Tuning nonradical in H2O2 activation via S-bridged asymmetric dual-metal centers for robust treatment of complex wastewater

Appropriate tuning of the nonradical pathway in the heterogeneous Fenton process is important for enhancing its anti-interference ability in wastewater treatment. However, the difficulty in O–H bond cleavage of H 2 O 2 hinders its oxidation routine for nonradical production. Herein, a charge-regulating linkage M–S–Fe (M = Co, Ni, Zn) with S-bridged asymmetric dual-metal centers was established on multiwall carbon nanotubes, i.e., M-FeS 2 /MWCNT, to effectively tune the H 2 O 2 nonradical pathway. The high-charge-positive M centers in M–S–Fe structure significantly reduced the H 2 O 2 oxidation energy barrier by 72%, thereby enhancing the 1 O 2 generation and model pollutant removal efficiency by 1.72 and ~24 times, respectively, compare to the sole-Fe center catalyst. Moreover, the S-bridged asymmetric dual-metal centers catalysts showed excellent complex pollutant adaptability (> 80% organic decontamination in phenolic, antibiotic and dye mixed matrices), ion-resistance and stability. This work offers a new strategy for constructing a charge-asymmetry dual-metallic-center for tunable nonradical pathways in H 2 O 2 activation.