Electron cycling mechanism in Fe/Mn DSAzyme accelerates BPA degradation and nanoenzyme regeneration

Abstract

Peroxidase-like (POD-like) as a kind of new Fenton-like catalyst can effectively activate H2O2 to degrade organic pollutants in water, but improving the catalytic activity and stability of POD-like remains a challenging task. Here, we synthesized a novel dual single-atom nanoenzyme (DSAzyme) FeMn/N-CNTs with Fe-N4 and Mn-N4 bimetallic single-atom active centers by mimicking the active centers of natural enzymes and taking advantage of the synergistic effect between the dual metals. FeMn/N-CNTs DSAzyme showed significantly enhanced POD-like activity compared to monometallic-loaded Fe/N-CNTs and Mn/N-CNTs. Within the FeMn/N-CNTs/H2O2 system, bisphenol A (BPA) could be removed 100 % within 20 min. DFT calculations show that Mn-N4 in FeMn/N-CNTs can readily adsorb negatively charged BPA molecules and capture electrons. Meanwhile, Fe-N4 sites can easily adsorb H2O2 molecules, leading to their activation and splitting into strongly oxidizing hydroxyl radicals (·OH). Throughout this process, electrons are continuously recycled in BPA → Mn-N4 → Fe-N4 → H2O2, effectively promoting the regeneration of Fe2+. Practical studies on wastewater and cycling experiments have demonstrated the great potential of this method for remediating water environments.