Alkali metal cations change the hydrogen evolution reaction mechanisms at Pt electrodes in alkaline media
Alkali metal cations change the hydrogen evolution reaction mechanisms at Pt electrodes in alkaline media
复制标题
碱金属阳离子改变碱性介质中铂电极的析氢反应机制
DOI：
10.1016/j.nanoms.2022.09.003
复制
发表时间：
2022
影响因子：
9.9
通讯作者：
Gubanova, Elena
中科院分区：
文献类型：
--
作者：
Taji, Yamen;Zagalskaya, Alexandra;Evazzade, Iman;Watzele, Sebastian;Song, Kun-Ting;Xue, Song;Schott, Christian;Garlyyev, Batyr;Alexandrov, Vitaly;Gubanova, Elena
近些年来，看似惰性的碱金属阳离子对电极材料对能量供应所必需的反应的电催化活性的影响已成为大量研究工作的重点。碱性水电解过程中的析氢、析氧反应以及燃料电池中发生的氧电还原反应尤为重要。电催化中AM阳离子效应的所有细节都没有统一的理论来解释。例如，目前还不清楚“旁观者”AM-离子如何改变电催化反应的动力学，通常比电极结构和组成的改变更显著。造成这种情况的部分原因是缺乏对这一现象的系统的实验和理论研究。本工作利用交流阻抗谱研究了AM离子对铂微电极析氢反应机理的影响。活性遵循如下趋势：Li+≥Na+&Gt；K+&Gt；Cs+，其中最高活性对应于0.1GMLiOH电解液在低过电位下的活性。我们证明，AM阳离子的性质也改变了Volmer-Heyrovsky和Volmer-Tafel机制对整个反应的相对贡献，其中前者对LiOH电解液更重要。我们基于密度泛函理论的热力学和分子动力学计算支持这些发现。
The effects of seemingly inert alkali metal (AM) cations on the electrocatalytic activity of electrode materials towards reactions essential for energy provision have become the emphasis of substantial research efforts in recent years. The hydrogen and oxygen evolution reactions during alkaline water electrolysis and the oxygen electro-reduction taking place in fuel cells are of particular importance. There is no universal theory explaining all the details of the AM cation effect in electrocatalysis. For example, it remains unclear how “spectator” AM-cations can change the kinetics of electrocatalytic reactions often more significantly than the modifications of the electrode structure and composition. This situation originates partly from a lack of systematic experimental and theoretical studies of this phenomenon. The present work exploits impedance spectroscopy to investigate the influence of the AM cations on the mechanism of the hydrogen evolution reaction at Pt microelectrodes. The activity follows the trend: Li+≥Na+>K+>Cs+, where the highest activity corresponds to 0.1 M LiOH electrolytes at low overpotentials. We demonstrate that the nature of the AM cations also changes the relative contribution of the Volmer–Heyrovsky and Volmer–Tafel mechanisms to the overall reaction, with the former being more important for LiOH electrolytes. Our density functional theory-based thermodynamics and molecular dynamics calculations support these findings.
EIS数据拟合混合算法的开发
DOI：
--
发表时间：
2013
期刊：
影响因子：
--
作者：
A. Bandarenka
通讯作者：
A. Bandarenka