Thermally synergized electron shuttling via Cu-O-Fe bridge redirects H₂O₂ activation pathways

The performance of conventional heterogeneous Fenton-like systems is fundamentally limited by inefficient H₂O₂ activation and poor control over reactive species pathways, especially for high-loading pollutants. To address this, we propose a strategy that synergistically couples thermal energy with an electronically tailored bimetallic center. Guided by density functional theory screening, we identify spinel CuFe₂O₄, characterized by a dynamic Cu-O-Fe bridge, as the optimal catalyst. The thermal/CuFe₂O₄/H₂O₂ system exhibits exceptional activity, achieving 99.8 % removal of 1000 mg/L acetaminophen within 6 min and a rate constant 21 times higher than that of the thermal/H₂O₂ baseline. This enhancement originates from a dual-scale synergy. At the material scale, the Cu-O-Fe bridge serves as an electron-redistribution center, where electron transfer from Cu to Fe sites sustains redox cycling. At the process scale, this bridge cooperates with thermal energy to reconfigure the activation pathway from a radical-dominated process to an efficient hybrid radical/non-radical regime, with a 42.5 % non-radical contribution confirmed by spectroscopic, electrochemical, and kinetic analyses. The system also demonstrates robust stability, minimal metal leaching, and effectiveness in complex water matrices. This work establishes a general principle of integrating electronic-structure-engineered active sites with external energy inputs for intelligent pathway control in advanced oxidation processes.