Remove humic acid from water quickly using only oxygen and sulfite at nickel cobalt spinel catalyst

The typical refractory organic pollutant, humic acid (HA), causes many water and wastewater treatment obstacles. In this study, a novel method was proposed to degrade HA based on the low-temperature (<100 °C) catalytic air oxidation technology (LTCAO) using the NiCo-spinel (NCO) as a catalyst and the sulfite as a promoter. Sulfite enhanced the quantity of mineralized HA to 2.4 times that without sulfite assistance, and the removal rate of total organic carbon reached 93.1% within 60 min at 90 °C. HA gradually degrades into small organic molecules and is mineralized through interfacial reactions and radical paths. Sulfite plays a triple role in these reactions. Sulfite sulfonated HA destroyed its pseudomicellar structure, making HA easily oxidized. Sulfite also coordinated with NCO and promoted the internal electronic hopping conduction of NCO because of the fast electron transfer between SO₃^2- and the h⁺sites, thus accelerating the electron transfer between HA and O₂ mediated by NCO. In addition, the coordinated SO₃^2- was activated to form the radical ∙SO₃^-, which strengthened the oxidation of HA. This study supports a simple and green method for efficiently cleaning water and wastewater rich in HA.