Catalytic Process Optimization of Birnessite‐based Fenton‐like Reaction with Surface Cu2+ Modification

Abstract Layer‐structured birnessite (δ‐MnO2) has been applied recently in the heterogeneous Fenton‐like process. However, easy deactivation and low utilization efficiency of H2O2 limit its practical application. The catalytic processes of H2O2 on birnessite were successfully regulated via surface chemical modification as Cu2+ ions were intercalated into the birnessite by the ion‐exchange method (CuBir). The triple‐corner‐sharing inner‐sphere surface complexes of Cu2+ ions (TCS species) formed above Mn vacancies could effectively weaken the over‐complexation of H2O2 on the surface of [MnO6] sheets, and then decrease the self‐consumption of surface‐formed superoxide radicals. The surface TCS species have excellent Fenton‐like performances and enhance the conversion efficiency of H2O2 into reactive oxygen species (ROS). Moreover, the surface Cu2+‐modification engineering could prevent deactivation owing to degradation intermediate residues and improve the recyclability of catalyst.