Critical Review on the Mechanisms of Fe²⁺ Regeneration in the Electro-Fenton Process: Fundamentals and Boosting...

This review presents an exhaustive overview on the mechanisms of Fe³⁺ cathodic reduction within the context of the electro-Fenton (EF) process. Different strategies developed to improve the reduction rate are discussed, dividing them into two categories that regard the mechanistic feature that is promoted: electron transfer control and mass transport control. Boosting the Fe³⁺ conversion to Fe²⁺ via electron transfer control includes: (i) the formation of a series of active sites in both carbon- and metal-based materials and (ii) the use of other emerging strategies such as single-atom catalysis or confinement effects. Concerning the enhancement of Fe²⁺ regeneration by mass transport control, the main routes involve the application of magnetic fields, pulse electrolysis, interfacial Joule heating effects, and photoirradiation. Finally, challenges are singled out, and future prospects are described. This review aims to clarify the Fe³⁺/Fe²⁺ cycling process in the EF process, eventually providing essential ideas for smart design of highly effective systems for wastewater treatment and valorization at an industrial scale.