Insight into electrochemically boosted trace Co(II)-PMS catalytic process: Sustainable Co(IV)/Co(III)/Co(II) cycling and side reaction blocking

A novel homogeneous electrocatalytic system was constructed by current-assisted trace Co(II) activating PMS (ECP) to remove reactive blue 19 (RB19). More than 93 % of RB19 was rapidly removed with only a trace dose, and the PMS was 98.35 % utilized during the reaction. By exploring the active species and analyzing the PMS consumption, it was found that current strongly accelerated the Co(III)/Co(II) redox cycle by providing electrons to Co(III), and inhibited the side reaction thus improving the PMS utilization. Electric energy per order was very low, only 0.26 kWh·m3. Radicals (SO4•-) and non-radicals (Co(III), Co(IV) and 1O2) participated in ECP system, in which SO4•- was dominant. By excluding the other three precursors (PMS, •OH and O2•-), the side reaction product SO5•- was identified as the source of 1O2 in ECP system. Combining chelating agent EDTA and chemical probe PMSO, Co(IV) was considered formed by single and double charge transfer. Five degradation pathways of RB19 were proposed using mass spectrometry and DFT calculation. The ecotoxicity and mutagenicity of RB19 and its transformation products were predicted using software simulation. These studies provided an interesting insights into the synergistic Co(II)-PMS systems and offered a new strategy for electrochemical processes.