Boosting the oxidative capacity of the Fe(0)/O₂ system via an air-breathing cathode

The corrosion of Fe(0) in the presence of O₂ in nature can lead to the oxidation of organic compounds, but the efficiency is very limited. Herein, attempts were made to establish a galvanic system that separates the anodic Fe(0) oxidation reaction and the cathodic O₂ reduction reaction using an air-breathing cathode. Compared with the chemical Fe(0)/O₂ system, it exhibited a substantially higher capability of destroying a variety of pollutants, such as organic dyes (12 types), phenol, nitrobenzene, acetaminophen, phenol, and ethylenediaminetetraacetic acid. The degradation rate constant of a model dye (i.e., Rhodamine B) increased from 0.047 min^-1 (chemical) to 1.412 min^-1 (galvanic) under the passive air-breathing condition. The electric circuit design promoted Fe(0) dissolution to Fe(II) and triggered electron transfer that drives O₂ reduction to H₂O₂, two important species responsible for the generation of HO^• at high abundance. In addition, the galvanic Fe(0)/O₂ system produces electricity while destroying pollutants. Tests with real Ni plating wastewater further demonstrated the capability of the system to oxidize complexed organics and phosphite. This study provides a new strategy for boosting the oxidative capacity of the Fe(0)/O₂ system, which shows promise for acid wastewater treatment.