Mn-Doped Spinel for Removing Cr(VI) from Aqueous Solutions: Adsorption Characteristics and Mechanisms

In this study, the manganese (Mn) was doped in the MnFe(2)O(4) crystal by the solid-phase synthesis method. Under the optimum conditions (pH = 3), the max removal rate and adsorption quantity of Cr(VI) on MnFe(2)O(4) adsorbent obtain under pH = 3 were 92.54% and 5.813 mg/g, respectively. The DFT calculation results indicated that the adsorption energy (E(ads)) between HCrO(4)(−) and MnFe(2)O(4) is −215.2 KJ/mol. The Cr(VI) is mainly adsorbed on the Mn atoms via chemical bonds in the form of HCrO(4)(−). The adsorption of Mn on the MnFe(2)O(4) surface belonged to chemisorption and conformed to the Pseudo-second-order equation. The mechanism investigation indicated that the Mn in MnFe(2)O(4) has an excellent enhancement effect on the Cr(VI) removal process. The roles of Mn in the Cr(VI) removal process included two parts, providing adsorbing sites and being reductant. Firstly, the Cr(VI) is adsorbed onto the MnFe(2)O(4) via chemisorption. The Mn in MnFe(2)O(4) can form ionic bonds with the O atoms of HCrO(4)(−)/CrO(4)(2−), thus providing the firm adsorbing sites for the Cr(VI). Subsequently, the dissolved Mn(II) can reduce Cr(VI) to Cr(III). The disproportionation of oxidized Mn(III) produced Mn(II), causing Mn(II) to continue to participate in the Cr(VI) reduction. Finally, the reduced Cr(III) is deposited on the MnFe(2)O(4) surface in the form of Cr(OH)(3) colloids, which can be separated by magnetic separation.