Microplasma Electrolytic Oxidation-Constructed Pd-Based Catalyst for Efficient and Green Selective Oxidation of Silanes

The green and selective oxidation of silanes to silanols has attracted considerable attention owing to its extensive applications across various industries. In this study, we introduce a novel instantaneous low-voltage microplasma electrolytic oxidation (ILVPEO) strategy to fabricate a highly efficient Pd/MgO/Mg catalytic system for the selective oxidation of silane to silanol. This approach leverages in situ microplasma effect to simultaneously decompose [PdCl4]2– and oxidize the Mg substrate, yielding Pd/MgO/Mg composites that features ultrasmall Pd nanoparticles (2.1 nm with high monodispersity) uniformly anchored on a porous and hydrophilic MgO support. These characteristics endow the catalyst with outstanding performance in the oxidation of phenylmethyldimethylsilane (PhMe2SiH) to the corresponding phenylmethyldimethylsilanol (PhMe2SiOH), achieving a remarkable turnover frequency (TOF) of 11,698 mol mol–1 h–1(129,260 mol mol–1 h–1), significantly surpassing conventional systems. Notably, the reaction proceeds using water as the primary oxygen source and generates hydrogen as the only byproduct, aligning closely with the principles of green chemistry. Moreover, the Pd/MgO catalyst demonstrates excellent durability, maintaining over a 90% product yield across 20 consecutive reaction cycles. It also displays broad substrate compatibility, efficiently oxidizing a diverse array of silanes with steric effects influencing the activity. This work presents a sustainable and scalable catalytic platform for silane oxidation, offering substantial potential for green industrial applications.