Efficient Homolytic Cleavage of H₂O₂ on Hydroxyl-Enriched Spinel CuFe₂O₄ with Dual Lewis Acid Sites

Traditional H₂O₂ cleavage mediated by macroscopic electron transfer (MET) not only has low utilization of H₂O₂, but also sacrifices the stability of catalysts. We present a non-redox hydroxyl-enriched spinel (CuFe₂O₄) catalyst with dual Lewis acid sites to realize the homolytic cleavage of H₂O₂. The results of systematic experiments, in situ characterizations, and theoretical calculations confirm that tetrahedral Cu sites with optimal Lewis acidity and strong electron delocalization can synergistically elongate the O-O bonds (1.47 Å → 1.87 Å) in collaboration with adjacent bridging hydroxyl (another Lewis acid site). As a result, the free energy of H₂O₂ homolytic cleavage is decreased (1.28 eV → 0.98 eV). H₂O₂ can be efficiently split into ⋅OH induced by hydroxyl-enriched CuFe₂O₄ without MET, which greatly improves the catalyst stability and the H₂O₂ utilization (65.2 %, nearly 2 times than traditional catalysts). The system assembled with hydroxyl-enriched CuFe₂O₄ and H₂O₂ affords exceptional performance for organic pollutant elimination. The scale-up experiment using a continuous flow reactor realizes long-term stability (up to 600 mL), confirming the tremendous potential of hydroxyl-enriched CuFe₂O₄ for practical applications.