，表明H(2)O在V(4)O(10)H(2)O（+）络合物中是解离吸附而不是分子吸附。
Vanadium oxide cluster cations V(x)O(y)(+) (x = 2-6) are prepared by laser ablation and are reacted with D(2)O in a fast flow reactor under room temperature conditions. A time-of-flight mass spectrometer is used to detect the cluster distribution before and after the reactions. Observation of the products (V(2)O(5))(1-3)D(+) indicates the deuterium atom abstraction reaction (V(2)O(5))(1-3)(+) + D(2)O → (V(2)O(5))(1-3)D(+) + OD. In addition, significant association products (V(2)O(5))(1-3)D(2)O(+) are also observed in the experiments. Density functional theory calculations are performed to study the reaction mechanisms of V(4)O(10)(+) with H(2)O. The calculated results are in agreement with the experimental observations and indicate that H(2)O is dissociatively rather than molecularly adsorbed in V(4)O(10)H(2)O(+) complex.