Carbon Free and Noble Metal Free Ni₂Mo₆S₈ Electrocatalyst for Selective Electrosynthesis of H₂O₂

Electrocatalytic two-electron reduction of oxygen is a promising method for producing sustainable H₂O₂ but lacks low-cost and selective electrocatalysts. Here, the Chevrel phase chalcogenide Ni₂Mo₆S₈ is presented as a novel active motif for reducing oxygen to H₂O₂ in an aqueous electrolyte. Although it has a low surface area, the Ni₂Mo₆S₈ catalyst exhibits exceptional activity for H₂O₂ synthesis with >90% H₂O₂ molar selectivity across a wide potential range. Chemical titration verified successful generation of H₂O₂ and confirmed rates as high as 90 mmol H₂O₂ g_cat⁻¹ h⁻¹. The outstanding activities are attributed to the ligand and ensemble effects of Ni that promote H₂O dissociation and proton-coupled reduction of O₂ to HOO*, and the spatial effect of the Chevrel phase structure that isolates Ni active sites to inhibit O O cleavage. The synergy of these effects delivers fast and selective production of H₂O₂ with high turn-over frequencies of ≈30 s⁻¹. In addition, the Ni₂Mo₆S₈ catalyst has a stable crystal structure that is resistive for oxidation and delivers good catalyst stability for continuous H₂O₂ production. The described Ni-Mo₆S₈ active motif can unlock new opportunities for designing Earth-abundant electrocatalysts to tune oxygen reduction for practical H₂O₂ production.