The efficient removal of hydrogen sulfide (H₂S) is of great importance for various industrial processes such as the sewage stream depollution and syngas upgrade. Oxidative desulfurization with polyoxometalates (POMs) has been proved one of the most attractive ways to remove H₂S from the systems, while the role of the central atom in POMs has not been well evaluated. Herein, we demonstrate the desulfurization activity of POMs could be well internally switched by the central atoms. In particular, the S^VI-centered POM of [Himi]SMo, exhibited greatly enhanced desulfurization performance compared to its structural analogs with Ge^IV or P^V as central atoms, with a breakthrough H₂S capacity of 627.0 mg g⁻¹ compared to 39.5 and 54.9 mg g⁻¹ respectively, well surpassing state-of-the-art H₂S desulfurizes. In addition, its activity was well maintained at a wide range of temperature (0–50 °C) and pH (4−9). More interestingly, electrochemical re-oxidation of the H₂S laden [Himi]SMo was found much more active than the fresh one, achieving H₂S capacity up to 2174 mg g⁻¹. Air involved in-situ re-oxidation and S-O metathesis mechanisms were proposed and experimentally evidenced to explain the high capacity. This work opens a new concept for the rational design of POMs in terms of H₂S removal.

硫化氢（H ₂ S）的有效去除对于污水流去污染和合成气升级等各种工业过程具有重要意义。_{使用多金属氧酸盐 (POM) 进行氧化脱硫已被证明是从系统中去除 H 2} S的最有吸引力的方法之一，而中心原子在 POM 中的作用尚未得到很好的评估。在此，我们证明了 POM 的脱硫活性可以通过中心原子在内部很好地转换。特别是，[Himi]SMo的 S ^{VI中心 POM 与以 Ge IV}或 P ^V为中心原子的结构类似物相比，表现出显着增强的脱硫性能，具有突破性的 H ₂S 容量分别为 627.0 mg g ^-1和 39.5 和 54.9 mg g ^-1，远远超过最先进的 H ₂ S 脱硫剂。此外，它的活性在很宽的温度（0-50°C）和pH（4-9）范围内都能很好地保持。_{更有趣的是，发现载有 H 2} S 的 [Himi] SMo的电化学再氧化比新鲜的更活跃，实现了高达 2174 mg g ^{-1的 H} ₂ S 容量。提出了空气参与原位再氧化和 SO 复分解机制并通过实验证明来解释高容​​量。这项工作为 POM 在 H ₂ S 去除方面的合理设计开辟了一个新概念。