Markedly boosted peroxymonosulfate- and periodate-based Fenton-like activities of iron clusters on sulfur/nitrogen codoped carbon: Key roles of a sulfur dopant and compared activation mechanisms

Highly dispersed iron nanoclusters on carbon (FeNC@C) hold great promise for wastewater purification in Fenton-like reactions. The microenvironment engineering of central Fe atom is promising to boost the activation capacity of FeNC@C, which is however remains a challenge. This study developed a self-sacrificed templating strategy to S, N-codoped carbon supported Fe nanoclusters (FeNC@SNC) activator and find the key role of sulfur heteroatoms in regulating the electron structure of Fe sites and final activation property. Investigations revealed that the FeNC@SNC composite exhibited unusual bifunctional activity in both peroxymonosulfate (PMS)- and periodate (PI)-based Fenton-like reactions. We also offered insights into the differences between the degradation of organics by the FeNC@SNC/PMS and FeNC@SNC/PI systems. Specifically, under identical conditions, the FeNC@SNC/PMS system delivered a higher oxidation capability and stronger resistance to nontarget matrix constituents, but showed more severe Fe leaching than the FeNC@SNC/PI system. Furthermore, while mediated electron-transfer process was identified as the major route for pollutant decomposition in both systems, the high-valent Fe-oxo species [Fe (IV)] was the auxiliary reactive species found only in the FeNC@SNC/PMS system. Based on these findings, our results provide profound insights into the design of active and durable Fe-based activators toward highly efficient Fenton-like reactions.