Site‐Specific Spin State Modulation in Spinel Oxides for Enhanced Nonradical Oxidation

Spinel oxides hold tremendous potential for driving advanced oxidation processes, yet the underlying mechanism for maximizing their activity remains unclear. In this study, we leverage tetrahedral and octahedral site interactions in MnxCo3‐xO4 to modulate the spin states, specifically spin alignment and spin moment, thereby enhancing periodate (PI) activation and catalytic performance in contaminant degradation. Through combined experimental and density functional theory (DFT) analyses, we elucidate the role of spin alignment at synergetic tetrahedral and octahedral sites in facilitating a quantum spin exchange interactions (QSEI) with an efficient electronic spin channel for charge transfer. Meanwhile, the engineered high spin configuration in CoMn2O4 raises the d‐band center, favoring stable PI* surface complex formation and accelerating the rate‐determining desorption of IO3‐ with a lower ‐ICOHP value during the catalytic degradation of ciprofloxacin. As a result, the fine‐tuned spin state of CoMn2O4 leads to enhanced overall reaction kinetics, with a 2.5‐fold increase compared to MnCo2O4and up to 22‐fold increase compared to the octahedrally‐active only catalysts. Such a site‐specific modulation has been found applicable to other spinel oxides, enlightening fine‐tuned electronic structure for maximizing catalytic performance.