Oxidation Engineering Activates Ni─Fe Nitrides for Efficient Mechanocatalytic Thiol Coupling

Abstract The selective oxidation of thiols to disulfides which characterized by low toxicity, mild odor, and high stability in the solid state not only mitigates environmental risks and simplifies storage and transport, but also increases their commercial appeal. Nevertheless, conventional oxidation techniques frequently suffer from limited selectivity and over‐oxidation, presenting significant barriers to industrial adoption. Here, a breakthrough is reported in mechanocatalytic disulfide synthesis through the innovative engineering of nitride@oxide core‐shell structures. The integrated theoretical and experimental investigations demonstrate that native oxide structures can induce non‐centrosymmetry in centrosymmetric Ni 3 FeN, endowing it with remarkable piezoelectric properties. Besides, the formation of oxide‐nitride interface also creates interfacial field and adjusts the electronic structures of Ni 3 FeN and oxides, thus facilitating charge separation and transfer. The optimized Ni 3 FeN─O─5 catalyst demonstrates exceptional performance in aerobic thiol coupling, achieving over 99% selectivity and a remarkable production rate of 67 mmol g −1 h −1 under ultrasonic irradiation, outperforming all existing catalytic systems. Mechanistic studies identify superoxide radicals as the key species governing the highly selective S─S coupling process. This work establishes a new paradigm for designing advanced mechanocatalysts and paves the way for sustainable organosulfur compound synthesis.