The important role of optimizing the coordination environment of single-atom catalysts (SACs) for selective production of singlet oxygen (O) in Fenton-like reactions is revealed. Herein, we introduce electron-depletion boron atoms to manipulate the coordination number and atom types of Fe site simultaneously and construct a six-coordination Fe-NB catalyst for peroxymonosulfte (PMS) activation. Particularly, it achieves 98.68% O generation selectivity superior to unregulated Fe-N catalyst (64.57%), exhibiting an exceptional bisphenol A (BPA) degradation performance with a reaction rate constant of 0.249 min. Experimental and theoretical results unveil that the tailored electronic structure of Fe not only enhances the adsorption selectivity of terminal oxygen atoms in PMS and alters the reaction pathway preference, but also facilitates the electron donation from PMS and lowers the energy barrier for O generation. This work provides a universal strategy for rational and precise modulation of SACs for specific reactive species conversion in environment remediation.

中文翻译：

---

Fe-N2B4 配置中 Fe 单原子电子结构的合理调节，以在类 Fenton 反应中优先生成 1O2

揭示了优化单原子催化剂（SAC）的配位环境对于类芬顿反应中选择性生产单线态氧（O）的重要作用。在此，我们引入贫电子硼原子来同时控制Fe位点的配位数和原子类型，并构建了用于过一硫酸盐（PMS）活化的六配位Fe-NB催化剂。特别是，它实现了 98.68% 的 O 生成选择性，优于未调节的 Fe-N 催化剂 (64.57%)，表现出优异的双酚 A (BPA) 降解性能，反应速率常数为 0.249 分钟。实验和理论结果表明，Fe的定制电子结构不仅增强了PMS中末端氧原子的吸附选择性并改变了反应路径偏好，而且有利于PMS的电子捐赠并降低了O生成的能垒。这项工作为环境修复中特定活性物质转化的 SAC 的合理和精确调节提供了一种通用策略。