Optimizing the energetics of the elementary steps of Oxygen Evolution Reaction (OER) by tuning the electrode-intermediate/product interaction through d-band center energy tailoring is an essential yet under-explored concept in oxygen electrocatalysis. Herein, the interplay between sulfur/phosphorus and selenium toward improved OER kinetics is investigated and the synergistic interaction between these task-specific anions along with additional metal–anion interaction provides suitable tailoring of the d-band center for facilitating efficient electrocatalysis. S/P regulation of FeSe₂ resulted in a transition from high-spin Fe^2+/3+ to intermediate-spin Fe^2+/3+ affording simultaneous adsorption/desorption optimization leading to ultralow overpotentials of <300 mV at a current density of 600 mA cm⁻² [376 A g⁻¹] with highly stable performance for 50 h. These improvements stem from the strong electronic modulation arising from anion regulation-induced electron transfer and anion vacancies due to the dynamic migration of P/S to the outermost electrode surface during OER. This dynamic migration brings forth surface enrichment of S/P anions, endowing a hydrophilic surface for accelerating OH⁻ adsorption while the Se-rich core facilitates the desorption of oxygen via reinforced electron repulsion between metal/Se d-band and oxygen p-band electrons. This work paves the way for optimizing oxygen electrocatalysis through descriptor-guided tuning from an experimental standpoint by introducing functional task-specific elements.

中文翻译：

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通过硫/磷动态迁移诱导阴离子调节硒化铁表面富集来促进析氧动力学


通过 d 带中心能量调整来调整电极-中间体/产物相互作用来优化析氧反应 (OER) 基本步骤的能量学是氧电催化中一个重要但尚未充分探索的概念。在此，研究了硫/磷和硒之间的相互作用以改善 OER 动力学，并且这些特定任务阴离子之间的协同相互作用以及额外的金属-阴离子相互作用为 d 带中心提供了适当的定制，以促进有效的电催化。 FeSe ₂的 S/P 调节导致从高自旋 Fe ^2+/3+到中自旋 Fe ^2+/3+的转变，提供同时吸附/解吸优化，导致在电流密度为 <300 mV 的超低过电势600 mA cm ^-2 [376 A g ^-1 ]，50 小时内性能高度稳定。这些改进源于阴离子调节引起的电子转移和阴离子空位（由于 OER 过程中 P/S 动态迁移到最外层电极表面而产生的阴离子空位）所产生的强电子调制。这种动态迁移带来了 S/P 阴离子的表面富集，赋予亲水性表面以加速^OH-吸附，而富 Se 核心则通过增强金属/Se d 带和氧 p 带电子之间的电子排斥促进氧的解吸。这项工作通过引入功能性任务特定元素，从实验的角度通过描述符引导的调整，为优化氧电催化铺平了道路。