Tuning the energy barrier of water exchange reactions on Al(III) by interaction with the single-walled carbon nanotubes
Tuning the energy barrier of water exchange reactions on Al(III) by interaction with the single-walled carbon nanotubes
复制标题
通过与单壁碳纳米管的相互作用调节Al(III)上水交换反应的能垒
DOI：
10.1039/c0dt01582b
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发表时间：
2011-01-01
影响因子：
4
通讯作者：
Chen, Jianrong
中科院分区：
文献类型：
--
作者：
Feng, Hui;Qian, Zhaosheng;Chen, Jianrong
用密度泛函理论的ONIOM方法模拟了Al(III)在单壁碳纳米管(SWCNTs)内外的极限解离(D)和交换解离(I-d)水交换路径，考察了SWCNTs对D和I-d路径的影响.揭示了具有相同长度的锯齿形单壁碳纳米管(13，0)、(14，0)和(15，0)相互作用的交换解离水交换途径。结果表明，当反应发生在直径相对较小的单壁碳纳米管内部时，单壁碳纳米管对势垒的约束作用较强，且随单壁碳纳米管直径的变化而变化较大。结果还表明，单壁碳纳米管作为反式激活配体，有效地降低了单壁碳纳米管外的D和I-d途径的能垒。水铝络合物与碳纳米管之间的相互作用能有效地降低碳纳米管的势垒，加快反应速度，这对于碳纳米管对氢氧化铝等矿物的溶解和转化具有重要意义。
The limiting dissociative (D) and interchange dissociative (I-d) water exchange pathways on Al(III) inside and outside single-walled carbon nanotubes (SWCNTs) were modelled using ONIOM calculations with density functional theory, and the influence of SWCNTs on both D and I-d pathways was examined. The interchange dissociative water exchange pathway was revealed, in which the zigzag SWCNTs (13,0), (14,0) and (15,0) with the same length were modelled for interaction. The results indicate that the confinement effect of SWCNTs on the energy barriers is strong when the reaction takes place inside SWCNTs with small diameter relative to reaction complexes, and varies heavily along with the change of diameters of SWCNTs. The results also indicate that SWCNTs act as trans-activating ligand to effectively lower the energy barriers of both D and I-d pathways outside SWCNTs. The interaction between aluminium-water complexes and SWCNTs can effectively lower the energy barriers in general and may accelerate the reaction rates, which has great importance for the influence of carbon nanotubes on dissolution and transformation rates of minerals such as aluminium (hydr) oxide.