Vertical Through‑Bond Co─O─Mo Bridge Enables Dual‑Site Nonradical Selective Oxidation.

Abstract

Selective oxidation via nonradical pathways is crucial for broad-ranged catalytic applications, yet it remains difficult to construct catalytic interfaces that efficiently activate oxidants while stabilize reactive intermediates at solid-liquid boundary for driving nonradical reactions. Conventional planar or quasi-planar interface-engineering strategies mainly tune local coordination environments or macroscopic phase contacts, and fail to couple two dissimilar redox centers at the atomic scale. Here, we propose the construction of asymmetric Co─O─Mo bridges at a buried interface to enable the formation of a vertical through-bond interface that preferentially catalyze nonradical reactions. Specifically, the bridging oxygen connects a CoOOH overlayer and a defect-rich MoS₂ substrate along the surface-normal direction, establishing a resting-state dipolar polarization and inducing site-specific charge redistribution to facilitate oxidant activation and stabilization while suppress solution-phase radical chemistry. This vertical interface spatially organizes complementary nonradical functions to favor high-valent Co(IV)═O and singlet oxygen generation. The resulting bridged catalyst shows high reactivity for oxidation of diverse organic micropollutants, superior tolerance to complex water matrices, and compatibility with flow-through membrane operation. More broadly, this work establishes vertical through-bond bridges as local catalytic units to couple structural asymmetry, electron polarization, and reactive-intermediate confinement, providing a transferable design principle for establishing selective oxidation heterogeneous catalytic system.