Solvation Properties of Silver and Copper Ions in a Room Temperature Ionic Liquid: A First-Principles Study.
Solvation Properties of Silver and Copper Ions in a Room Temperature Ionic Liquid: A First-Principles Study.
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DOI：
10.1021/acs.jpcb.8b10559
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发表时间：
2018-11
期刊：
影响因子：
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通讯作者：
T. Pham;C. Horwood;A. Maiti;Vanessa Peters;T. Bunn;M. Stadermann
中科院分区：
文献类型：
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作者：
T. Pham;C. Horwood;A. Maiti;Vanessa Peters;T. Bunn;M. Stadermann
了解金属离子在室温离子液体（IL）中的行为对于预测和优化金属电沉积等技术的性能至关重要;然而，许多机械细节仍然是谜，包括离子液体中离子的溶剂化特性以及它们如何受到离子和液体物质之间的内在相互作用的影响。在这里，我们利用第一性原理分子动力学模拟解开和比较的关键结构特性的Ag+和Cu+离子在一个共同的室温IL，1-乙基-3-甲基咪唑三氟甲磺酸盐。我们发现，当与Cu+相比，较大的Ag+显示出更无序和灵活的溶剂化结构，其溶剂化壳层之间的IL物种的更频繁的交换。此外，我们的模拟揭示了一个有趣的模拟在IL和水环境中的离子的溶剂化行为，特别是在离子的电子结构对它们的溶剂化性质的影响。这项工作提供了基本的理解的内在属性的金属离子在IL，同时提供机械的理解和战略，为未来选择的IL的金属电沉积过程。
Understanding the behavior of metal ions in room temperature ionic liquids (ILs) is essential for predicting and optimizing performance for technologies like metal electrodeposition; however, many mechanistic details remain enigmatic, including the solvation properties of the ions in ILs and how they are governed by the intrinsic interaction between the ions and the liquid species. Here, we utilize first-principles molecular dynamics simulations to unravel and compare the key structural properties of Ag+ and Cu+ ions in a common room temperature IL, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate. We find that, when compared to Cu+, the larger Ag+ shows a more disordered and flexible solvation structure with a more frequent exchange of the IL species between its solvation shells. In addition, our simulations reveal an interesting analog in the solvation behavior of the ions in the IL and aqueous environments, particularly in the effect of the ion electronic structures on their solvation properties. This work provides fundamental understanding of the intrinsic properties of the metal ions in the IL, while offering mechanistic understanding and strategy for future selection of ILs for metal electrodeposition processes.