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.