Reduced graphene oxide (rGO) is one of the most widely used carbon nanomaterials. When it is released into the environment, rGO can markedly affect the transformation of many pollutants, and change their fate and risk. In this work, the synergetic effects of rGO and Cu(II) on the oxidation of 2-naphthol were examined in water in the dark. It was found that the coexistence of rGO and Cu(II) significantly promoted the oxidation of 2-naphthol. Corresponding products were identified as the coupling oligomers of 2-naphthol (dimer, trimer and tetramer) and hydroxylated compounds (OH-2-naphthol, OH-dimer, di–OH–dimer and naphthoquinone derivatives). In the oxidation reaction, rGO played dual roles, i.e. adsorbent and electron-transfer mediator. rGO firstly adsorbed Cu(II) and 2-naphthol on its surface, and then transferred electrons from 2-naphthol to Cu(II) to yield 2-naphthol radicals and Cu(I). 2-Naphthol radicals coupled to each other to form different oligomers of 2-naphthol. Cu(I) was re-oxidized back to Cu(II) by dissolved oxygen, which sustained the continuous oxidation of 2-naphthol. During the autoxidation of Cu(I), reactive oxygen species were generated, which further reacted with 2-naphthol to form hydroxylated products. These findings provide new insights into the risk assessment of rGO and 2-naphthol in aquatic environments.

Copper ferrite (denoted as CuFe₂O₄MOF), prepared via a complexation reaction to obtain bimetal–organic frameworks (Cu/Fe bi-MOFs), followed by a combustion process to remove the MOF template, is employed as a heterogeneous activator to promote sulfite autoxidation for the removal of organic contaminants. At pH 8.0, more than 80% of the recalcitrant organic contaminant iohexol (10 μM) can be removed within 2 min by the activation of sulfite (500 μM) with CuFe₂O₄MOF (0.1 g L⁻¹). CuFe₂O₄MOF exhibits more pronounced catalytic activity in accelerating sulfite autoxidation for iohexol abatement compared to that fabricated by hydrothermal and sol–gel combustion methods. Radical quenching studies suggest that the sulfate radical (SO₄•⁻) is the main reactive species responsible for iohexol abatement. The performance of CuFe₂O₄MOF/sulfite for iohexol abatement can be affected by several critical influencing factors, including the solution pH and the presence of humic acid, Cl⁻, and HCO₃⁻. The effect of the ionic strength and the results of the attenuated total reflectance–Fourier transform infrared (ATR–FTIR) analysis indicate that sulfite autoxidation in the presence of CuFe₂O₄MOF involves an inner-sphere interaction with the surface Cu(II) sites of CuFe₂O₄MOF. X-ray photoelectron spectroscopy (XPS) characterization suggests that the surface Cu(II)–Cu(I)–Cu(II) redox cycle is responsible for efficient SO₄•⁻ production from sulfite. Overall, CuFe₂O₄MOF can be considered an alternative activator for sulfite autoxidation for potential application in the treatment of organic-contaminated water.

Efficient abatement of an iodinated X-ray contrast media iohexol by an emerging sulfite autoxidation advanced oxidation process is demonstrated, which is based on transition metal ion–catalyzed autoxidation of sulfite to form active oxidizing species. The efficacy of the combination of sulfite and transition metal ions (Ag(I), Mn(II), Co(II), Fe(II), Cu(II), Fe(III), or Ce(III)) was tested for iohexol abatement. Co(II) and Cu(II) are proven to show more pronounced catalytic activity than other metals at pH 8.0. According to the quenching studies, sulfate radical (SO₄•⁻) is identified to be the primary species for oxidation of iohexol. Increasing dosages of metal ion or sulfite and higher pH values are favorable for iohexol abatement. Inhibition of iohexol abatement is observed in the absence of dissolved oxygen, which is vital for the production of SO₅•⁻ and subsequent formation of SO₄•⁻. Overall, activation of sulfite to produce reactive radicals with extremely low Co(II) or Cu(II) concentrations (in the range of μg L⁻¹) in circumneutral conditions is confirmed, which offers a potential SO₄•⁻-based advanced oxidation process in treatment of aquatic organic contaminants.