Experimental and Theoretical Study of the Reactions between Vanadium−Silicon Heteronuclear Oxide Cluster Anions with n-Butane
Experimental and Theoretical Study of the Reactions between Vanadium−Silicon Heteronuclear Oxide Cluster Anions with n-Butane
复制标题
DOI：
10.1021/jp1045244
复制
发表时间：
2010-06
影响因子：
3.7
通讯作者：
Yan-xia Zhao;Xiao-Nan Wu;Jiabi Ma;Sheng‐Gui He;Xunlei Ding
中科院分区：
文献类型：
--
作者：
Yan-xia Zhao;Xiao-Nan Wu;Jiabi Ma;Sheng‐Gui He;Xunlei Ding
采用激光烧蚀法制备了钒硅异核氧化簇阴离子VxSiyOz−(x + y≥2,z≥4)，并与正丁烷（C4H10）在快流反应器中反应。用飞行时间质谱仪检测了反应前后的团簇分布。通过对含氢产物（V2O5）m(SiO2)nOH−(m = 1, n = 1−4;m = 2, n = 1)的观察，可以得出以下反应：（V2O5）m(SiO2)nO−+ C4H10→（V2O5）m(SiO2)nOH−+ C4H9。虽然在簇源中产生了V2O6−，但在相同的实验条件下没有产生V2O6H−。结果表明，特定的异核氧化物团簇V2O5(SiO2)1−40o−和（V2O5）2SiO2O−比同核氧化物团簇V2O6−（或v2o50−）更具有活性。采用密度泛函理论（DFT）研究了v2o5sioo2o−（或V2SiO8−）+ C4H10的反应机理。计算结果与实验结果吻合较好。（V2O5）m(SiO2)nO−…
Vanadium and silicon heteronuclear oxide cluster anions VxSiyOz− (x + y ≥ 2, z ≥ 4) are prepared by laser ablation and reacted with n-butane (C4H10) in a fast flow reactor. A time-of-flight mass spectrometer is used to detect the cluster distribution before and after the reactions. The observation of hydrogen-containing products (V2O5)m(SiO2)nOH− (m = 1, n = 1−4; m = 2, n = 1) strongly suggests the following reactions: (V2O5)m(SiO2)nO− + C4H10 → (V2O5)m(SiO2)nOH− + C4H9. Although V2O6− is produced in the cluster source, no V2O6H− product is produced under the same experimental condition. It indicates that specific heteronuclear oxide clusters V2O5(SiO2)1−4O− and (V2O5)2SiO2O− are more reactive than the homonuclear oxide cluster V2O6− (or V2O5O−). Density functional theory (DFT) calculations are performed to study reaction mechanisms of V2O5SiO2O− (or V2SiO8−) + C4H10. The calculated results are in good agreement with the experimental observations. The structural and bonding properties of (V2O5)m(SiO2)nO− ...