An extra-chelator-free fenton process assisted by electrocatalytic-induced in-situ pollutant carboxylation for target refractory organic efficient treatment in chemical-industrial wastewater.

For traditional Fenton processes, the quenching behavior of radical contenders (e.g., most aliphatic hydrocarbons) on hydroxyl radicals (·OH) usually hinders the removal of target refractory pollutants (aromatic/heterocyclic hydrocarbons) in chemical industrial wastewater, leading to excess energy consumption. Herein, we proposed an electrocatalytic-assisted chelation-Fenton (EACF) process, with no extra-chelator addition, to significantly enhance target refractory pollutant (pyrazole as a representative) removal under high ·OH contender (glyoxal) levels. Experiments and theoretical calculations proved that superoxide radical (·O2-) and anodic direct electron transfer (DET) effectively converted the strong ·OH-quenching substance (glyoxal) to a weak radical competitor (oxalate) during the electrocatalytic oxidation process, promoting Fe2+ chelation and therefore increasing radical utilization for pyrazole degradation (reached maximum of ∼43-fold value upon traditional Fenton), which appeared more obviously in neutral/alkaline Fenton conditions. For actual pharmaceutical tailwater treatment, the EACF achieved 2-folds higher oriented-oxidation capability and ∼78% lower operation cost per pyrazole removal than the traditional Fenton process, demonstrating promising potential for future practical applications.

Efficient Fenton-like Process Induced by Fortified Electron-Rich O Microcenter on the Reduction State Cu-Doped CNO Polymer.

The discharge of organic pollutants threatens the environment and health and is also a waste of organic energy. Here, the reduction state Cu (RSC) species-doped carbon-nitrogen-oxygen polymer (RSC-CNOP) is synthesized from high-temperature polymerization of a Cu-polyimide precursor, which is used as a Fenton-like catalyst and exhibits excellent performance for pollutant degradation, accompanied by the utilization of the electron energy of the pollutants. Experiments and theoretical calculations reveal the promotion mechanism. The formed Cu(RSC)-O-C(π) electron-transfer bridges in RSC-CNOP induce the bidirectional electron transfers from RSC to O and from C(π) to O (RSC → O ← π), forming the polarized reaction micro-areas (reinforced electron-rich O microcenters and electron-poor C(π) microcenters). The free electrons in electron-rich centers of RSC-CNOP are as many as ∼8 times that of the pure CNOP sample from the electron paramagnetic resonance measurement. Pollutants are oxidized by supplying electrons to electron-poor microcenters, and H2O2 can be selectively reduced to •OH (also destruct pollutants) in the electron-rich microcenter over RSC-CNOP. This work reveals that the energy and electrons of pollutants can be efficiently utilized in the Fenton-like system through constructing and reinforcing the polarized dual reaction microcenters.