Linking Electric Double Layer Formation to Electrocatalytic Activity
Linking Electric Double Layer Formation to Electrocatalytic Activity
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电双电层的形成与电催化活性的关系
DOI：
10.1021/acscatal.3c04255
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发表时间：
2023-12
期刊：
影响因子：
12.9
通讯作者：
Matthew A. Gebbie;Beichen Liu;Wenxiao Guo;Seth R. Anderson;Samuel G. Johnstone
中科院分区：
文献类型：
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作者：
Matthew A. Gebbie;Beichen Liu;Wenxiao Guo;Seth R. Anderson;Samuel G. Johnstone
双电层在电极-电解质界面处形成，并且通常在控制电化学反应速率和选择性方面起决定性作用。虽然双电层的形成仍然是一个活跃的研究领域超过世纪，大多数框架用于预测双电层的性质，如局部离子浓度，电位梯度和反应物的化学势，仍然植根于经典的Gouy-Chapman-Stern理论，它忽略了离子-离子相互作用，并假设非反应界面。然而，最近的研究结果从表面力和电催化社区强调了如何出现离子-离子相互作用从根本上改变双电层形成机制和界面特性。值得注意的是，最近对离子液体的研究表明，离子相关性和聚集可以显著改变反应速率和选择性，特别是在浓电解质中。此外，新兴的研究表明，双电层结构和动力学显着变化的电位发生电催化反应。在这里，我们提供了我们的观点，离子-离子相互作用如何影响双电层特性，并有助于调制电催化系统，特别是在高离子浓度和大的外加电位导致偏离经典电解质理论的条件下。我们还总结了日益增长的问题和机会，以进一步探讨电化学反应如何可以大大改变双电层的性质。最后，我们的观点，这些研究结果如何打开大门，使用电催化反应研究双电层的形成，并实现工程电极-电解质界面的电化学转换。
Electric double layers form at electrode–electrolyte interfaces and often play defining roles in governing electrochemical reaction rates and selectivity. While double layer formation has remained an active area of research for more than a century, most frameworks used to predict electric double layer properties, such as local ion concentrations, potential gradients, and reactant chemical potentials, remain rooted in classical Gouy–Chapman–Stern theory, which neglects ion–ion interactions and assumes nonreactive interfaces. Yet, recent findings from the surface forces and electrocatalysis communities have highlighted how the emergence of ion–ion interactions fundamentally alters electric double layer formation mechanisms and interface properties. Notably, recent studies with ionic liquids show that ionic correlations and clustering can substantially alter reaction rates and selectivity, especially in concentrated electrolytes. Further, emerging studies suggest that electric double layer structures and dynamics significantly change at potentials where electrocatalytic reactions occur. Here, we provide our perspective on how ion–ion interactions can impact electric double layer properties and contribute to modulating electrocatalytic systems, especially under conditions where high ion concentrations and large applied potentials cause deviations from classical electrolyte theory. We also summarize growing questions and opportunities to further explore how electrochemical reactions can drastically alter electric double layer properties. We conclude with a perspective on how these findings open the door to using electrocatalytic reactions to study electric double layer formation and achieve electrochemical conversion by engineering electrode–electrolyte interfaces.