Species transformation and removal mechanism of various iodine species at the Bi2O3@MnO2 interface

Abstract

Long-term exposure to excessive iodine via drinking water significantly increases the risk of thyroid diseases. Further, the mechanisms and feasible technologies for iodine removal are far from being well elucidated. In this study, we constructed a heterogeneous Bi2O3@MnO2 interface with oxidation and adsorption efficiency toward iodide (I−), and investigated the performance and mechanisms involved in iodine removal. Bi2O3@MnO2 at the optimized Bi/Mn ratio of 0.05:1 had a maximum adsorption capacity of 1.19, 1.21, and 1.06 mg/g toward I−, iodine elemental (I2), and iodate (IO3−), respectively. According to the density functional theory (DFT) calculation, Bi2O3@MnO2 had an adsorption energy of -2.34, -2.11, and -3.89 eV for I−, I2, and IO3−, and exhibited a better band structure and state density character for iodine removal. Based on the results of XPS, HPLC, and LC-ICP-MS characterization, Bi2O3 plays an important role in adsorbing and capturing I− whereas MnO2 dominates the moderate oxidation of I− and the adsorption of I− and I2. The adsorbed I− and I2 concentrations on the Bi2O3@MnO2 surfaces were 146.3 μg/L and 18.3 μg/L. Notably, IO3− was not detected owing to its moderate oxidation effect. The coexisting ions of chloride (Cl−) and bromide (Br−) tended to occupy the Bi2O3 lattice and form insoluble BiOCl and BiOBr. Further, reductive species, such as sulphite (SO32−), may reduce MnO2 to Mn(III) and Mn(II). The synergistic effect between moderate oxidation and adsorption led to Bi2O3@MnO2 with high iodine removal capability. Overall, this study proposes a strategy for designing suitable interfaces and adsorbents for iodine removal; however, further studies are necessary to advance its application in practice.