Activation of persulfate/copper by hydroxylamine via accelerating the cupric/cuprous redox couple

Cuprous copper [Cu(I)] reacts with sodium persulfate (PDS) to generate sulfate radical SO₄⁻•, but it has been seldom investigated owing to its instability and difficulty in dissolving it. This study proposes a new method to regenerate Cu(I) from cupric copper [Cu(II)] by addition of hydroxylamine (HA) to induce the continuous production of radicals through active PDS, and investigates the resulting enhanced methyl orange (MO) degradation efficiency and mechanism in the new system. HA accelerated the degradation of MO markedly in the pH range from 6.0 to 8.0 in the HA/Cu(II)/PDS process. Both SO₄⁻• and hydroxyl radicals (•OH) were considered as the primary reactive radicals in the process. The MO degradation in the HA/Cu(II)/PDS process can be divided into three stages: the fast stage, the transitory stage, and the low stage. MO degradation was enhanced with increased dosage of PDS. Although high dosage of HA could accelerate the transformation of the Cu(II)/Cu(I) cycle to produce more reactive radicals, excess HA can quench the reactive radicals. This study indicates that through a copper-redox cycling mechanism by HA, the production of SO₄⁻• and •OH can be strongly enhanced, and the effective pH range can be expanded to neutral conditions.