Study on Preferential Solvation of Water by Electrochemical Method
Study on Preferential Solvation of Water by Electrochemical Method
复制标题
电化学法优先溶解水的研究
DOI：
10.1002/elan.201900243
复制
发表时间：
2019-07
期刊：
影响因子：
3
通讯作者：
Huibo Shao
中科院分区：
文献类型：
--
作者：
Chunxia Yan;Ximing Huang;Jingchao Chen;Haixia Guo;Huibo Shao
水的优先溶剂化在二茂铁的研究中起着重要的作用，是当前研究的热点。对金电极在乙腈/水溶液中的伏安特性进行了研究，结果表明金电极优先溶于水。本文采用循环伏安法、电化学阻抗谱法和双步计时电流法等电化学方法研究了水在乙腈/水中的优先溶剂化。二茂铁乙醇（FcCH2OH）分子作为溶质在无水乙腈中自发吸附在电极表面，导致乙腈分子倾向于在电极表面形成乙腈溶剂层，并且乙腈溶剂层比水溶剂层具有更低的能垒，这是通过模拟溶剂化得到的。溶剂对溶质的电化学行为影响很大。一旦乙腈溶剂中有一定量的水，吸附在电极表面的FcCH2OH就会解吸。这是因为就溶剂和溶质之间的分子间作用力而言，水优先与FcCH2OH溶剂化。此外，在溶剂化效应中，水分子与FcCH2OH分子之间的氢键比乙腈分子与FcCH2OH分子之间的偶极-偶极相互作用更强。通过改变FcCH2OH的电化学行为，用电化学方法分析了水的优先溶剂化。
The preferential solvation of water plays an important role in ferrocene research which is a subject of current interest. Voltammetric investigations were carried out for Au electrode in acetonitrile/water, showing preferential solvation of water. In our work, the preferential solvation of water in acetonitrile/water was studied by electrochemical methods including cyclic volitammetry, electrochemical impedance spectra and double‐step chronoamperometry. Ferrocenemethanol (FcCH2OH) molecules as a solute spontaneously adsorb on the electrode surface in anhydrous acetonitrile, resulting from acetonitrile molecules tend to form an acetonitrile solvent layer on the surface of the electrode and acetonitrile solvent layer has a lower energy barrier than the aqueous solvent layer, which has been obtained by modeling solvation. The solvent strongly influences electrochemical behavior of solute. Once there is an amount of water in acetonitrile solvent, FcCH2OH that adsorbed on the electrode surface desorb. This is because water preferentially solvate with FcCH2OH in term of intermolecular forces between solvent and solute. Moreover, hydrogen bond between water molecules and FcCH2OH molecules is stronger than dipole‐dipole interaction between acetonitrile molecules and FcCH2OH molecules in solvation effect. Through electrochemical behavior of FcCH2OH changing, preferential solvation of water is analyzed by electrochemical methods.
登录
查看更多内容
影响因子：
2.9
作者：
Królicki, R;Jarzeba, W;Lampre, I
通讯作者：
Lampre, I
影响因子：
3.7
作者：
F. F. Batista-F.;L. Siqueira;Luciano T. Costa;T. L. Ferreira
通讯作者：
F. F. Batista-F.;L. Siqueira;Luciano T. Costa;T. L. Ferreira
影响因子：
6
作者：
F. Naderi;A. Farajtabar;F. Gharib,
通讯作者：
F. Naderi;A. Farajtabar;F. Gharib,
DOI：
10.1016/j.physa.2017.11.113
发表时间：
2018-02
影响因子：
3.3
作者：
S. Shimizu;N. Matubayasi
通讯作者：
S. Shimizu;N. Matubayasi
DOI：
--
发表时间：
1999
期刊：
Hungarian Journal of Industrial Chemistry
影响因子：
--
作者：
Mc. Iliuta;F. Thyrion
通讯作者：
Mc. Iliuta;F. Thyrion