In situ modulation of surface reaction is a powerful approach to drive high-yield H₂O₂ electrosynthesis on metal-free carbon. Here, we discover that cationic surfactants can work efficiently as an in situ kinetic promoter for the oxygen-to-peroxide reaction on a carbon black electrode, achieving a peroxide yield above 90% (up to 95.2%) across a >0.8 V window in alkaline media, the best among reported H₂O₂ electrocatalysts. Our characterizations and kinetic model analysis show that the high peroxide selectivity is attributable to surface carboxylates (–COO⁻) with weak peroxide binding under a Coulombic pull imposed by an adsorbed cationic layer. Although surface carbonyls (–C=O) also participate in the peroxide synthesis, they exhibit strong binding to peroxide and promote on-site reduction at moderate-to-high overpotential. At only a minute amount of cationic surfactant, a chronoamperometry experiment with a carbonyl-free system can deliver a peroxide production at a sustainably high selectivity (∼96%) over 10 h.

表面反应的原位调节是驱动无金属碳上高产率H ₂ O ₂电合成的有效方法。在这里，我们发现阳离子表面活性剂可以有效地作为原位动力学促进剂，用于炭黑电极上的氧-过氧化物反应，在> 0.8 V的窗口中实现90％以上的过氧化物收率（高达95.2％）。碱性介质，在报道的H ₂ O ₂电催化剂中最好。我们的表征和动力学模型分析表明，高选择性的过氧化物是由于表面羧酸盐（-COO ^-）在吸附的阳离子层施加的库仑力作用下具有弱的过氧化物结合力。尽管表面羰基（–C = O）也参与过氧化物的合成，但它们与过氧化物具有很强的结合力，并在中高电位下促进现场还原。仅需极少量的阳离子表面活性剂，使用无羰基体系的计时电流法实验可以在10小时内以持续较高的选择性（〜96％）提供过氧化物的生成。