Fe@Fe2O3 promoted electrochemical mineralization of atrazine via a triazinon ring opening mechanism

In this study, an electrochemical/electro-Fenton oxidation (EC/EF) system was designed to degrade atrazine, by utilizing boron-doped diamond (BDD) and Fe@Fe 2 O 3 core-shell nanowires loaded active carbon fiber (Fe@Fe 2 O 3 /ACF) as the anode and the cathode, respectively. This EC/EF system exhibited much higher degradation rate, decholorination and mineralization efficiency of atrazine than the electrochemical (EC) and electrochemical/traditional electro-Fenton (EC/TEF) oxidation counterpart systems without Fe@Fe 2 O 3 core-shell nanowires. Active species trapping experiment revealed that Fe@Fe 2 O 3 could activate molecular oxygen to produce more OH through Fenton reaction, which favored the atrazine degradation. High performance liquid chromatography , high performance liquid chromatography-mass spectrometry and gas chromatography-mass spectrometry were applied to probe the decomposition and mineralization of atrazine during this novel EC/EF process, which revealed that two intermediates of triazinons (the isomerization of hydroxylated atrazine) were generated during the electrochemical/electro-Fenton oxidation of atrazine in the presence of Fe@Fe 2 O 3 core-shell nanowires. The experimental and theoretical calculation results suggested that atrazine might be degraded via a triazinon ring opening mechanism, while the presence of Fe@Fe 2 O 3 notably accelerated the decholorination process, and produced more hydroxylated products to promote the generation of trazinons and the subsequent ring cleavage as well as the final complete mineralization. This work provides a deep insight into the triazine ring opening mechanism and the design of efficient electrochemical advanced oxidation technologies (EAOTs) for persistent organic pollutant removal .