Developing a membrane-free oxidation reaction, especially using water as the oxygen source, to generate high-value chemicals with high selectivity for replacing low-value O₂ over a cost-effective catalyst is significant. In this study, nickel phosphide (Ni₂P) hollow nanocubes are designed and shown to enable membrane-free selective oxidation of thioethers to sulfoxides and sulfones with H₂O. In situ Raman data reveal the surface reconstruction of Ni₂P to NiOOH, and the resulting Ni^II/Ni^III redox couple promotes this transformation. The ¹⁸O-labeling experiments confirm H₂O as the oxygen source. A cross-coupling of the sulfur-related radical with the hydroxyl radical is proposed. Sulfoxides and sulfones with high yields and selectivity can be controlled via potential modulation, which is challenging for traditional methods. Deuterated sulfoxides and sulfones are readily synthesized via one-pot thioether oxidation and the tandem H/D exchange processes. Wide substrate scopes, good functional group compatibilities, integrating hydrogen production, and paired synthesis of deuterated sulfoxide and arene highlight the potential of this membrane-free strategy.

开发无膜氧化反应，特别是使用水作为氧源，以产生具有高选择性的高价值化学品以通过具有成本效益的催化剂替代低价值的 O ₂具有重要意义。在这项研究中，磷化镍 (Ni ₂ P) 中空纳米立方体的设计和展示能够用 H ₂ O将硫醚无膜选择性氧化为亚砜和砜。原位拉曼数据揭示了 Ni ₂ P 到 NiOOH的表面重构，由此产生的 Ni ^II / Ni ^III氧化还原对促进了这种转变。的¹⁸ O型标记实验确认ħ ₂O 作为氧源。提出了硫相关自由基与羟基自由基的交叉偶联。具有高产率和选择性的亚砜和砜可以通过电位调节来控制，这对传统方法来说是一个挑战。氘代亚砜和砜很容易通过一锅硫醚氧化和串联 H/D 交换过程合成。广泛的底物范围、良好的官能团兼容性、集成制氢以及氘代亚砜和芳烃的配对合成突出了这种无膜策略的潜力。