Hydrogen peroxide (H₂O₂) is a widely used green oxidant. Until now, research has focused on the development of efficient catalysts for the two-electron oxygen reduction reaction (2e^– ORR). However, electrolyte effects on the 2e^– ORR have remained little understood. We report a significant effect of alkali metal cations (AMCs) on carbons in acidic environments. The presence of AMCs at a glassy carbon electrode shifts the half wave potential from −0.48 to −0.22 V_RHE. This cation-induced enhancement effect exhibits a uniquely sensitive on/off switching behavior depending on the voltammetric protocol. Voltammetric and in situ X-ray photoemission spectroscopic evidence is presented, supporting a controlling role of the potential of zero charge of the catalytic enhancement. Density functional theory calculations associate the enhancement with stabilization of the *OOH key intermediate as a result of locally induced field effects from the AMCs. Finally, we developed a refined reaction mechanism for the H₂O₂ production in the presence of AMCs.

中文翻译：

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阳离子对碳表面酸性氧还原反应的影响

过氧化氢（H ₂ O ₂）是一种广泛使用的绿色氧化剂。到目前为止，研究重点是开发用于双电子氧还原反应 (2e ^– ORR) 的高效催化剂。然而，电解质对 2e ^– ORR 的影响仍知之甚少。我们报告了碱金属阳离子（AMC）在酸性环境中对碳的显着影响。玻碳电极上 AMC 的存在将半波电位从 -0.48 V RHE 移至 -0.22 V _RHE。这种阳离子诱导的增强效应表现出独特的敏感开/关切换行为，具体取决于伏安法协议。伏安法和原位X 射线光电子能谱证据显示，支持催化增强的零电荷电势的控制作用。密度泛函理论计算将*OOH 关键中间体的增强与稳定性联系起来，这是 AMC 局部感应场效应的结果。最后，我们开发了一种在 AMC 存在下生产H ₂ O ₂的精细反应机制。