Aminopolycarboxylic acids modified oxygen reduction by zero valent iron: Proton-coupled electron transfer, role of iron ion and reactive oxidant generation

Abstract

The oxygen reduction reaction (ORR) activated by Fe0 in the presence of three aminopolycarboxylic acids (CAs), i.e. nitrilotriacetic acid (NTA), ethylenediamine-N,N′-disuccinic acid (EDDS) and ethylenediaminetetraacetic acid (EDTA), for the degradation of sulfamethazine (SMT) was investigated. At optimum conditions, Fe0/EDDS/O2, Fe0/EDTA/O2 and Fe0/NTA/O2 systems presented SMT removal of 58.2%, 75.3% and 93.8%, respectively, being much higher than that in the Fe0/O2 system (1.36%). The generation of surface-bound Fe2+ (Fe2+) and dissolved iron ion was enhanced by CAs. ORR through a two-electron transfer pathway was mainly responsible for H2O2 generation in NTA and EDTA systems, while a single-electron ORR was the major source for producing H2O2 in EDDS system. •OH produced by the homogeneous reaction of Fe2+ and H2O2 was the main species for SMT degradation. Fe0/EDDS/O2 produced more 1O2 than Fe0/EDTA/O2 and Fe0/NTA/O2; however, the radical contributed negligibly to SMT removal. The caging effect of CAs might be a major factor influencing the reaction rate of Fe2+ and O2. CAs provided protons to accelerate the electron transfer, the production of Fe2+ and thus the contaminant removal. This study is of great significance for revealing ORR mechanisms in the Fe0-chelate system.