乙腈基电解质的双层结构和阳离子依赖溶剂分解

IF 2.6 4区 化学 Q3 ELECTROCHEMISTRY
Pavithra Gunasekaran, Angel Cuesta
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引用次数: 0

摘要

我们利用衰减全反射模式下的表面增强红外吸收光谱(ATR-SEIRAS)结合伏安数据,分析了金电极和乙腈基电解质之间界面的微观结构。研究的重点是电位诱导的界面乙腈分子之间相互作用的变化,以及在含Li+-和Na+电解质中乙腈还原性分解的开始。乙腈分子表现出电位依赖的重定向,导致负电位下界面上反平行二聚体的浓度增加,因为分子的氮端被推离表面。在Li+-和Na+基电解质中乙腈还原分解的初始阶段是不同的。在LiClO4乙腈溶液中可以观察到胺的光谱特征,而在NaClO4中也可以观察到酰胺的光谱特征。由于乙腈中痕量的水必须是界面乙腈还原为胺和酰胺的质子源,因此在这些过程中也必须产生OH -。事实上,ATR-SEIRA光谱揭示了LiOH的形成和随后的沉淀。然而,在NaClO4中似乎没有NaOH的沉淀。随着负电位的增加,乙腈的还原裂解导致几种氰化物的形成。相应的氰化物特征带显示出电位依赖的拉伸频率,表明它们对应于吸附的物质。这些发现强调了电位诱导的溶剂重定向对界面上溶剂-溶剂相互作用的影响,以及电解质阳离子对乙腈还原分解产物的影响。图形抽象
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Double-layer structure and cation-dependent solvent decomposition in acetonitrile-based electrolytes

We present an analysis of the microscopic structure of the interface between a gold electrode and acetonitrile-based electrolytes, utilising surface-enhanced infrared absorption spectroscopy in attenuated total reflection mode (ATR-SEIRAS) combined with voltammetric data. The investigation focuses on the potential-induced changes in the interactions between interfacial acetonitrile molecules and on the onset of reductive acetonitrile decomposition in Li+- and Na+-containing electrolytes. The acetonitrile molecules exhibit a potential-dependent reorientation, leading to an increase in the concentration of antiparallel dimers at the interface at negative potentials, as the nitrogen end of the molecule is pushed away from the surface. The initial stages of reductive decomposition of acetonitrile are different in the Li+- and Na+-based electrolytes. Spectral signatures characteristic of amines are seen in LiClO4 acetonitrile solutions, while amide bands are also observed in NaClO4. Because traces of water in acetonitrile must be the proton source for the reduction of interfacial acetonitrile to amines and amides, OH must also be generated during those processes. In fact, ATR-SEIRA spectra reveal the formation and subsequent precipitation of LiOH. Precipitation of NaOH in NaClO4 seems to be absent, though. With increasingly negative potential, the reductive cleavage of acetonitrile results in the formation of several cyanide species. The corresponding cyanide-characteristic bands show a potential-dependent stretching frequency that suggests they correspond to adsorbed species. These findings highlight the effect of potential-induced solvent reorientation on solvent–solvent interactions at the interface as well as the impact of the electrolyte cation on the products of the reductive decomposition of acetonitrile.

Graphical Abstract

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来源期刊
CiteScore
4.80
自引率
4.00%
发文量
227
审稿时长
4.1 months
期刊介绍: The Journal of Solid State Electrochemistry is devoted to all aspects of solid-state chemistry and solid-state physics in electrochemistry. The Journal of Solid State Electrochemistry publishes papers on all aspects of electrochemistry of solid compounds, including experimental and theoretical, basic and applied work. It equally publishes papers on the thermodynamics and kinetics of electrochemical reactions if at least one actively participating phase is solid. Also of interest are articles on the transport of ions and electrons in solids whenever these processes are relevant to electrochemical reactions and on the use of solid-state electrochemical reactions in the analysis of solids and their surfaces. The journal covers solid-state electrochemistry and focusses on the following fields: mechanisms of solid-state electrochemical reactions, semiconductor electrochemistry, electrochemical batteries, accumulators and fuel cells, electrochemical mineral leaching, galvanic metal plating, electrochemical potential memory devices, solid-state electrochemical sensors, ion and electron transport in solid materials and polymers, electrocatalysis, photoelectrochemistry, corrosion of solid materials, solid-state electroanalysis, electrochemical machining of materials, electrochromism and electrochromic devices, new electrochemical solid-state synthesis. The Journal of Solid State Electrochemistry makes the professional in research and industry aware of this swift progress and its importance for future developments and success in the above-mentioned fields.
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