H/D Isotope Effects in the Electrochemistry of Electrochromic Iron Hexacyanoruthenate

IF 3.5 4区 化学 Q2 ELECTROCHEMISTRY
Lena Gerhards, Izabella Brand, Gunther Wittstock
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Abstract

The electrochemical deposition of iron hexacyanoruthenate (Fe−HCR) on gold electrodes was studied in electrolytes prepared with light and heavy water. Cyclic voltammetry of the material during preparation and after transfer to a precursor-free solution exhibits two reductions peaks in H2O-based electrolytes but only one reduction peak in D2O-based electrolytes. The voltammetric behavior changes reversibly upon transfer of the material between D2O-based and H2O-based 1 mol L−1 KCl solutions. No clear structural differences between samples prepared in D2O and H2O were detected by means of X-ray photoelectron spectroscopy (XPS) and polarization modulation infrared reflection absorption spectroscopy (PM IRRAS). We noted a relatively slow exchange of coordinated water and a fast exchange of zeolitic water. Using voltammetric experiments we could rule out simple effects of solution conductivity for K+, participation of H+/D+ in the charge compensation and surface effects on the observed dependence of the peak splitting on the isotopic composition of the solvent. The most likely reason for the observed behavior is the different structure of the H-bonded water network of coordinated H2O and zeolitic H2O/D2O which is supported by the PM IRRAS data.

Abstract Image

电致变色六氰钌酸铁电化学中的 H/D 同位素效应
在用轻水和重水制备的电解质中,研究了金电极上六氰基钌酸铁(Fe-HCR)的电化学沉积。材料在制备过程中和转移到不含前驱体的溶液中后的循环伏安特性在以 H2O 为基质的电解质中显示出两个还原峰,而在以 D2O 为基质的电解质中只有一个还原峰。材料在 D2O 基和 H2O 基 1 mol L-1 KCl 溶液之间转移时,伏安行为会发生可逆变化。通过 X 射线光电子能谱(XPS)和偏振调制红外反射吸收光谱(PM IRRAS)检测,在 D2O 和 H2O 溶液中制备的样品没有明显的结构差异。我们注意到配位水的交换相对较慢,而沸石水的交换较快。通过伏安实验,我们可以排除 K+ 溶液电导率的简单影响、H+/D+ 参与电荷补偿以及表面效应对观察到的峰值分裂与溶剂同位素组成的依赖关系的影响。观察到的行为最可能的原因是配位 H2O 和沸石 H2O/D2O 的 H 键水网络结构不同,这一点得到了 PM IRRAS 数据的支持。
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来源期刊
ChemElectroChem
ChemElectroChem ELECTROCHEMISTRY-
CiteScore
7.90
自引率
2.50%
发文量
515
审稿时长
1.2 months
期刊介绍: ChemElectroChem is aimed to become a top-ranking electrochemistry journal for primary research papers and critical secondary information from authors across the world. The journal covers the entire scope of pure and applied electrochemistry, the latter encompassing (among others) energy applications, electrochemistry at interfaces (including surfaces), photoelectrochemistry and bioelectrochemistry.
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