Decomposition of Hydrogen Peroxide Driven by Photochemical Cycling of Iron Species in Clay

The reactivity of iron-bearing clays to catalyze the decomposition of hydrogen peroxide (H2O2) under light irradiation was investigated. Free iron oxides and structural iron in clay octahedral lattice are contained simultaneously in montmorillonite K10 (MK10), a representative natural clay mineral. By pretreatment of clay with the particular method, the reactivities of the two kinds of iron species were differentiated. It was found that free iron oxides on clay surface efficiently catalyzed the decomposition of H2O2 under UV light irradiation but structural iron in the octahedral lattice showed poor reactivity. This was found to result from the difference in production of Fe(II) species under UV irradiation between iron oxides and structural iron. When photoreactive substances such as N,N-dimethylaniline (DMA), rhodamine B (RhB), or malachite green (MG) were introduced, structural iron was found to promote greatly the decomposition of H2O2. The reduction of clay iron(III) to iron(II) is essential for the decomposition of H2O2, which is achieved by light-induced ligand to metal charge transfer (for iron oxides) or organic matters donating electrons upon irradiation (for structural iron). The light-induced redox cycling of iron did not lead to the release of iron and decomposition of H2O2 primarily localized on the clay surface. This work implies that iron-bearing clays could be a sink of H2O2 in the environmental system.