Effective oxidation and adsorption of As(III) in water by nanoconfined Ce-Mn binary oxides with excellent reusability

Herein, a highly efficient As(III) purifier Ce-Mn@N201 with excellent reusability was developed by stepwise precipitating hydrated cerium(IV) oxides (HCO) and hydrated manganese(IV) oxides (HMO) inside N201, a widely-used gel-type anion exchange resin. Owing to confinement of unique nanopores in N201, the in-situ generated nanoparticles (NPs) inside Ce-Mn@N201 were highly dispersed with ultra-small sizes of around 2.6 nm. Results demonstrated that HMO NPs effectively oxidized As(III) to As(V) with the conversion of Mn(IV) to Mn(II), while the generated Mn²⁺ was mostly re-adsorbed onto the negatively-charged surface of HMO NPs. During the regeneration process by simple alkaline treatment, the re-adsorbed Mn²⁺ was firstly precipitated as (hydr)oxides of Mn(II) and then oxidized to HMO NPs by dissolved oxygen to fully refresh its oxidation capacity. Though HCO NPs mainly served as adsorbent for arsenic, they could partially oxidize As(III) to As(V) at the beginning, while the oxidation capacities continuously diminished with the irreversible conversion of Ce(IV) to Ce(III). In 10 consecutive adsorption-regeneration cycle, Ce-Mn@N201 efficiently decontaminated As(III) from 500 μg/L to below 5 μg/L with Mn²⁺ leaching less than 0.3% per batch. During 3 cyclic fixed-bed adsorptions, Ce-Mn@N201 steadily produced 8500-9150 bed volume (BV) and 3150-3350 BV drinkable water from the synthesized and real groundwater, respectively, with Mn leaching in effluent constantly < 100 μg/L.