Mechanistic investigation of the electricity and gallic acid synergistically accelerated Fe(III)/Fe(II) cycle for the degradation of carbamazepine

This study investigated the application of a natural plant polyphenol, gallic acid (GA) to form complex with iron to promote the redox cycle of Fe(III)/Fe(II) under neutral initial pH conditions in the electrochemical (EC) system for activation of peroxymonosulfate (PMS) to efficiently degrade carbamazepine (CBZ). Results demonstrated that the synergistic effects of GA and EC significantly improved the removal efficiency, and the EC/GA/Fe(III)/PMS system effectively removed 100% of CBZ within a wide initial pH range of 3.0–7.0. The optimum stoichiometric ratio of GA to Fe(III) was found as 2:1. Investigations including quenching experiment, chemical probe analysis, and electron paramagnetic resonance (EPR) analysis were conducted to identify the primary reaction radicals as •OH, SO4•−, along with the 1O2 and Fe(IV). In the EC/GA/Fe(III)/PMS system, the synergistic effect of GA and electrochemistry led to a remarkable enhancement in the generation of •OH. Furthermore, the complexation reduction mechanism of GA and Fe(III) was proposed based on experimental and instrumental analyses, which demonstrated that the semi-quinone products of GA were the main substances promoting the Fe(III)/Fe(II) cycle. Mass spectrometry results showed that CBZ generated 27 byproducts during degradation, with formic acid as the main product of GA. The degradation efficiency of the EC/GA/Fe(III)/PMS system remained stable and excellent, exhibiting remarkable performance in the presence of various inorganic anions, including Cl− and NO3−, as well as naturally occurring organic compounds such as fulvic acid (FA). Overall results indicated that the EC/GA/Fe(III)/PMS system can be applied to effectively treat practical wastewater treatment without requirement of pH adjustment.