The hydrogenation of small molecules (like O2 and CO2) often exhibits strong activity dependence on pHs because of discrepant proton donor environments. However, some catalysts can show seldom dependence on two‐electron oxygen electroreduction, a sustainable route of O2 hydrogenation to hydrogen peroxide (H2O2). In this work, a pH‐resistant oxygen electroreduction system arising from the pseudo‐Jahn–Teller effect is demonstrated. Thorough operando Raman spectra, local environment analyses and density function theory simulations, the lattice distortion of TiOxFy that introduces the pseudo‐Jahn–Teller effect contributing to regulating local pHs at electrode–electrolyte interfaces and the absorption/desorption of key *OOH intermediate is revealed. Consequently, as comparison to 78.6% activity attenuation for common catalyst, the TiOxFy displays minor activity decay (3.2%) in the pH range of 1–13 with remarkable Faradaic efficiencies (93.4–96.4%) and H2O2 yield rates (595–614 mg cm−2 h−1) in the current densities of 100–1000 mA cm−2. Further techno‐economics analyses display the H2O2 production cost dependent on pHs, giving the lowest H2O2 price of $0.37 kg−1. The present finding is expected to provide an additional dimension to pseudo‐Jahn–Teller effect that leverages systems beyond traditional conception.

中文翻译：

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赝 Jahn-Teller 效应打破了双电子氧电还原中的 pH 依赖性


由于质子供体环境的差异，小分子（如 O2 和 CO2）的氢化通常表现出对 pH 值的强烈活性依赖性。然而，一些催化剂很少表现出对双电子氧电还原的依赖性，双电子氧电还原是 O2 氢化成过氧化氢 (H2O2) 的可持续途径。在这项工作中，证明了由伪 Jahn-Teller 效应产生的耐 pH 氧电还原系统。通过彻底的操作拉曼光谱、局部环境分析和密度函数理论模拟，揭示了 TiOxFy 的晶格畸变，该畸变引入了伪 Jahn-Teller 效应，有助于调节电极-电解质界面的局部 pH 值以及关键 *OOH 中间体的吸收/解吸。因此，与普通催化剂 78.6% 的活性衰减相比，TiOxFy 在 pH 1-13 范围内表现出较小的活​​性衰减 (3.2%)，具有显着的法拉第效率 (93.4-96.4%) 和 H2O2 产率 (595-614 mg) cm−2 h−1)，电流密度为 100–1000 mA cm−2。进一步的技术经济分析显示，H2O2 的生产成本取决于 pH 值，给出的 H2O2 最低价格为 0.37 kg−1 美元。目前的发现预计将为伪贾恩-泰勒效应提供一个额外的维度，利用超越传统概念的系统。