New insight into the mechanism of ferric hydroxide-based heterogeneous Fenton-like reaction

The heterogeneous Fenton-like reaction (HeFR) has always been a research focus for environmental applications. However, it has long been difficult to reach a consensus on the reaction mechanism because the process of metal ions dissolution and its role were not well understood. In this paper, we propose the courses of organics-mediated coordination or/and reduction dissolution of ferric hydroxide to initiate the autocatalytic kinetics of phenol degradation and illustrate it through density functional theory (DFT) and experiments. With the increase of hydrogen peroxide concentration, the degradation of phenol changes from autocatalytic kinetics to first-order kinetics. Furthermore, a novel "limit segmentation method" initiated by us indicates that homogeneous reaction plays a decisive role in the phenol degradation process. The dominant roles of the reactive organics in both iron dissolution and the iron cycle and of the homogeneous reaction in the whole degradation process in the ferric hydroxide-based HeFR system are brand-new insights that pave the pathway for future research. [Display omitted] •The reactive intermediates of phenol promote the dissolution of ferric hydroxide.•Phenol degradation conforms to autocatalytic kinetics in the HeFR system.•Excess H2O2 dosage impels phenol degradation from autocatalytic to first-order kinetics.•Homogeneous phenol degradation plays a decisive role in the ferric hydroxide-based HeFR system.