Modulating the >Co(II)/Co(III) redox cycling via confinement of cobalt with WS₂ for the ultrafast sulfite activation

Sulfite autoxidation in combination with the cobalt-based heterogeneous activators, has recently emerged as the efficient sulfate radical (SO4 center dot-) generation process for organic micropollutant abatement in the water and wastewater treatment, yet the sluggish >Co(II)/Co(III) redox cycling currently compromises the efficacy of radical generation and the potential applications. Herein, regarding that the reductive W(IV) species in WS2 can modulate the >Co(II)/Co(III) redox cycling in the advanced oxidation processes, confinement of cobalt with WS2 (Co-WS2) is designed and characterized. The Co-WS2/sulfite process achieves an ultrafast tetracycline (TC) abatement (similar to 100 % abatement of TC within 1 min) under circumneutral conditions with lower dosage of sulfite and activator, outperforming the current cobalt-based heterogeneous counterparts. The dominant reactive radicals are identified as SO4 center dot- and hydroxyl radical (HO center dot), which are quantified to be 9.7 mu M and 4.5 mu M, respectively. The superior radical generation efficiency and the concomitant TC abatement rely on the excellent redox properties and electron transfer capability of Co-WS2. The inter-transformation of >Co(II)/>Co(III) can be accelerated via the involvement of the reductive W(IV) species with the redox-reversibility of the W(IV)/W(VI) couple in the presence of sulfite. The TC degradation intermediates and the corresponding pathways are also proposed according to the ultra-performance liquid chromatography and quadrupole-time of flight mass spectrometry (UPLC-QTOF-MS) analysis. In addition, the influences of the reactant dosage, coexisting anions (HCO3-, HPO42-, Cl- and NO3-), humic acid and the various real water matrices on TC abatement are thoroughly explored. Especially, the Co-WS2/sulfite process is advantageous owing to the negligible effect of the coexisting anions on the TC abatement. This study provides a novel heterogeneous activator for significantly improving sulfite activation efficacy to achieve the efficient organic micropollutant abatement.