Abstract

The photo–Fenton process offers a promising alternative for the oxidation of complex heavy metals. However, the potential influence of coexisting substrates may be overlooked. The •OH radicals generated in the photo–Fenton process ensure superior oxidation ability. In this study, we used a vacuum ultraviolet (VUV) light-assisted photo–Fenton (VPF) process to explore its performance in the synergistic oxidation of Ni-ethylenediaminetetraacetic acid (EDTA) and coexisting hypophosphite, typical pollutants in electroless nickel plating (ENP) wastewater. Based on electron spin resonance (ESR) and DMSO-probing results, •OH was the predominant reactive oxygen species, and VPF possessed the highest •OH concentration compared to other photochemical processes under identical conditions (pH, Fe, H2O2). Enhanced •OH generation in VPF was attributed to various photochemical reactions, including photo–Fenton, UV/H2O2, and VUV/H2O. Consequently, VPF exhibited efficient Ni-EDTA decomplexation and hypophosphite oxidation. Notably, the evolution and rate-limiting steps during hypophosphite oxidation were demonstrated by experimental results and density functional theory calculations. Hypophosphite was initially oxidized to phosphite, which subsequently oxidized to phosphate. The oxidation of phosphite could be considered the rate-limiting step as it exhibits higher energy barriers than hypophosphite oxidation. Adequate •OH generation in the VPF process could overcome this energy barrier, indicating its potential for application in pollutant removal and resource recovery from ENP wastewater.

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