Interfacial Structures of Trihexyltetradecylphosphonium-bis(mandelato)borate Ionic Liquid Confined between Gold Electrodes

详细信息    查看全文

• 作者：Yong-Lei Wang ; Mikhail Golets ; Bin Li ; Sten Sarman ; Aatto Laaksonen
• 刊名：ACS Applied Materials & Interfaces
• 出版年：2017
• 出版时间：February 8, 2017
• 年：2017
• 卷：9
• 期：5
• 页码：4976-4987
• 全文大小：798K
• ISSN：1944-8252

文摘

Atomistic molecular dynamics simulations have been performed to study microscopic the interfacial ionic structures, molecular arrangements, and orientational preferences of trihexyltetradecylphosphonium-bis(mandelato)borate ([P_6,6,6,14][BMB]) ionic liquid confined between neutral and charged gold electrodes. It was found that both [P_6,6,6,14] cations and [BMB] anions are coabsorbed onto neutral electrodes at different temperatures. The hexyl and tetradecyl chains in [P_6,6,6,14] cations lie preferentially flat on neutral electrodes. The oxalato and phenyl rings in [BMB] anions are characterized by alternative parallel–perpendicular orientations in the mixed innermost ionic layer adjacent to neutral electrodes. An increase in temperature has a marginal effect on the interfacial ionic structures and molecular orientations of [P_6,6,6,14][BMB] ionic species in a confined environment. Electrifying gold electrodes leads to peculiar changes in the interfacial ionic structures and molecular orientational arrangements of [P_6,6,6,14] cations and [BMB] anions in negatively and positively charged gold electrodes, respectively. As surface charge density increases (but lower than 20 μC/cm²), the layer thickness of the mixed innermost interfacial layer gradually increases due to a consecutive accumulation of [P_6,6,6,14] cations and [BMB] anions at negatively and positively charged electrodes, respectively, before the formation of distinct cationic and anionic innermost layers. Meanwhile, the molecular orientations of two oxalato rings in the same [BMB] anions change gradually from a parallel–perpendicular feature to being partially characterized by a tilted arrangement at an angle of 45° from the electrodes and finally to a dominant parallel coordination pattern along positively charged electrodes. Distinctive interfacial distribution patterns are also observed accordingly for phenyl rings that are directly connected to neighboring oxalato rings in [BMB] anions.