Theoretical insight into the degradation of p-nitrophenol by OH radicals synergized with other active oxidants in aqueous solution

Abstract

The degradation of p-nitrophenol (p-NP) based on OH radicals (HO^∙), HO₂ radicals (HO₂^∙) and O₂ in aqueous solution was investigated using theoretical computational methods. The complete degradation mechanisms of reaction between p-NP and HO^∙ were explored by density functional theory (DFT) methods. The 4-nitrophenoxy radicals and 1,2-dihydroxy-4-nitrocylohexadienyl radicals are confirmed to be major intermediates of the HO^∙-initiated reactions in aqueous phase, which consistent with experimental results. The chemical structures of some products (2,4-dihydroxycyclohexa-2,4-dien-1-one and 4-nitrocyclohexa-3,5-diene-1,2-dione) which were not identified in the experiment are determined. New favorable formation channels for some intermediates were found. The primary reactions initiated by HO^∙ or HO₂^∙ with p-NP reveals that HO^∙-initiated degradation is the dominant reaction. HO₂^∙ and O₂ can enhance the degradation extent of p-NP in further reactions. Rate constants of the elementary reactions and overall rate constants were calculated. In addition, the HO^∙-initiated primary reactions in a water box of 500 water molecules were studied using Monte Carlo simulation. All the OH-addition reactions are barrierless and highly feasible. The observed dynamic reaction process is similar to the DFT calculation prediction. Furthermore, the eco-toxicity evaluation shows that important products are harmless or harmful to aquatic organisms, and are much less toxic than p-NP.

Keywords: Degradation mechanism; Density functional theory; Monte Carlo simulation; OH radicals; p-NP.