Selective Arsenic Removal from Groundwaters Using Redox-Active Polyvinylferrocene-Functionalized Electrodes: Role of Oxygen

Abstract

In this work, we investigate selective sorption of arsenic from simulated groundwaters at pH 8 by a redox-active polyvinylferrocene (PVF)-functionalized electrode using a modified double potential step chronoamperometry (DPSC) method. Our results show that effective and sustainable As(III) removal can be achieved at 0 V once the electrode is activated via anodic polarization. During activation, ferrocene (Fc) in PVF is oxidized to the ferrocenium ion (Fc⁺) with the latter facilitating As(III) sorption and subsequent oxidation as well as As(V) sorption. The high affinity of Fc⁺ to As and weak attraction to competing anions at 0 V ensure high selectivity of As over Cl^-, SO₄^2-, and NO₃^- at concentrations typical of groundwaters. Following the removal process, efficient regeneration of the electrode is achieved at -1.2 V wherein Fc⁺ is reduced to Fc thereby facilitating As desorption from the electrode surface. Our results further show that O₂ and associated generation of hydrogen peroxide during the regeneration step drive the oxidation of Fc to Fc⁺, thereby maintaining the constant generation of Fc⁺ required to achieve As(III) removal in subsequent cycles. Our results show that 91.8 ± 0.6% of As(III) could be selectively removed from simulated groundwater over 10 cycles at an ultralow energy consumption of 0.12 kWh m^-3.