Theoretical insight into hydroxyl production via H₂O₂ decomposition over the Fe₃O₄(311) surface

Fenton's reagent provides a method to produce active hydroxyl radicals (˙OH) for chemical oxidation by mixing iron oxide and hydrogen peroxide, which divides into homogeneous and heterogeneous Fenton's reagent. Heterogeneous Fenton's reagent is fabricated from H₂O₂ and various iron oxide solid materials, such as α-FeOOH, α-Fe₂O₃, and Fe₃O₄. Fe₃O₄ possesses the Fe²⁺/Fe³⁺ mixed valence oxidational state and has been reported to have good catalytic activity. However, the reaction mechanism of H₂O₂ decomposition on Fe₃O₄ surfaces is still unclear. In this work, we performed DFT calculations to investigate the H₂O₂ decomposition mechanisms over the Fe₃O₄(311) surface. There are two iron environments for H₂O₂ adsorption and decomposition on the Fe₃O₄(311) surface, a Fe²⁺/Fe³⁺ environment and a Fe³⁺/Fe³⁺ environment. We found that the H₂O₂ can adsorb on the Fe²⁺/Fe³⁺ environment by molecular adsorption but by dissociative adsorption on the Fe³⁺/Fe³⁺ environment. Our results show that both adsorption structures can produce two OH groups on the Fe₃O₄(311) surface thermodynamically. In addition, based on the electronic property analysis, H₂O₂ on the Fe²⁺/Fe³⁺ environment follows the Haber-Weiss mechanism to form one OH anion and one OH radical. On the other hand, H₂O₂ on the Fe³⁺/Fe³⁺ environment follows the radical mechanism to form two OH radicals. In particular, the OH radical formed on Fe²⁺/Fe³⁺ has energy levels on both sides of the Fermi energy level. It can be expected that this OH radical has good redox activity.