Catalytic activity and mechanism of typical iron-based catalysts for Fenton-like oxidation

Heterogeneous Fenton-like systems were exploited for the degradation of Reactive Red X-3B (RR X-3B) using iron-carbon composite, sponge iron, chalcopyrite and pyrite as catalysts. The effect of operational variables on the catalytic activity and metal leaching behavior of catalysts was evaluated and the catalytic mechanism was discussed. The experimental results showed that under the optimum conditions, chemical oxygen demand (COD) removals by Fenton-like systems could reach 89.91%, 86.84%, 80.11% and 60.02% with iron-carbon composite, sponge iron, chalcopyrite and pyrite, respectively. Micro-electrolysis of iron-carbon composite and sponge iron resulted in higher COD removal at acid pH range. Electron Paramagnetic Resonance (EPR) analysis and quenching tests showed that ^•OH was the main reactive oxygen species responsible for the degradation of RR X-3B. A large amount of Fe²⁺ leached from iron-carbon composite and sponge iron, which served as a homogeneous Fenton catalyst during the degradation of RR X-3B. In contrast, much lower amount of Fe²⁺ was leached from chalcopyrite and pyrite, and surface catalysis of the minerals played more important role in the generation of ^•OH. Surface characterization and density functional theory (DFT) calculation results illustrated that ≡Fe(II) was the primary surface catalytic site during the reaction. The reduction of ≡Fe(III) and ≡Cu(II) can be facilitated by sulfides on the mineral surface. The Fenton-like systems catalyzed by iron-based materials exhibited higher H₂O₂ utilization and COD removal than classical Fenton system. With the lower metal leaching concentration and stable surface property, chalcopyrite and pyrite may be more practical applicable from a long-term catalytic activity point of view.