Boosted H2O2 Utilization and Selective Hydroxyl Radical Generation for Water Decontamination: Synergistic Roles of Dual Active Sites in H2O2 Activation

H2O2 as a green oxidant plays a crucial role in numerous green chemical reactions. However, how to improve its activation and utilization efficiency as well as regulate the distribution of ROS remains a pressing challenge. In this work, a sulfur quantum dots (SQDs) modified zero-valent iron (SQDs@ZVI) was delicately designed and prepared, whose iron sites can coordinate with strongly electronegative sulfur atoms to construct highly reactive Fe-S dual active sites, for high-efficient selective H2O2 activation and utilization with potent •OH production. Experimental tests, in situ FTIR/Raman spectra and theoretical calculations demonstrated that SQDs modulates the local coordination structure and electronic density of iron centers, thus effectively enhancing its Fenton reactivity and promoting the rate-limiting H2O2 adsorption and subsequent barrierless dissociation of peroxyl bonds into •OH via the formation of bridged S–O–O–Fe complexes. Consequently, substantial generated surface-bound •OH induced by the highly reactive Fe-S dual sites enabled excellent degradation of miscellaneous organic pollutants over a broad pH range (3.0–9.0). The developed device-scale Fenton filter realized durable performance (up to 200 h), verifying the vast potential of SQDs@ZVI with diatomic sites for practical application. This work presents a promising strategy to construct metal-nonmetal diatomic active sites toward boosting selective activation and effective utilization of H2O2, which may inspire the design of efficient heterogeneous Fenton reaction for water decontamination.