Enhancing the efficiency of zero valent iron by electrolysis: Performance and reaction mechanism

Electrolysis was applied to enhance the efficiency of micron-size zero valent iron (mFe⁰) and thereby promote p-nitrophenol (PNP) removal. The rate of PNP removal by mFe⁰ with electrolysis was determined in cylindrical electrolysis reactor that employed annular aluminum plate cathode as a function of experimental factors, including initial pH, mFe⁰ dosage and current density. The rate constants of PNP removal by Ele-mFe⁰ were 1.72-144.50-fold greater than those by pristine mFe⁰ under various tested conditions. The electrolysis-induced improvement could be primarily ascribed to stimulated mFe⁰ corrosion, as evidenced by Fe²⁺ release. The application of electrolysis could extend the working pH range of mFe⁰ from 3.0 to 6.0 to 3.0-10.0 for PNP removal. Additionally, intermediates analysis and scavengers experiments unraveled the reduction capacity of mFe⁰ was accelerated in the presence of electrolysis instead of oxidation. Moreover, the electrolysis effect could also delay passivation of mFe⁰ under acidic condition, as evidenced by SEM-EDS, XRD, and XPS analysis after long-term operation. This is mainly due to increased electromigration meaning that iron corrosion products (iron hydroxides and oxides) are not primarily formed in the vicinity of the mFe⁰ or at its surface. In the presence of electrolysis, the effect of electric field significantly promoted the efficiency of electromigration, thereby enhanced mFe⁰ corrosion and eventually accelerated the PNP removal rates.