Phase Engineering of Amorphous Ru‐O‐C ₆₀ for Efficient Electrosynthesis of Sulfoxides

Abstract

ABSTRACT The diverse short/medium‐range structures of amorphous nanomaterials dictate their phase structures, which ultimately govern their catalytic behaviors. However, the inherent high Gibbs free energy caused by disordered atomic arrangement makes the controlled phase regulation of amorphous nanomaterials challenging. Herein, we regulated the phase structure of amorphous RuO x nanosheets by constructing a novel amorphous Ru‐O‐C 60 motif. Integrated differential phase contrast image confirms the incorporation and spatial distribution of C 60 within the amorphous RuO x nanosheets. X‐ray absorption fine structure measurements reveal that amorphous RuO x nanosheets anchored onto C 60 (A‐RuO x /C 60 NSs) possess an edge‐sharing RuO 6 octahedral configuration. The A‐RuO x /C 60 NSs exhibit outstanding performance in the electro‐oxidation of methyl phenyl sulfide, achieving 99.1% conversion, 99.63% selectivity, 99.57% Faradaic efficiency, and excellent stability over 50 cycles, while maintaining high conversion and selectivity toward various para‐ and meta‐substituted methyl phenyl sulfide derivatives. Density functional theory calculations reveal that the edge‐sharing RuO 6 octahedral configuration enhances methyl phenyl sulfide adsorption, facilitate Ru─O bond cleavage and S═O bond formation, thereby accelerating product formation and release. Moreover, the synthesis strategy is extendable to the preparation of various monometallic and bimetallic amorphous oxides/C 60 nanosheets.