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Solution pH is one of the primary factors affecting the efficiency of water decontamination. Although the influence of pH on oxidants activation, catalyst activity, and reactive oxygen species have been widely explored, there is still a scarcity of systemic studies on the changes in the oxidation behavior of organic pollutants at different pH levels. Herein, we report the influence laws of pH on the forms, reactivities, active sites, degradation pathways, and products toxicities of organic pollutants. Changes in pH cause the protonation or deprotonation of organic pollutants and further affect their forms and chemistry (e.g., electrostatic force, hydrophobicity, and oxidation potential). The oxidation potential of organic pollutants follows the order: protonated form > pristine form > deprotonated form. Moreover, protonation or deprotonation can modify the active sites and degradation pathways of organic pollutants, wherein deprotonation renders them more susceptible to electrophilic attack, while protonation reduces their activity against electrophilic and nucleophilic attacks. Additionally, pH adjustments can modify the degradation pathway and the toxicity of transformation products. Overall, pH changes can affect the oxidation fate of organic pollutants by altering their structure, which distinguishes it from the effect of pH on oxidants or oxidant activation processes. [Display omitted] • Solution pH alters the oxidation behavior of organic pollutants. • Deprotonation augments the reactivity of organic pollutants while protonation diminishes it. • Protonation and deprotonation modify the active sites and degradation pathways. • The toxicity of the transformation products can be controlled by adjusting the solution pH [ABSTRACT FROM AUTHOR]

Given high selectivity and excellent stability, zirconium oxides are very promising in selective removal of arsenic, fluorine, and phosphorus from water. Nevertheless, it remains challenging to prepare sub-10 nm zirconium oxides of ultra-high adsorptive reactivity. Herein, we prepared hydrated zirconium oxides (HZO) of 4.88 ± 1.02 nm by conducting in-situ precipitation of nanoparticles (NPs) inside the gel-type anion exchanger (GAE). GAE was swollen in water and contained lots of < 10 nm swollen pores, restricting excess growth of HZO NPs. In comparison, the NPs formed inside the macroporous anion exchanger (MAE) possessed an average diameter of 30.91 ± 8.98 nm. XPS O1s analysis indicated that the oxygen sites in the gel-type nanocomposite (HZO@GAE) possessed a much higher proportion (48.9%) of reactive terminal oxygen (-OH) than the macroporous nanocomposite (HZO@MAE, 21.2%). Thus, HZO@GAE exhibited significantly enhanced adsorption reactivity toward As(V)/As(III) than HZO@MAE. The exhausted HZO@GAE could be fully regenerated by alkali treatment for repeated use without any loss in decontamination efficiency. In column assays, the HZO@GAE column successively produced ~2400 bed volume (BV) clean water ([As]<10 μg/L) from synthetic groundwater, exceeding twice the amount produced by the HZO@MAE column. This study may shed new light on developing highly efficient nanocomposites for water decontamination. [Display omitted] • A novel gel-type nanocomposite HZO@GAE containing sub-10 nm HZO NPs was developed. • The sub-10 nm nature endows HZO@GAE with more reactive terminal oxygen (-OH). • HZO@GAE possesses enhanced adsorption reactivity toward As(III/V) than HZO@MAE. • HZO@GAE exhibits excellent pH stability, storage stability and reusability. • Effective treatment amount of HZO@GAE column is above twice that of HZO@MAE column. [ABSTRACT FROM AUTHOR]