Performance of electrocatalyst in an aqueous electrolyte is greatly influenced by the structure of electrolyte-electrocatalyst interface. Regulating mass transfer is important in controlling surface reactions to alter the overall reaction kinetics. Thus, modification of interfacial structures is an effective approach to improving the electrocatalytic performance. In this paper, we report the use of functionalized amine-based covalent organic frameworks (COFs) as the modifier of electrocatalytic properties by facilitating the proton transfer of hydrogen evolution reaction (HER) in an acidic medium. Results from the electrochemical solid-liquid interface (ESLI)-based density functional theory (DFT) calculations suggest that functionalized COFs increase the local hydrogen concentration at the COF-electrocatalyst interface. Our simulation data indicates the enhancement in HER activity is achieved partially through the protonation site of the secondary amine of the COF on electrode surface, suggesting a new mode of controlling interfacial proton transfer for improving the HER kinetics.

中文翻译：

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胺基共价有机骨架对铂电催化剂析氢反应性能的影响


水性电解质中电催化剂的性能很大程度上受电解质-电催化剂界面结构的影响。调节传质对于控制表面反应以改变整体反应动力学非常重要。因此，界面结构的修饰是提高电催化性能的有效途径。在本文中，我们报告了使用官能化胺基共价有机框架（COF）作为电催化性能的改性剂，通过促进酸性介质中析氢反应（HER）的质子转移。基于电化学固液界面 (ESLI) 的密度泛函理论 (DFT) 计算结果表明，功能化 COF 增加了 COF-电催化剂界面处的局部氢浓度。我们的模拟数据表明，HER 活性的增强部分是通过电极表面 COF 仲胺的质子化位点实现的，这提出了一种控制界面质子转移以改善 HER 动力学的新模式。